CN109928516B - Efficient wetting purifying agent and application thereof in environmental purification - Google Patents
Efficient wetting purifying agent and application thereof in environmental purification Download PDFInfo
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- CN109928516B CN109928516B CN201910320785.3A CN201910320785A CN109928516B CN 109928516 B CN109928516 B CN 109928516B CN 201910320785 A CN201910320785 A CN 201910320785A CN 109928516 B CN109928516 B CN 109928516B
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Abstract
The invention provides an efficient wetting water purifying agent, which has the water content of 12-23%, effectively improves the wetting capacity of the water purifying agent through reduction-vulcanization and crosslinking reaction, has stronger purifying capacity for pollutants with less water, such as sludge, farmland soil and the like, and has strong purifying endurance and higher mechanical strength of a carrier of the purifying agent.
Description
The invention belongs to the field of environmental purification, and particularly relates to an efficient wetting purifying agent and application thereof in the field of environmental purification.
Background
Research shows that in the current aquaculture process, due to the problems of low bait utilization rate, excessive discharge of residual baits and feces of cultured animals and the like, eutrophication of water bodies, C, N, P enrichment pollution of bottom mud and reduction of oxidation-reduction potential of the bottom mud are caused. The eutrophication degree of the water body is increased, ammonia nitrogen and nitrite can exceed the standard, and the aquatic animals are poisoned. The discharge of a large amount of breeding wastewater causes great influence on the surrounding environment, the water area environment deteriorates, red tide frequently occurs, and the ecological balance and biodiversity are also damaged. The water quality of the aquaculture water area is reduced, so that the fishery economy of China is greatly lost, and the scale of intensive industrial aquaculture is gradually enlarged along with the rapid development of the aquaculture industry. Meanwhile, the natural water area is polluted by the random discharge of the untreated aquaculture wastewater industrial domestic sewage, the aquaculture ecological environment is worsened, and the disease problem of aquatic animals is getting worse. At present, chemical drugs such as antibiotics are mainly used for controlling the occurrence of diseases, but the overuse of the antibiotics not only enhances the drug resistance of pathogenic bacteria, but also interferes the normal growth and reproduction of beneficial microbial floras to cause the imbalance of microecology. Drug residues generated by long-term use of antibiotics seriously affect water quality and aquatic product quality and directly threaten human health and safety.
At present, the methods for controlling the water quality by the physical chemistry of sulfides such as coal cinder particle adsorption, ferric iron oxidation and the like have the defects of high cost, poor durability, secondary pollution and the like. In contrast, biological control of sulfides has the advantages of environmental protection, high efficiency, durability and the like, and is a sulfide control technology with a relatively prospect. The microbial immobilization technology is a method for immobilizing free microbial cells on a carrier by using a physical or chemical method so that the microbial cells can keep activity and can be repeatedly utilized, and is successfully applied to the field of prevention and treatment of water, atmosphere and soil pollution to obtain better effect. For example, in the cell immobilization technique, the entrapment method is a method for immobilizing cells by dispersing cells into a porous carrier or entrapping cells in a gel formed by a polymer, and is currently the most widely used method for immobilizing cells, but when sulfur-containing wastewater is treated by using the biological metabolic function of sulfur-oxidizing bacteria, the metabolic activity of functional microorganisms in a reactor is often inhibited due to high concentration of sulfide in the influent water, so that the functional microorganisms require a long adaptation period, and since the sulfur-oxidizing bacteria have low adhesion properties and are easily lost with effluent water, it is very difficult to maintain a high concentration of sulfur-oxidizing bacteria in the reactor.
For example, CN 103951052A, beijing university of industry, discloses preparation and application of a sulfur-oxidizing bacteria immobilized bioactive filler based on a polyurethane carrier, a massive polyurethane foam is used for extruding, adsorbing, immobilizing and cutting a granular bioactive filler obtained by adsorbing, immobilizing and cutting an embedding liquid immobilized with sulfur-oxidizing bacteria by an embedding liquid, but the polyurethane material has the following problems: (1) the density is single, only two states of floating and sinking exist, and the water-soluble polymer can not be effectively suspended in the water body for a long time in a water body change dynamic system; (2) the surface of the polyurethane polymer has no sites and is not suitable for establishing the sites, so the polyurethane polymer is not suitable for selective adsorption of sulfur oxidizing bacteria; (3) the polyurethane has a single aperture and only has irregular macropores, although the macropores are beneficial to adsorption, the specific surface area is extremely small, the fixing effect is poor, and the stability is improved a little; (3) polyurethane as organic high polymer can cause serious pollution, for example, the patent records that the biological filler can be a cube with the side length of 3-5 mm, a cuboid with the length, the width and the height of 3-5 mm, a cylinder with the diameter of 3-5 mm and the height of 3-5 mm, and the like, and is similar to a carrier of particles, so that the polyurethane has great problem in recycling after purifying large-area water bodies such as lakes, oceans and the like, and is very easy to cause pollution.
In addition, CN 109382075A Wuhan university of light industry, a composite microbial inoculum, a preparation method thereof and a sewage treatment method are provided, the composite microbial inoculum comprises a composite carrier and composite microbial bacteria, and the composite carrier comprises sodium alginate, molasses, diatomite, micron-sized activated carbon and shell powder. According to the invention, sodium alginate, molasses, diatomite, micron-sized active carbon and shell powder are used as a composite carrier, and then the composite microbial bacteria are solidified and loaded on the composite carrier to prepare the composite microbial bacteria adsorbent, so that the content, the survival rate and the effective survival time of the microbial bacteria in the adsorbent are improved, and when the composite microbial bacteria adsorbent is used for treating sewage, harmful substances such as nitrite, ammonia nitrogen, hydrogen sulfide and the like in the sewage can be effectively degraded, and the effect of purifying the water quality is achieved. However, the polyurethane material has the following problems: (1) the carrier is complex and difficult to mix uniformly, and homogeneous mixing cannot be realized, so that the stability of the adsorption effect of the whole adsorbent is poor; (2) no effective adsorption vacancy exists, only disordered macroporous adsorption flora is relied on, and the adsorption is single.
In addition, in the same-day series applications of the present inventors, the method for identifying the attached sulfur oxidizing bacteria and the water purifying agent obtained by the method described therein have the following problems to be improved: (1) the purifying agent has excellent purifying effect and high efficiency when being used for purifying water, but when being used for purifying domestic sludge such as sludge on the coast of the wuxi mei beam lake, the purifying effect of the purifying agent cannot be fully exerted due to the low water quantity of the sludge; (2) although the calibration can effectively attach sulfur-oxidizing bacteria, the adsorption force is still poor and needs to be improved; (3) the carrying capacity of sulfur oxidizing bacteria needs to be improved; (4) the purifying agent can continuously purify the water body for 1 to 1.5 years under stable laboratory conditions, but has poor continuous purification capability in a complex practical use process; (5) the existence of macropores and mesopores of the silicon oxide carrier causes the mechanical strength of the silicon oxide carrier to become a fatal defect in the application process.
Disclosure of Invention
Based on the problems of the prior art, the invention aims to provide a water purifying agent which is pollution-free, does not need to be recycled, and has large adsorption capacity, high water content, strong adsorption capacity and high mechanical strength.
An efficient wetting purifying agent comprises a carrier and sulfur oxidizing bacteria loaded in pore channels of the carrier, wherein the carrier is provided with a communicated and penetrated macroporous structure, pore windows are attached to the pore walls of the carrier, the pore walls of the carrier are formed by mesoporous morphology structures, macromolecular cross-linking agents are filled or attached to the outer surfaces of the mesoporous macroporous structure or the carrier, the sulfur oxidizing bacteria are aerobic and/or facultative anaerobic mixtures, and the water content of the wetting purifying agent is 12-23%.
Furthermore, the macromolecular cross-linking agent is calcium alginate and is formed by cross-linking sodium alginate, polyvinyl alcohol and calcium chloride.
Further, the concentration of sodium alginate is 1-2wt.%, the concentration of polyvinyl alcohol is 2-5wt.%, and the concentration of calcium chloride is 1-2 wt.%.
Further, the sulfur oxidizing bacteria are aerobic and/or facultative anaerobic mixtures.
Further, the sulfur oxidizing bacteria include thiobacillus or filamentous sulfur bacteria among colorless sulfur bacteria, or thiobacillus violaceus, thiobacillus viridis, and rhodobacter palustris among colored sulfur bacteria.
Further, the parameter characteristics of the carrier are as follows: the size of the macropore is 20-30 μm, the size of the mesopore is 3.5-3.8nm, and the specific surface area is 90-130m2/g。
Furthermore, the number of effective viable bacteria carried on the surface of the carrier is more than or equal to 8 multiplied by 1010Per gram.
Further, the fixed sulfur oxidizing bacteria are sown or sprayed on the surfaces of water bodies and sludge pollutants.
The environment purifying application of efficient wetting purifying agent can be used in the field of water quality purification or deodorization of water bodies such as sludge, farmlands, septic tanks, domestic sewage, industrial wastewater, ponds, swamps, rivers, seas, lakes, aquariums and the like.
The silicon oxide carrier used in the invention is an inert carrier containing macropores and mesopores, and the carrier is nontoxic to microorganisms; the mass transfer performance is good; the immobilized product has high mechanical strength; the physical and chemical properties are stable and are not easy to be decomposed by microorganisms; the immobilization operation is easy; the service life is long; the carrier is a non-acid and non-alkali neutral material, namely the carrier does not change the pH value of the water body to be purified, namely the carrier does not have adverse effect on the pH balance of a stable water body biological system, namely the carrier is suitable for water body purification in any pH value environment.
The preparation method of the macropore and mesopore of the invention comprises a sol-gel method and a template method existing in the prior art,the method is characterized by comprising a microemulsion method, a hydrothermal method and a precipitation method, wherein a template method is preferred, common macroporous and mesoporous carriers such as a hard template taking integral polystyrene as a macroporous structure and a soft template component taking a nonionic surfactant P123 as a mesoporous structure can effectively control the structures of macropores and mesopores, and the carrier is convenient to prepare and high in stability. The carrier is provided with a pore structure which is communicated and penetrated with each other, a connected pore window with the diameter of 1-10 mu m is attached to the pore wall, and the pore wall is formed by a mesoporous morphology structure; the size of the macropore is 20-30 μm, the size of the mesopore is 3.5-3.8nm, and the specific surface area is 90-130m2G, pore volume of 0.17-0.25cm3g, wherein the size of the large pores is preferably 23-27 μm, mainly because the sulfur oxidizing bacteria used in the invention are mainly filamentous sulfur oxidizing bacteria with the width size of 0.5-10 μm, and the bacteria can be selectively loaded in the large pores and the empty windows of the porous carrier, secondly, the porous carrier particles used are of a size of 0.1-2cm, because the sulfurised bacterial species are relatively small in size, therefore, the bacteria are more suitable to be loaded on the surface of porous particles with small particle size, the combination mode of the specific large pore size and the particle size can not cause other bacteria to occupy the pore channel position of the filamentous sulfur bacteria, and the filamentous sulfur bacteria occupying the pore channel position can not easily flow out of the pore channel, and in addition, the settling velocity of the porous particles in the particle size range is low, and the porous particles are more suitable for slowly dispersing towards the depth direction of the water body.
The pore size of the mesopores is 3.5-3.8nm, the existence of the mesopores can effectively improve the specific surface area of the carrier, further improve the adsorption capacity to the water body, facilitate the contact between the polluted water body and the carrier, and finally improve the contact probability between the polluted water body and sulfur oxidizing bacteria.
Secondly, carrying out reduction-vulcanization on the carrier, wherein the specific treatment mode is that the carrier is placed in a corundum cup in a vacuum tube furnace, argon is introduced for emptying, and then a gas path is switched to be 1-5 vol2Mixed gas of/Ar, literThe temperature is up to 550-oC, the time is 1-1.5h, the temperature is naturally reduced to 200-oC, after argon is exhausted, CS is introduced2Gas in the range of 10-15oC/min is increased to 700oAnd C, keeping the temperature for 1-2h, and naturally cooling to room temperature. The infrared result test of the silicon oxide carrier can obtain that the silicon oxide carrier has an obvious peak value at 3100-3500 and can be assigned to the surface of the silicon oxide carrier to be rich in hydroxyl which is an unavoidable group, so that the silicon oxide carrier is endowed with certain hydrophilicity, but the hydroxyl has no practical beneficial value for water purification and is not beneficial to the adsorption of bacteria, so that the hydroxyl on the surface of the silicon oxide carrier is vulcanized into a sulfur-oxygen bond through reduction and subsequent vulcanization, the sulfur-oxygen bond can be used as a nutrient source of sulfur-oxidizing bacteria, the adsorption of the sulfur-oxidizing bacteria in a culture medium to the surface of a solid carrier is facilitated, the concentration of the sulfur-oxidizing bacteria carried on the surface of the carrier is further improved, and the effective viable count carried on the surface of the carrier can be effectively increased to be more than or equal to 6 x 10 through reduction vulcanization treatment8Per gram.
In addition, the reduction treatment process can effectively sterilize and disinfect the carrier while reducing the surface hydroxyl so as to reduce the pore occupation of external bacteria and generate adverse effects on subsequent inoculation. Regarding the adsorption time of sulfur-oxidizing bacteria on the surface of the carrier, if the adsorption time is too short, the cells cannot be sufficiently adsorbed; if the adsorption time is too long, the experimental time is prolonged, unnecessary waste is caused, and the bacterial cells may be aged. In either case, this results in experiments that are not optimal. Therefore, it is necessary to determine the optimum adsorption time, which is determined by the present invention to be 2 to 3 days of standing.
However, the number of the effective viable bacteria is still limited, and the purification efficiency is further affected, specifically: the carrier has a macroporous and mesoporous structure, so the mass transfer rate is high, but the adsorption force is mainly between the thalli and the carrier, so the binding force between the thalli and the carrier is weak, and the hyphae are easy to fall off, therefore, the cross-linked gel with high water content is formed in the macroporous pore channel by the gel, the cross-linking agent and the reinforcing agent, so the problem that the adsorbed thalli are separated can be effectively solved, and the method causes the bacteria to be separatedThe number of effective viable bacteria carried on the surface of the bright carrier is more than or equal to 8 multiplied by 1010Per gram. However, in the case of the desired bacterial cells, the presence of the crosslinked material adversely affects the diffusion of the substrate, the reactant and the oxygen molecules, so that the reaction rate is lowered, and the metabolic behavior of the bacterial cells in the gel particles is sometimes changed even by mass transfer limitation, and therefore, the water content of the carrier needs to be adjusted.
In addition, because the water content of the invention is higher, the dependence of the water purifying agent applied on the invention on water bodies on the same day can be effectively reduced, and the application range of the water purifying agent is expanded to the extent that the water purifying agent can purify sludge and farmlands with reduced water content.
As for bacteria, the bacteria selected for use in the present invention are sulfur oxidizing bacteria, which means that reductive sulfide or elemental sulfur in a low valence state is completely oxidized into Sulfate (SO)4 2–) Or partially oxidized to higher sulfur compounds, such as by oxidizing hydrogen sulfide by: 2H2S+O2→2H2O+S2+ energy; s2+3O2+2H2O→+2H2SO4+ energy.
The sulfur oxidizing bacteria used in the present invention are aerobic and/or facultative anaerobic mixtures, or Thiobacillus or filamentous sulfur bacteria among colorless sulfur bacteria, or Thiobacillus violaceum, Thiobacillus viridans, Rhodobacter palustris among colored sulfur bacteria. In particular, the method of manufacturing a semiconductor device,
colorless sulfur bacteria, such as thiobacillus (aerobic), are the most important chemoautotrophic sulfur bacteria in soil and water, and they are capable of oxidizing hydrogen sulfide, pyrite, elemental sulfur, etc. to form sulfuric acid, taking energy from the oxidation process: 2H2S＋O2→2H2O + 2S + energy, 2FeS2＋7O2＋2H2O→2FeSO4+ 2H2SO4+ energy 2S + 3O2＋2H2O→2H2SO4+ energy, optimum growth temperature 28-30 deg.c. Some Thiobacillus species can endure very acid environment, even acidophilic, and commonly, Thiobacillus oxysporum, Thiobacillus ferrooxidans and thiobacillus thioparus.
Filamentous sulfur bacteria: there are two main genera, the Behcet genus, which has filaments free, and the Thiobacillus genus, which has filaments usually fixed to a solid substrate. In addition, sulfur can be metabolized by intracellular sulfur granules, such as thiospira having a spiral shape, sulfolobus having a spherical cell with a lobe, and oomycetes having a round to oval cell shape.
The photosynthetic bacteria mainly use simple fatty acid, alcohol and the like as carbon sources or electron donors, and also can use sulfide or thiosulfate as electron donors, and can anaerobically oxidize elemental sulfur and H under the illumination anaerobic condition2S。
Purple sulfur bacteria, which are less tolerant to sulfides than green sulfur bacteria. However, purple sulfur bacteria are capable of sulfur oxidation under aerobic and micro-aerobic conditions, and are more suitable as the sulfur oxidizing bacteria flora of the present invention.
The rhodobacter palustris is heterotrophic and anaerobic, but can tolerate high-concentration organic wastewater, has strong conversion capability and has a certain decomposition effect on phenol and cyanogen.
Compared with the prior art, the invention has the following beneficial effects:
(1) the carrier has the advantages of large bacterial carrying capacity, high survival rate, large flora dominance and high purification efficiency.
(2) The carrier of the invention is an inert carrier, has rich sources and is suitable for purifying water bodies with various pH values.
(3) The water purifying agent of the invention is storage-resistant, used at normal temperature and convenient to transport.
(4) The purifying agent of the invention can be used for purifying sludge and farmland soil, and has strong purifying endurance.
(5) The mechanical strength of the carrier is further improved.
Detailed Description
In order to better understand the present invention, the following examples are further illustrated, which are only used for explaining the present invention and do not constitute any limitation to the present invention.
Example 1
The preparation method of the wetting water body purifying agent comprises the following steps:
(1) preparing carrier particles: the carrier is a macroporous mesoporous silica carrier and has a pore structure which is communicated and penetrated with each other, a connected pore window with the diameter of 1-10 mu m is attached to the pore wall, and the pore wall is formed by a mesoporous morphology structure.
(2) Reduction-sulfiding the support: placing the carrier in a corundum cup in a vacuum tube furnace, introducing argon gas for evacuation, and then switching a gas path to 3vol2Heating the mixed gas of/Ar to 570oC, the time is 1.25h, the temperature is naturally reduced to 250oC, after argon is exhausted, CS is introduced2Gas, in 13oC/min is increased to 700oAnd C, keeping the temperature for 1.5h, naturally cooling to room temperature, and forming a sulfur-oxygen bond on the surface of the silicon oxide carrier to serve as a culture medium sulfuration bacteria adsorption site.
(3) Preparing a sulfur oxidizing bacteria culture medium; the sulfur oxidizing bacteria culture medium comprises KH2P04，NaHP04，MgSO4KCl, and deionized water, and Cu2+，Zn2+，Ca2+，Fe3+,Mn2+Sterilizing trace elements at 121 deg.C under high pressure for 20 min, inoculating sulfur oxidizing bacteria under aseptic condition, 30oAnd C, carrying out shake cultivation at 150r/min to obtain the sulfur oxidizing bacteria liquid.
(4) Adding the cultured bacterial liquid into the porous carrier reduced and vulcanized in the step (2), shaking by a shaking table, standing for 3 days at 28 ℃, and fully adsorbing sulfur-oxidizing bacteria on the surface of the carrier;
(5) and (4) removing the redundant culture solution in the step (4), washing for 2 times by using deionized water, immersing in a sodium alginate solution, soaking for 2 hours, then adding polyvinyl alcohol, stirring uniformly, adding into a calcium chloride solution, and carrying out crosslinking reaction for 3 hours.
(6) And taking out the carrier subjected to the crosslinking reaction, washing the carrier by using normal saline, and naturally evaporating and drying the carrier.
The bacteria are selected from the group consisting of thiobacillus autoaerobically aerobic and purple sulfur heterotrophic bacteria.
The obtained water purifying agent is named as S-1.
Examples 2 to 3
The preparation method is the same as that of example 1, except that sodium alginate(SA), polyethylene glycol (PVA), calcium chloride (CaCl)2) See in particular table 1, named S-2 and S-3.
Comparative example 1
The method comprises the following steps:
(1) preparing a macroporous mesoporous carrier, consistent with the carriers of examples 1-3;
(2) preparing a sulfur oxidizing bacteria culture medium; the sulfur oxidizing bacteria culture medium comprises KH2P04，NaHP04，MgSO4KCl, and deionized water, and Cu2+，Zn2+，Ca2+，Fe3+,Mn2+Sterilizing trace elements at 121 deg.C under high pressure for 20 min, inoculating sulfur oxidizing bacteria under aseptic condition, 30oAnd C, carrying out shake cultivation at 150r/min to obtain the sulfur oxidizing bacteria liquid.
(3) Adding the cultured bacterial liquid into the porous carrier reduced and vulcanized in the step (2), shaking by a shaking table, standing for 3 days at 28 ℃, and fully adsorbing sulfur-oxidizing bacteria on the surface of the carrier;
(4) and (4) removing the redundant culture solution in the step (4), washing for 2 times by using deionized water, immersing in a sodium alginate solution, soaking for 2 hours, then adding polyvinyl alcohol, stirring uniformly, adding into a calcium chloride solution, and carrying out crosslinking reaction for 3 hours.
(5) And taking out the carrier subjected to the crosslinking reaction, washing the carrier by using normal saline, and naturally evaporating and drying the carrier.
The bacteria are selected from the group consisting of thiobacillus autoaerobically aerobic and purple sulfur heterotrophic bacteria.
The obtained water purifying agent is named as D-1.
Comparative example 2
The method comprises the following steps:
(1) preparing carrier particles: the carrier is a macroporous mesoporous silica carrier and has a pore structure which is communicated and penetrated with each other, a connected pore window with the diameter of 1-10 mu m is attached to the pore wall, and the pore wall is formed by a mesoporous morphology structure;
(2) reduction-sulfiding the support: placing the carrier in a corundum cup in a vacuum tube furnace, introducing argon gas for evacuation, and then switching a gas path to 3vol.H2Heating the mixed gas of/Ar to 570oC, the time is 1.25h, the temperature is naturally reduced to 250oC, after argon is exhausted, CS is introduced2Gas, in 13oC/min is increased to 700oAnd C, keeping the temperature for 1.5h, naturally cooling to room temperature, and forming a sulfur-oxygen bond on the surface of the silicon oxide carrier to serve as a culture medium sulfuration bacteria adsorption site.
(3) Preparing a sulfur oxidizing bacteria culture medium; the sulfur oxidizing bacteria culture medium comprises KH2P04，NaHP04，MgSO4KCl, and deionized water, and Cu2+，Zn2+，Ca2+，Fe3+,Mn2+Sterilizing trace elements at 121 deg.C under high pressure for 20 min, inoculating sulfur oxidizing bacteria under aseptic condition, 30oAnd C, carrying out shake cultivation at 150r/min to obtain the sulfur oxidizing bacteria liquid.
(4) Adding the cultured bacterial liquid into the porous carrier reduced and vulcanized in the step (2), shaking by a shaking table, standing for 3 days at 28 ℃, fully adsorbing sulfur-oxidizing bacteria on the surface of the carrier, removing redundant culture solution, washing with deionized water for 1-2 times, and air-drying at normal temperature to obtain the carrier carrying the sulfur-oxidizing bacteria;
the bacteria are selected from the group consisting of thiobacillus autoaerobically aerobic and purple sulfur heterotrophic bacteria.
The obtained water purifying agent is named as D-2.
Comparative example 3
The method comprises the following steps:
(1) preparing carrier particles: the carrier is a macroporous mesoporous silica carrier and has a pore structure which is communicated and penetrated with each other, a connected pore window with the diameter of 1-10 mu m is attached to the pore wall, and the pore wall is formed by a mesoporous morphology structure;
(2) preparing a sulfur oxidizing bacteria culture medium; the sulfur oxidizing bacteria culture medium comprises KH2P04，NaHP04，MgSO4KCl, and deionized water, and Cu2+，Zn2+，Ca2+，Fe3+,Mn2+Sterilizing trace elements at 121 deg.C under high pressure for 20 min, inoculating sulfur oxidizing bacteria under aseptic condition, 30oC, carrying out shake cultivation at 150r/min to obtain sulfur oxideBacterial liquid.
(3) Adding the cultured bacterial liquid into the porous carrier reduced and vulcanized in the step (2), shaking by a shaking table, standing for 3 days at 28 ℃, fully adsorbing sulfur-oxidizing bacteria on the surface of the carrier, removing redundant culture solution, washing with deionized water for 1-2 times, and air-drying at normal temperature to obtain the carrier carrying the sulfur-oxidizing bacteria;
the bacteria are selected from the group consisting of thiobacillus autoaerobically aerobic and purple sulfur heterotrophic bacteria.
The obtained water purifying agent is named as D-4.
The soil used in the tests of all the examples and comparative examples was selected from the soil along the bank of Wuxi Meilianhu lake, the sampling time was 7 months, the soil was dried at 30 degrees, and the tests showed that the EC value of the sulfide content was 1.984 mus/cm and the sulfide content was 4.1 mg/g.
TABLE 1
The data in the table above are explained:
first, it is known that sulfur oxidizing bacteria are widely distributed in various types and are found in the ocean, hot water ports, cold springs, water,
The discovery of various environments such as humid soil, rivers, lakes and the like shows that the dependence of sulfur oxidizing bacteria on water can be obtained, so that the water content in the purifying agent is precious enough for soil purification, particularly dry soil, and the water content is more or less than SA \ PVA \ CaCl2In general, when the amount of PVA used is reduced, the water content in the carrier is reduced, but if the amount of SA used is reduced too much, the water content of the carrier is reduced greatly, and the water content is highest only when the ratio of SA to PVA is 1:5, in addition, the amount of CaCI2 cross-linking agent is in direct proportion to the degree of calcium alginate cross-linking, the optimal amount of 1.5 percent is used, in addition, the formed calcium alginate can be effectively filled in the macropores and the mesopores, thereby effectively compensating the situation that the carrier is used for the reason that the macroporous structure is too muchThe problem of insufficient mechanical strength arises, wherein the higher the water content, the better the mechanical strength, and finally the endurance of the carrier is effectively improved.
TABLE 2
The above table is explained:
first, it should be clear that if the carrier is not subjected to reduction-sulfidation treatment, such as D-1, and the carrier is not subjected to reduction-sulfidation treatment, the bacteria are adsorbed only by capillary or van der Waals forces in a small amount, i.e., the subsequent calcification-filling treatment does not significantly improve the increase in the number of bacteria bodies, 5.8 x 106Per gram. In addition, when the carrier is calibrated, the adsorption capacity is obviously increased due to calibration, but the adsorption force of sulfur oxidizing bacteria on the surface of the carrier is weak, so that adsorbed hyphae are easy to fall off, calcium alginate crosslinking filling is avoided subsequently, the adsorption force of the bacteria and the carrier is improved, and the maximum vertical and horizontal adsorption capacity is reduced by 9.3 x 108Per g, adsorption capacity of 7.4 x 10 when neither calibration nor filling is present5Each/g, i.e., comparative examples 1-3 above, does not differ from S-1 of the present invention in terms of effective loading number, sulfide and EC treatments.
Finally, the water purifying agent can also be used in the fields of water quality purification or deodorization of water bodies such as septic tanks, domestic sewage, industrial wastewater, ponds, swamps, rivers, seas, lakes, aquariums and the like, and the effect of the water purifying agent is far better than the effect of purifying sludge, and the details are not repeated.
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (6)
1. An efficient wetting purifying agent is characterized in that the purifying agent comprises a silicon oxide carrier and sulfur oxidizing bacteria loaded in pore channels of the silicon oxide carrier, the silicon oxide carrier has a mutually communicated and penetrated macroporous structure, pore windows are attached to the pore walls of the silicon oxide carrier, the pore walls of the silicon oxide carrier are formed by a mesoporous morphology structure, wherein the size of the macropores is 20-30 mu m, the size of the mesopores is 3.5-3.8nm,
the outer surface of the mesoporous macroporous structure or the carrier is filled or attached with a macromolecular cross-linking agent, the sulfur oxidizing bacteria is an aerobic and/or facultative anaerobic mixture, the water content of the wetting purifying agent is 12-23%, the macromolecular cross-linking agent is calcium alginate formed by cross-linking sodium alginate, polyvinyl alcohol and calcium chloride, the concentration of the sodium alginate is 1-2wt.%, the concentration of the polyvinyl alcohol is 2-5wt.%, and the concentration of the calcium chloride is 1-2wt.%, and the carrier is at least subjected to reduction-vulcanization treatment before cross-linking: and (3) placing the carrier in a corundum cup in a vacuum tube furnace, introducing argon for evacuation, and then switching a gas path to be 1-5 vol2Heating the mixed gas of Ar and Ar to the temperature of 550-600 ℃ for 1-1.5h, naturally cooling to the temperature of 200-300 ℃, introducing CS after argon evacuation2Heating the gas to 700 ℃ at a speed of 10-15 ℃/min, keeping the temperature for 1-2h, and naturally cooling to room temperature.
2. The efficient wetting purifying agent as claimed in claim 1, wherein the sulfur oxidizing bacteria include thiobacillus or filamentous sulfur bacteria among colorless sulfur bacteria, or thiobacillus violaceus, thiobacillus viridis, rhodobacter palustris among colored sulfur bacteria.
3. The efficient wetting purifying agent according to claim 1, wherein the specific surface area of the carrier is 90 to 130m2/g。
4. The efficient wetting purifying agent as claimed in claim 1, wherein the number of active bacteria carried on the surface of said carrier is greater than or equal to 8 x 1010Per gram.
5. A high efficiency wetting cleaning agent as claimed in any one of claims 1 to 4, wherein the cleaning agent is applied by spreading or spraying on the surface of the water or sludge contaminant.
6. The environmental purification application of the efficient wetting purifying agent as claimed in claim 1, which is used in the fields of water quality purification or deodorization of water bodies of sludge, farmlands, septic tanks, domestic sewage, industrial wastewater, ponds, marshes, rivers, seas, lakes and aquariums.
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