TW201634400A - Preparation of a composition for removing wastewater and restoring river course, and application method thereof - Google Patents

Abstract

The present invention is a composition of the porous substance and microbe for removing wastewater and restoring river course and its application method. The fixed embedded biological catalyst in the present invention is not easy to be washed away after being added into the polluted river. Not only can the catalyst be used in the degradation of wastewater and channel water body pollutant, but the fixed material can also have the adsorption and fixation function for releasing the pollutant from the bottom mud of a river course, thereby achieving the purpose of reducing pollution of the bottom mud towards the covering water body.

Description

Preparation and application method of composition for removing sewage and re-cultivating river channel

The invention relates to a porous hole substance and microbial composition for removing sewage and re-cultivating river channels, and the composition is used for controlling river pollution, urban sewage, and aquaculture wastewater.

Due to the long-term settlement and accumulation of domestic pollutants, black muddy sediments in urban rivers are deposited. Urban river channel sediment pollution is an important source of black body odor. The external pollution and sediment pollution of black and odor river waters become river water pollution. The main source.

The black odor of urban rivers is mainly the result of excessive oxygen pollution and oxygen imbalance and oxygen consumption. The water body is under oxygen and even anaerobic conditions convert pollutants and produce ammonia nitrogen, hydrogen sulfide, volatile organic acids and other stench substances and iron and manganese. Black substance such as sulfide. Domestic sewage is the most common and major source of pollution that causes black odor in urban rivers. Other sources of pollution include: domestic waste, organic industrial wastewater, overflow sewage from confluent pipe network, tail water from sewage plants, and sewage from livestock and poultry farms.

Organic pollution in water is the most important factor causing black odor water. Most of the pollutants in water are organic pollutants. Organic pollutants are the most important oxygen-consuming substances in water. These organic pollutants are discharged into rivers. In the early stage, under the decomposition of aerobic microorganisms, the organic matter was decomposed into CO ₂ and H ₂ O, causing the oxygen dissolved in the water to be greatly reduced, resulting in anoxic. The anaerobic microorganisms then replaced the organic matter in the water and produced sulfides. The water body turns black, and the odor of various small molecule compounds of H ₂ S, NH ₃ and CH ₄ produced by anaerobic decomposition of organic substances mixes and floats out of the water surface, causing the water body to scatter the odor. Some studies have also pointed out that when there is a large amount of organic carbon, organic nitrogen and organic phosphorus in the water, no matter the amount of dissolved oxygen in the water, it will be degraded by aerobic actinomycetes and anaerobic microorganisms at a suitable temperature. And generate different types of substances to cause the body of water to become black and smelly.

Contains a large amount of organic substances, nutrients, high oxygen consumption rate, generally in a strong reducing environment, secondary pollution of river bottom sediments easily lead to excessive levels of harmful substances such as ammonia nitrogen, nitrite, sulfide, fecal odor in water bodies, resulting in black body water Stinky, affecting urban landscapes and residents' lives. River polluted sediment has a great impact on the water quality of the overlying water. The treatment of sediment can effectively control and reduce the release of COD (Chemical Oxygen Demand), nitrogen and phosphorus nutrients, and the overlying water. Pollution, therefore controlling the sediment pollution of rivers, is an important part of the improvement of urban river water environment.

In the past, the measures used to control sediment pollution were mainly dredging and dredging. The cost of this method is relatively high. The re-disposal of sediment is also a complicated environmental protection problem: the aeration of water can increase the sediment pollution to a certain extent, but For shallow rivers, it is easy to resuspend the sediment: adding microbial preparations in the river channel, this method has a certain effect on enhancing the self-purification ability of the water body. The disadvantage is that the microbial preparations in the river channel are easily lost, frequently placed, and the cost is too high.

Bioremediation refers to the process by which organisms, especially microbes, catalyze the degradation of organic pollutants to repair contaminated environments or eliminate pollutants in the environment. There are many types of microorganisms in the water body, various types of metabolism, and strong adaptability. The original microorganisms in the water body are used to repair the polluted water bodies, and the purification ability of the natural environment is strengthened to control the polluted water bodies, which has less investment, low energy consumption, convenient management, safety, etc. The advantages are in line with the concept of establishing economic savings, resource recycling and sustainable development.

Microbial immobilization refers to the basic technique of using chemical or physical methods to locate free microorganisms in a defined spatial region and maintain integrity and can be used repeatedly. Immobilization technology can immobilize intact cells, maximally maintain the integrity and stability of biological enzymes, increase microbial density and flow rate per unit volume, and the repair process is not limited by the dilution rate higher than the growth rate of microorganisms. The micro-environment is conducive to masking the adverse effects of the external environment. The hydraulic properties and sedimentation performance of the immobilized particles can be flexibly controlled, and it is an efficient and practical pollution-remediation technology.

At present, there are no unified classification standards for immobilization methods of microorganisms at home and abroad, and there are various methods, but mainly surface adsorption (binding) immobilization, cross-linking (bonding) immobilization, (multimer) embedding immobilization. Several methods such as self-immobilization (self-crosslinking immobilization between microbial cells). Among the immobilized microbial techniques, the embedding method is the most common. The embedding method is to immobilize microorganisms by blocking microorganisms in a network of natural polymer polysaccharides or synthetic polymer gels. It is characterized in that the immobilized microorganisms can be prepared into various shapes (spherical, massive, cylindrical, membrane, cloth, tubular, etc.), and the immobilized microorganisms can be added, so the research on it is the most, and the application is also The widest. The materials used in the embedding method mainly include sodium alginate, polyvinyl alcohol, triacetate, agar, etc., and auxiliary materials such as activated carbon, rectorite, limestone, etc. are added to improve the performance of the embedding material. In the microbial treatment process of wastewater, the biochemical action of microorganisms is mainly utilized, and the organic pollutants in the wastewater are used as nutrients required for the life activities of microorganisms, and are absorbed and utilized in the life activities of microorganisms, and are converted into A substance that is easy to separate or harmless. Microorganisms have functions of improving water quality, self-purification, inhibiting algae overgrowth, controlling water eutrophication, increasing dissolved oxygen, reducing COD, reducing ammonia nitrogen, reducing phosphorus content, and improving ecological balance of water environment. Studies have shown that in the absence of treatment of river sediments, through the treatment of oxidation pond pretreatment, river water aeration, water body in situ enhanced bioremediation, the water body downstream of the river gradually recovers black odor. After the bio-enhanced oxidation repair of the river sediment, the river channel The quality of polluted water has been significantly improved and improved.

The advantages of embedding immobilized biocatalysts (IBC) include: low cost, easy immobilization, and various shapes, which can be immobilized at normal temperature and pressure, and immobilized to microorganisms, and immobilized. In vivo, the cells leak less, other microorganisms in the environment are not easy to enter, the matrix permeability is good, physical strength and chemical stability are good (Wang Jianlong, 2002).

Biocatalyst refers to proteases or biological living cells with catalytic ability. In special cases, it may also be nucleic acids (Cech, 1993). Enzymes are essential substances in all living organisms. Enzymes can be efficient and selective. Sexually catalyzes the chemical transformation in various living organisms. In 1839, Payen and Persozu studied the process of germinated barley hydrolyzed starch as dextrin and sugar, and purified amylase (Payen, 1839). In 1973, Japanese Chihiro Ichiro was immobilized with Escherichia coli aspartic acid (H. Ichiro, 1975) with high activity aspartase. After that, related research on immobilized biocatalyst (Immobilized biocatalyst) has been rapidly developed.

Zeolite is a common biocatalyst carrier. The microbial cells are adsorbed to the surface of the zeolite by solid adsorption. The structure of the zeolite is based on the tetrahedral framework structure of yttrium or aluminum oxide (SiO ₄ or AlO ₄ ) as the basic unit. The tetrahedrons of tantalum and aluminum form a three-dimensional skeleton structure (Oliveira and Rubio, 2007, Malekian et al., 2011). Because the aluminum atom carries a trivalent charge and combines with the oxygen atom to form an AlO ₄ tetrahedral skeleton structure, the entire structure exhibits a negatively charged state, so it adsorbs negatively charged ions in the vicinity to neutralize its electrical properties, and also because of such A skeleton structure produces a large number of cavities and voids. The zeolite has a large surface area (400-800 m ² /g) of other minerals. This structure gives the zeolite a strong adsorption capacity and ion exchange capacity, and the pore size of the zeolite surface is uniform and average. At 0.3mm-1.0mm, substances smaller than this diameter are adsorbed (Popov et al., 2012). The use of zeolite as a biocatalyst carrier, in addition to the surface of the zeolite has a large number of pores and no damage to microbial cells. In the biological nitrogen removal process, on the one hand, the zeolite itself can also adsorb ammonia nitrogen in the water through ion exchange, another In the aspect, the nitrifying bacteria are fixed by the electrostatic action of the zeolite and form a biofilm on the surface of the zeolite. The biofilm converts the ammonia nitrogen adsorbed by the zeolite itself into a nitrate by chemical conversion. A self-absorption and self-nitration cycle occurs on the surface of the zeolite. The ability of ammonia nitrogen is continuously regenerated by the action of surface microorganisms. Therefore, the use of zeolite as a microbial catalyst carrier in the process of biological nitrogen removal has simultaneously resulted in three processes of physical adsorption, ion exchange and biological nitrification (Bai et al. , 2010).

The immobilized composite probiotics (CBM) of the present invention are not easily lost after being put into a polluted river channel, and not only enhance the degradation of pollutants by microbial agents, but also the immobilized matrix can promote the release of pollutants from the sediment. Adsorption and fixation can further reduce the pollution of the overlying water by the sediment.

The invention selects zeolite as the carrier, the average specific gravity of the zeolite is 2.12, and the volume is suitable in the range of 0.05-0.15 cm ³ , and the porosity is suitable for adsorption fixation of the micro-bulb, and the intact microbial cells can be fixed to avoid artificial destruction of the biological enzyme. The integrity and stability of biochemical reactions; rapid proliferation and good results. The immobilized cell particles with zeolite as the carrier can directly add to the sediment in the water body of static or slow-flow pollution according to the degree of pollution, and the operation is simple, and it is not necessary to change the natural environment and build a large-scale structure, and no secondary pollution is generated. Zeolite is rich in source and cheap. Save investment, simplify the process, safe and reliable in practice, low in economic cost, engineering investment is only 30-50% of physical and chemical repair.

The carrier used in the present invention may be replaced by a spherical algin. The use of composite bacteria (nitrifying bacteria and denitrifying bacteria), coupled with the use of two-phase (aerobic and anoxic) algae embedding, the principle is to use the oxygen distribution inside the spherical algae, due to the penetration of oxygen, The interior of the algin is an anaerobic zone; the exterior of the algin is an aerobic zone. Effective removal of ammonia nitrogen from wastewater is divided into two steps: nitrification (aerobic state) product is nitric acid (NO ₃ ), and nitrous acid (NO ₂ ); denitrification (denitrification; anaerobic state) product is nitrogen ( N ₂ ). In an aerobic environment, nitrification can only be carried out; conversely, denitrification can only be carried out. Generally, polluted rivers or sewage treatment tanks are difficult to maintain aerobic and anaerobic conditions at the same time, or only a single nitrifying strain is embedded, and the effect of removing ammonia nitrogen is not good; the algin rubber used in the present invention has two phases (there are Oxygen and anoxic) algae-embedded composite bacteria composition, more efficient for ammonia nitrogen in sewage

The microorganism selected by the invention is a facultative anaerobic mixed bacteria, and the immobilized microorganism can be kept clean for a long time; the microenvironment of the immobilized cell particles is favorable for masking the vicious competition, phagocytosis and poisoning of the indigenous protozoa and toxic substances to the microorganisms, It enables high performance in a stable environment under complex environmental conditions. The invention adopts bioremediation mainly refers to microbial remediation, specifically adsorption and immobilization of microorganisms by inorganic carrier zeolite, and the adsorption speed of the composite bacteria is fast and the proliferation effect is good.

The invention also belongs to a sediment biological repairing agent, which is composed of a composite microbial agent, an oxygenating agent and an immobilized carrier, and can also comprise a biological nutrient and a biological antidote auxiliary drug, so as to achieve the purpose of efficiently removing pollutants in the sewage. Because most rivers have large pollution areas and are fluid, it is difficult for primary microorganisms to form dominant degradation bacteria. The special nature of contaminated sediments undoubtedly puts forward higher requirements for bioremediation. It is necessary to screen combined dominant degradation bacteria and microbial immobilization. The density of the particles can make the dominant degrading microbial flora contact the contaminated sediment and achieve the purpose of removing organic pollutants.

The ecological dredging agent is an environmental purifying agent with excellent performance. It is an economical purification method by improving the vitality and self-purification ability of the water body and rapidly improving the water quality. Ecological dredging The agent has the function of sedimentation, and the microorganism itself and its attached microorganisms are not easily lost, even in the rivers, lakes, reservoirs, and beaches and harbors where water flows, which can effectively function. Even in deep waters, you can sink to the bottom, absorb and decompose the organic matter in the mud, and achieve the effects of purifying water, increasing oxygen, and eliminating malodor. In practical applications, other biological carriers need to be fixed in the river to function, and they are often washed away by water, and this phenomenon is not the case with ecological dredging agents.

The application of the ecological dredging agent does not require dredging machinery, clearing and transporting sludge, and there is no dredging scene with odor. Due to different pollution conditions and sludge conditions, according to the previous application examples, an ecological dredging agent is applied, and the sludge in the river can be reduced by 20-30 cm in 4-6 months. After the application of the ecological dredging agent, there is no need for aeration and oxygenation equipment, and the original oxygen-deficient black and odorous river channel is quickly purified. After the water is purified, many aquatic animals can be seen to promote the restoration of the food chain of aquatic organisms. This process eliminates the need to release fry and other species, and has grown many aquatic organisms and fish stocks for decades, making it ideal for purifying sedimentary and ecological restorations.

The use of ecological dredging agent to eliminate sludge instead of dredging and repair aquatic ecology can be docked with the original river comprehensive management task, greatly reducing the difficulty of treatment, improving the treatment effect, and no secondary pollution. After the application of the ecological dredging agent, the purifying agent and the microorganisms adsorbed and immobilized are huge in biomass, and can absorb ammonia nitrogen, nitrate, nitrite, hydrogen sulfide, sulfur compounds and other nutrients contained in the decomposed water and sludge, and cause odor. Things. The function of the ecological dredging agent is to absorb and decompose the organic matter contained in the sludge. When the organic matter is completely absorbed and decomposed, the surface of the sediment is a layer of sandstone inorganic matter that is not absorbed and decomposed, and the mud surface becomes grayish white. The ecological dredging agent can also be placed in the sewage treatment tank and the sludge tank, which can decompose and remove the remaining sludge, purify the water, and eliminate the foul odor. The ecological dredging agent purifies the beach sludge, decomposes the silt of the aquaculture farm, and improves the water quality of the sewage treatment. It has excellent purification ability to remove odor, remove toxic algae and purify lake water.

A composition for removing sewage from a reforestation channel, the composition comprising a modified zeolite and a microbial composition.

A composition for removing sewage and a reforestation channel, the composition comprising an algin and a microbial composition.

The co-culture condition of the microbial composition is continuous culture for 7 days under the illumination of 28 ° C, 200 rpm, and light intensity of 1000 lux; after adding 5% molasses, 0.4% urea and 0.15% potassium dihydrogen phosphate, the temperature is controlled. The fermentation was continued for 5 days at 28 ° C in a fermentation tank.

The modified zeolite is prepared by washing mordenite (mordenite, chemical formula (Ca, Na ₂ , K ₂ ) Al ₂ Si ₁₀ O24‧7H ₂ O) with distilled water, and then immersing the zeolite in 5% hydrochloric acid. After 2 hours; wash with distilled water until the pH is neutral and dry, and soak the zeolite in 5% sodium hydroxide for 2 hours, wash with distilled water until the pH is neutral and dry.

A method of using a composition to remove sewage and a reforestation channel, the composition comprising a modified zeolite and a microbial composition.

By putting the composition into sewage or a river, the pollutants in the water can be degraded.

The composition is added to the amount of sewage plus 3-8 grams per liter of sewage.

The composition is added to the river channel with an area of 400-750 per square meter of river water. Gram.

Figure 1 Scanning electron microscope to capture modified zeolite and zeolite coated CBM; Figure 2 analyzes the adsorption of modified zeolite on ammonia nitrogen by the Langmode isotherm adsorption equation; Figure 3 shows the ability of composite biocatalyst to adsorb ammonia nitrogen with zeolite; Figure 4 shows the concentration of ammonia nitrogen in freshwater wastewater treated by immobilized biocatalyst (B)亚 nitrite ion concentration; Figure 5 immobilized biocatalyst treatment of seawater wastewater (A) ammonia nitrogen concentration, (B) nitrite ion concentration; Figure 6 immobilized biocatalyst treatment of marine aquaculture wastewater (A) ammonia nitrogen concentration, (B) nitrite ion concentration, (C) COD concentration, (D) sulfur-containing molecular concentration; Figure 7 immobilized biocatalyst for treatment of black odorous wastewater at the bottom of the channel (A) ammonia nitrogen concentration, (B) nitrite ion concentration (C) COD concentration, (D) suspended solid particle concentration, (E) phosphorus-containing molecular concentration, and (F) sulfur-containing molecular concentration.

Preparation of CBM compound probiotics by fermentation

Enrichment and cultivation of photosynthetic bacteria, Bacillus subtilis, nitrifying bacteria, lactic acid bacteria, molds, actinomycetes, yeasts, and 7 major strains using pure strains purchased from the Bioresources and Preservation Center (BCRC) of the Hsinchu Food Industry Research Institute Co-cultured composite probiotics (CBM), including the following species: Rhodopseudomonas palustris , Rhodospirillum rubrum , Rhodobacter sphaeroides , Lactobacillus pentosus , Lactococcus lactis , Bacillus subtilis , Saccharomycopsis fibuligera , Ochrobactrum anthropi , Thiosphaera pantotropha , Achromobacter denitrificans , Pseudomonas Stutzeri , Penicillium citrinum , Chaetomium globosum , Aspergillus oryzae , Aspergillus niger , Myrothecium verrucaria , Pichia psedopastoris , Streptomyces albulus . The culture was carried out according to the culture medium of each strain and the optimal growth conditions; the medium formula was as follows: YM MEDIUM ( Saccharomycopsis fibuligera )

YPD MEDIUM( Pichia psedopastoris )

YEAST STARCH MEDIUM II ( Streptomyces albulus )

LACTOBACILLI MRS BROTH( Lactobacillus pentosus , Lactococcus lactis )

NURIENT MEDIUM ( Rhodopseudomonas palustris , Rhodospirillum rubrum , Rhodobacter sphaeroides , Achromobacter denitrificans , Ochrobactrum anthropi , Pichia psedopastoris , Bacillus subtilis )

NS (non-sulfur) MEDIUM ( Rhodopseudomonas palustris , Rhodospirillum rubrum , Rhodobacter sphaeroides ) Mineral solution: MgSO ₄ ‧ H ₂ O: 0.2 g, K ₂ HPO ₄ : 1.0 g FeSO ₄ ‧ H ₂ O: 0.5 g CaCl ₂ : 0.02 g MnCl ₂ ‧ H ₂ O: 0.002 g NaMoO ₄ ‧ H ₂ O: 0.001 g Finally add distilled water to 1.0L

MALT EXTRACT MEDIUM I (Blakeslaa's Formula) ( Aspergillus oryzae , Chaetomium globosum , Penicillium citrinum )

POTATO DEXTROSE MEDIUM (PDA) ( Aspergillus niger )

After the above pure seed strains reached ¹⁰⁹ cfu/ml, the pure seed culture liquids were mixed in equal amounts, and then cultured for 5-7 days by anaerobic irradiation with 60 Lux light and agitation at 50 rpm for the purpose of symbiotic culture. The mixed anaerobic bacteria and aerobic bacteria culture medium are supplied to different bacteria (including carbon source and nitrogen source; amino acid, sugar, fat, vitamin), and these nutrient substrates can ensure the formation of these microbial flora. A stable microbial ecosystem that is mutually beneficial and symbiotic.

The pre-step eucommia mixed culture group was continuously cultured for 7 days at 28 ° C, a rotation speed of 200 rpm, and an illumination intensity of 1000 lux. This step is the first amplification.

The pre-co-mixed culture group was further added with 5% molasses, 0.4% urea and 0.15% potassium dihydrogen phosphate. The temperature was controlled at 28 ° C and the fermentation tank was continuously fermented for 5 days to obtain CBM compound probiotic liquid. This step is a second amplification.

Carrier prepared with zeolite

HCl-NaOH modification method: The zeolite was washed with distilled water and dried, and the zeolite was immersed in 5% HCl for 2 hours. Wash with distilled water until the pH is neutral and dry. Finally, the zeolite is immersed in 5% NaOH for 2 hours, washed with distilled water until the pH is neutral and dried for use.

The novel immobilized composite sediment purifying agent uses zeolite as a microorganism to immobilize the main matrix, and adds a slow-release oxygenator and activated carbon. The zeolite has been thermally modified to increase the specific surface area and porosity, and the organic modification improves the adsorption capacity of the anion. After modification, the zeolite is filled with micropores and channels inside the frame structure, which can provide a huge bio-attached surface area for the microbial community. The internal pores also have the function of screening molecules, and can select dominant microbial populations and help them to multiply. In order to provide micro-oxygen conditions in the sediment, a slow-release oxygenator calcium peroxide can also be used. Its effective content is 80%, the theoretical oxygen increase is 0.22 O ₂ mg/mg, and it can produce 1.38 mg/mg alkalinity. This patent screens strains from indigenous sediments, enriches and enriches and cultures photosynthetic bacteria, Bacillus subtilis, nitrifying denitrifying bacteria and other 8 types of more than 20 strains in a commensal manner to prepare composite probiotics (CBM). The immobilized composite substrate purifying agent was made into pellets, having a water content of 15% and an average density of 2.6.

Carrier prepared with algin

Add water to 100 g with 10% polyvinyl alcohol (PVA) and 2% sodium alginate as the basic carrier, heat at 80 ° C until PVA is completely dissolved, then add 2 g of modified zeolite powder at 121 ° C, 1.5 atm. The force (atm) was sterilized for 20 minutes, and allowed to stand to cool to room temperature. Add 10% centrifuged slime, pour the mixture into a 50mL syringe, slowly drop it into a saturated solution of boric acid containing 2% calcium chloride (CaCl ₂ ) and fix it at 4 ° C to form a diameter of 3 mm (mm). The pellets are fixed for 24 hours. After being taken out, rinse with physiological distilled water for 2 to 3 times to be used.

Example 1 Comparison of Modified Zeolite Surfaces

In this experiment, the surface of the modified zeolite was compared with the surface of the unmodified zeolite by scanning electron microscopy (SEM). The experimental results showed that the surface of the modified zeolite had traces of strong acid and alkali corrosion, and the surface was obviously extended. The pore size increases, indicating that the surface area of the modified zeolite will increase, thereby increasing the adsorption capacity of ammonia nitrogen (Fig. 1). Studies have shown that in the process of sodium hydroxide modification, the surface area to total pore volume ratio of zeolite is reduced, indicating that the pore size of the pores on the surface of the zeolite will also increase, which is beneficial to the substitution of the ions, thereby increasing the adsorption capacity of the zeolite for ammonia nitrogen ( Zhu Fenghua et al., 2010), Sun Xingbin et al. used the modified zeolite to study its ability to remove phosphorus. The results show that the surface of the unmodified zeolite is irregular and the pores are small. Although the surface is filled with pores, most of the pores are Blocked by other substances, the surface layer of the modified zeolite becomes distinct, and the pores on the surface become larger, forming a coral-like surface structure. This surface structure increases the surface area of the zeolite surface and also increases the adsorption capacity of the zeolite ( Sun Xingbin et al., 2010).

Langmuir isotherm Among them, in the equation, q _e is the adsorption amount per unit of adsorbent (mg/g), C is the equilibrium concentration of the adsorbate, q _m is the adsorbent saturated adsorption amount (mg/g), and K _L is a constant. . Count the Langmuir equation: . The ratio of 1/q _e to 1/C was plotted, and the saturated adsorption amount of the adsorbent qm=17.89 mg/g and the adsorption constant KL=3.42 L/mol were obtained from the intercept and the slope.

The linear regression of the Langmuir isotherm adsorption mode has a high R Spuare value, which represents the adsorption mode of modified mordenite for ammonia nitrogen, which is consistent with the Langmuir isotherm adsorption mode. The higher the adsorption constant K _{L , the} higher the adsorption capacity of the adsorbent (Fig. 2). Englert et al. studied the properties of natural intellectual zeolite (mainly composed of zeolite and mordenite) and its adsorption capacity for ammonia nitrogen. The results show that the surface area of natural Chilean zeolite is 177 m ² /g, and the exchange capacity of ammonia nitrogen is 1.02meq/g, the results of the adsorption of ammonia nitrogen showed that the natural Chilean zeolite adsorption rate of ammonia nitrogen is quite fast, the adsorption capacity can reach 0.68 meq/g, and the adsorption mode can be consistent with the Langmuir adsorption mode (Englert and Rubio, 2005). ).

Example 2 Analysis of Sewage Treatment by Surface Adsorption and Immobilization of CBM Composite Microbial Zeolite

The modified mordenite and composite biocatalyst were used to compare the ammonia nitrogen adsorption capacity of the ammonia-nitrogen simulated wastewater treatment. The experimental results show that the ammonia-nitrogen adsorption capacity of the composite biocatalyst is significantly better than that after modification. Mordenite has a strong ammonia nitrogen adsorption capacity. The experimental results show that the ammonia nitrogen removal rate of zeolite can reach 52%, and the ammonia nitrogen removal rate of composite biocatalyst can reach 63% (Fig. 3).

CBM is embedded in immobilized biocatalyst to treat freshwater wastewater. Ammonia nitrogen freshwater simulated wastewater was added with CBM embedded immobilized biocatalyst. The original concentration of NH ⁴⁺ was 4.5ppm, the added amount was 5g/L, the control group was not added, the NH ⁴⁺ concentration was detected daily, and 3 repeated for 7 consecutive days. It shows that CBM has the ability to significantly degrade ammonia ions in water, and the efficacy can last for more than 7 days (Fig. 4A). Adding CBM-embedded immobilized biocatalyst to nitrous acid fresh water wastewater, the original concentration of NO ^2- is 0.4ppm, the addition amount is 5g/L, the control group is not added, the NO ^2- concentration is detected daily, and 3 repetitions are repeated for 7 consecutive days. It shows that CBM has the ability to significantly degrade nitrite ions in water, and the efficacy can last for more than 7 days (Fig. 4B).

CBM embeds immobilized biocatalyst to treat seawater wastewater. Ammonia-nitrogen seawater wastewater was added with CBM-embedded immobilized biocatalyst. The original concentration of NH ⁴⁺ was 4.5 ppm, the added amount was 5g/L, the control group was not added, the NH ⁴⁺ concentration was detected daily, and 3 repetitions were repeated for 7 days. The results showed CBM has the ability to significantly degrade ammonia ions in water, and its efficacy can last for more than 7 days (Fig. 5A). The nitrite seawater simulated wastewater was added with CBM embedded immobilized biocatalyst. The original concentration of NO ^2- was 0.4ppm, the addition amount was 5g/L, the control group was not added, the concentration of NO ^{2- was} detected daily, and 3 repetitions were repeated for 7 days. The results show that CBM has the ability to significantly degrade nitrite ions in water, and the efficacy can last for more than 7 days (Fig. 5B).

CBM embeds immobilized biocatalyst to treat marine aquaculture wastewater. Ammonia nitrogen marine aquaculture wastewater was added with CBM embedded immobilized biocatalyst. The original concentration of NH ⁴⁺ was 1.38ppm, the addition amount was 5g/L, the control group was not added, the NH ⁴⁺ concentration was detected daily, and 3 repetitions were repeated for 15 days. The results show that CBM has the ability to significantly degrade ammonia ions in water, and the efficacy can last for more than 15 days (Fig. 6A). The nitrite seawater simulated wastewater was added with CBM embedded immobilized biocatalyst. The original concentration of NO ^2- was 0.73ppm, the addition amount was 5g/L, the control group was not added, the NO ^2- concentration was detected daily, and 3 repetitions were repeated for 15 days. The results show that CBM has the ability to significantly degrade nitrite ions in water, and the efficacy can last for more than 15 days (Fig. 6B).

CBM-embedded immobilized biocatalyst was added to marine aquaculture wastewater. The original COD concentration was 2.54ppm, the addition amount was 5g/L, the control group was not added, the COD concentration was measured daily, and 3 repetitions were repeated for 15 days. The results showed that CBM was significant. The ability to degrade COD in water, and the efficacy can last for more than 15 days (Figure 6 C). Seawater simulated wastewater added CBM embedded immobilized biocatalyst, sulfide The original concentration of (sulfide) was 41 ppb, the addition amount was 5g/L, the control group was not added, the sulfide concentration was measured every day, and 3 repetitions were repeated for 15 days. The results showed that CBM has the ability to significantly degrade sulfide in water, and the effect can be continued. More than 15 days (Fig. 6D).

Example 3 Improving black odorous sewage with a novel CBM composite biocatalyst

CBM embeds immobilized biocatalyst to treat black odorous sewage. Adding CBM-embedded immobilized biocatalyst to the black odorous sewage at the bottom of the river, adding the experimental results of the immobilized biocatalyst and adding the modified mordenite to the ammonia removal rate in the sewage (Fig. 7A), and adding the immobilized organism The experimental results of the catalyst and the addition of the modified mordenite to the nitrite removal rate in the sewage (Fig. 7B), each experimental group consists of three repetitions, and the experimental data are expressed as mean and standard deviation.

Adding CBM-embedded immobilized biocatalyst to the black odorous sewage at the bottom of the river, adding the experimental results of the immobilized biocatalyst and adding the modified mordenite to the COD removal rate in the sewage (Fig. 7C), and adding the immobilized organism The experimental results of the catalyst and the addition of the modified mordenite to the removal rate of suspended solid particles in the sewage (Fig. 7D), the suspended particle unit is NTU (nephelometric turbidity unit), and each experimental group includes three repetitions. Experimental data is expressed as mean and standard deviation.

Adding CBM-embedded immobilized biocatalyst to the black odorous sewage at the bottom of the river, adding the experimental results of the immobilized biocatalyst and adding the modified mordenite to the removal rate of phosphorus-containing molecules in the sewage (Fig. 7E), and adding and fixing The experimental results of the biocatalyst and the addition of the modified mordenite to the removal rate of sulfur-containing molecules in the sewage (Fig. 7F), each experimental group includes three repetitions, and the experimental data are expressed by the mean value and the standard deviation.

Example 4 Synchronous in situ ecological restoration application of water and sediment

The substrate-purifying agent for fixing the complex beneficial microorganism (CBM) is 400-750 g/m ² and spread evenly on the bottom of the river. There are 2 sets of 2.2Kw water-lifting aerators, and the aerator runs 8 hours a day. After 17 days, the water body eliminates the black odor phenomenon. From the upstream to the downstream, the dark gray-grey yellow-yellow-green gradient process appears. The transparency increases from about 12cm in the upstream water body to about 45cm in the downstream, and it gradually increases from upstream to downstream. . After 30 days, a large amount of yellow-brown floating sludge appeared in the upstream. After 60 days, the sediment was degraded by 45 cm, and the floating brown sludge in the upstream gradually decreased. At this time, 0.3-0.5m submerged and emergent plant belts were planted at the water and land junctions, and 250g/m ^{2 of} substrate purifying agent was added to enter the water quality maintenance period.

Compare the water quality of the river after adding the sediment purifying agent. The water pollution factors are listed in Table 1 and Table 2 as follows:

There is no primer purifying agent, and the sediment is black and has a strong odor. Three months after the release of the substrate purifying agent, the sediment was purified and had no odor, and the river bottom sludge and suspended solids SS were reduced by 45-60 cm. The biological factors that cause the smell of river water are listed in Table 3 as follows:

Example 5 Quantitative Analysis of Various Microorganisms

In order to confirm the content of each species in the composite beneficial microorganism (CBM), quantitative analysis of each culture period in the complex beneficial microbial preparation (quantitative culture, first culture, second culture) by quantitative nucleic acid polymerase chain reaction (quantitative PCR) ) The number and proportion of each species. The quantitative analysis of each culture period is shown in Fig. 8.

This technology is especially suitable for occasions where dredging is not possible. Overcome the problems of high cost, excessive noise, easy to smell, and difficult to handle. The use of a composite substrate purifying agent can play a stable and harmless effect on heavy metals and phosphorus. For example, both chromium and phosphorus can be transferred to the sediment as sediment to reduce the release of the overlying water. The use of a new type of substrate purifying agent can carry out muddy water integration and ecological restoration of seriously polluted rivers. The technology is simple to operate and has no adverse effects on river flood control, and there is no additional cost during operation.

The above-mentioned multiple functions are the statutory invention patents that fully meet the novelty and progress. If you apply in accordance with the law, you are requested to approve the invention patent application to encourage invention.

Claims (10)

A composition for removing sewage and a reforestation channel, the composition comprising a porous cavity material and a microbial composition. The composition according to claim 1, wherein the porous hole material is a modified zeolite or algin. The composition of the microbial composition according to claim 1, wherein the microbial composition is continuously cultured for 7 days at 28 ° C, a rotation speed of 200 rpm, and an illumination intensity of 1000 lux; and then 5% molasses, 0.4% is added. After urea and 0.15% potassium dihydrogen phosphate, the temperature was controlled at 28 ° C and the fermentation was continued for 5 days in a fermentation tank. A method for producing a modified zeolite according to the composition of claim 2, which comprises washing and drying the mordenite with distilled water, immersing the zeolite in 5% hydrochloric acid for 2 hours, and then washing with distilled water. The net to pH was neutral and dried, and the zeolite was soaked in 5% sodium hydroxide for 2 hours, and finally washed with distilled water until the pH was neutral and dried. A method for using a composition to inject sewage to remove pollution, which is to be used for sewage decontamination by the composition referred to in claim 1 of the patent application. For example, in the method described in claim 5, the sewage refers to fresh water wastewater, seawater wastewater, freshwater aquaculture wastewater, or marine aquaculture sewage. The method of claim 6, wherein the composition is added in an amount of 3-8 grams per liter of sewage. For example, in the method described in claim 5, the sewage refers to sewage in a ditch, a reservoir, a sewage sewer, a river, and the like. The method of claim 8, wherein the composition is added to the sewage volume of 400-750 grams per square meter of sewage area. According to the method described in claim 5, the method for removing pollution includes reducing the concentration of amine ions, nitrite ions, sulfur compounds, phosphorus compounds, solid suspended particles, etc., and reducing biological oxygen demand and chemical oxygen demand. the amount.