CN110776103B - Adsorption membrane system using immobilized microcystis and preparation method thereof - Google Patents
Adsorption membrane system using immobilized microcystis and preparation method thereof Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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Abstract
The invention relates to an adsorption membrane system utilizing immobilized microcystis and a preparation method thereof. The system at least comprises: the device comprises a bracket, wherein a plurality of immobilized microcapsule algae membrane assemblies are arranged on the bracket at intervals, and an aeration device is arranged between every two adjacent immobilized microcapsule algae membrane assemblies. The invention provides an immobilized microcystis adsorption membrane system for purifying nitrogen and phosphorus in a water body by using the immobilized microcystis adsorption membrane, which not only increases the contact area of the system and wastewater, but also enhances the strength of immobilized microalgae, solves the problems of swelling, small contact area, low efficiency and the like in the use process, and simultaneously has the function of effectively utilizing microcystis to efficiently remove nutrient salts and partial organic matters in the water body, thereby achieving the purpose of purifying water quality. Meanwhile, the system of the invention provides dissolved oxygen, can ensure the problem of the supply of microcystis in wastewater, has complete whole system and is convenient to install and use.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a system for purifying nitrogen and phosphorus in water by using an immobilized microcystis adsorption membrane.
Background
Along with the aggravation of human activities in river and lake watershed, a large amount of nutritive salt enters into water body through various ways, so that the river and lake enter into eutrophication state. The international organization for economic development cooperation (OECD) defines the phenomenon that the use of water is affected by a series of changes such as increase of productivity of algae and aquatic plants, decrease of water quality and the like caused by increase of nutritive salts in water bodies as eutrophication of rivers and lakes, and establishes corresponding standards. River and lake eutrophication is a major water environment problem in China at present and for a long time in the future, and a common phenomenon accompanied with water eutrophication is the transition growth of phytoplankton to form algal bloom, so that water quality is reduced, and ecological system lesions and other water environment problems are caused. Moreover, the problem of water bloom is not only a simple water pollution problem, but also a problem of ecosystem imbalance, which is a disaster that occurs after the structural functions of the ecosystem have been significantly changed by the intervention of human activities.
The water environment treatment and protection are extremely complex system engineering, and besides the eutrophication of water bodies is treated on the engineering level, the algae is controlled by applying a single or a combination of multiple algae control technologies in the water environment protection. Various algae control technologies are developed to date, and the algae control technologies can be mainly divided into the following steps according to the algae removal mode: flocculating to remove algae, killing algae with medicament, dissolving algae by microorganism and inhibiting algae, mechanically removing algae, phytochemical inhibiting algae, air floating to remove algae, removing algae by aquatic animals, etc. However, the subsequent treatment problem of the blue algae by the processes is not well solved, so that the problems of high outward transportation cost, secondary pollution risk and the like of the blue algae are caused. Therefore, how to effectively treat the microcystis is one of the key problems in the blue algae pollution treatment process.
Most of the immobilized microalgae in the past are single in type, most of the immobilized microalgae are immobilized small spheres with the diameter of less than 1cm, and the immobilized microalgae spheres are easy to immobilize due to small volume, but have a plurality of application barriers, such as collection problems, immobilization efficiency and the like. However, when the volume of immobilized microalgae is increased, the problem of swelling is prominent, and the immobilization strength is reduced, causing problems such as leakage of algae and dissolution of the immobilizing agent.
Disclosure of Invention
In order to solve the problems, the invention provides a system for purifying nitrogen and phosphorus in a water body by using an immobilized microcystis adsorption membrane on the basis of the prior art, which not only ensures that the contact area with sewage is large enough, but also enhances the strength of immobilized microalgae, solves the problems of swelling, small contact area, low efficiency and the like in the using process, and also effectively removes nutritive salt and partial organic matters in the water body by using microcystis in a recycling manner, thereby achieving the purpose of purifying the water. Meanwhile, the system of the invention provides dissolved oxygen, can ensure the problem of the supply of microcystis in wastewater, has complete whole system and is convenient to install and use.
In order to achieve the above object, the present invention relates to a system for purifying nitrogen and phosphorus in water by using an immobilized microcystis adsorption membrane, the system at least comprises: the device comprises a bracket, wherein a plurality of immobilized microcapsule algae membrane assemblies are arranged on the bracket at intervals, and an aeration device is arranged between every two adjacent immobilized microcapsule algae membrane assemblies.
Preferably, the microcapsule algae solution in the immobilized microcapsule algae membrane is prepared by the following method:
21) centrifuging the microcystis obtained by the salvage or culture method and then concentrating for later use;
22) preparing a fixing agent: preparing a mixed solution of sodium alginate and polyvinyl alcohol;
23) adding a cross-linking agent into the prepared mixed solution;
24) adding the concentrated algae solution into the cross-linked fixing agent, and performing constant volume;
25) after the volume is fixed, the fixing agent added with the algae liquid is further crosslinked, so that the fixing agent is fully mixed and connected with the algae liquid.
Preferably, the immobilized microcapsule algae membrane component comprises a membrane clamping plate for clamping the microcapsule algae membrane, and the membrane clamping plate is provided with a plurality of liquid through holes.
Preferably, the microcapsule algae membrane is prepared by the following method:
41) brushing a polyvinyl alcohol coating on the flat plate, wherein the concentration of the polyvinyl alcohol is 8-15%;
42) then putting the mixture into an oven to be dried at 40-50 ℃ until the coating is completely dried;
43) brushing a layer of cross-linking agent on the surface of the polyethylene coating, wherein the cross-linking agent is glutaraldehyde;
44) uniformly pouring the microcapsule algae mixed solution mixed with the fixing agent and the cross-linking agent onto the polyethylene coating brushed with the cross-linking agent prepared in the step 43);
45) fixing the single side of the microcapsule algae solution on the polyethylene coating by using the shaping solution, and taking down the microcapsule algae solution from the flat plate.
Preferably, the volume ratio of the fixing agent to the microcapsule algae liquid is 30:1-1000: 1.
Preferably, the cross-linking agent is glutaraldehyde, the concentration of the cross-linking agent is 3% -6%, and the cross-linking time without adding the fixing agent before algae is 10-24 hours.
Preferably, the setting solution is a mixed solution of calcium chloride and boric acid, wherein the content of the calcium chloride is 1-3% (w/v), and the content of the mixed solution of boric acid is 2-5% (w/v).
Preferably, the micropore aeration device is connected with the fan through an air supply pipeline for joint operation.
In order to achieve the above purpose, the preparation method of the immobilized microcapsule algae membrane comprises the following steps:
91) brushing a polyvinyl alcohol coating on the flat plate, wherein the concentration of the polyvinyl alcohol is 8-15%; the flat plate is an anti-corrosion plate with certain strength, and the anti-corrosion plate is an organic glass plate, a toughened glass plate or a stainless steel plate;
92) then putting the mixture into an oven to be dried at 40-50 ℃ until the coating is completely dried;
93) brushing a layer of cross-linking agent on the surface of the polyethylene coating, wherein the cross-linking agent is glutaraldehyde;
94) uniformly pouring the micro-capsule algae liquid on the polyethylene coating which is brushed with the cross-linking agent and is prepared in the step 93);
95) fixing the single side of the microcapsule algae solution on the polyethylene coating by using the shaping solution, and taking down the microcapsule algae solution from the flat plate.
In order to achieve the purpose, the invention also relates to an application of the immobilized microcystis adsorption membrane in adsorbing nitrogen and phosphorus in a water body.
The invention provides an immobilized microcystis adsorption membrane system for purifying nitrogen and phosphorus in a water body by using the immobilized microcystis adsorption membrane, which not only increases the contact area of the system and wastewater, but also enhances the strength of immobilized microalgae, solves the problems of swelling, small contact area, low efficiency and the like in the use process, and simultaneously has the function of effectively utilizing microcystis to efficiently remove nutrient salts and partial organic matters in the water body, thereby achieving the purpose of purifying water quality. Meanwhile, the system of the invention provides dissolved oxygen, can ensure the problem of the supply of microcystis in wastewater, has complete whole system and is convenient to install and use.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a diagram of an apparatus for purifying nitrogen and phosphorus in water by using an immobilized microcapsule algae adsorption membrane in example 1;
FIG. 2(a) is a schematic structural diagram of an immobilized microcystis membrane module according to an embodiment of the present invention.
Fig. 2(b) is a schematic side view of fig. 2 (a).
FIG. 3(a) is a schematic structural view of an immobilized microcystis membrane module according to another embodiment of the present invention.
Fig. 3(b) is a schematic side view of fig. 3 (a).
Detailed Description
The invention is further described in the following with reference to the description.
Example 1
The microcapsule algae liquid is salvaged, expanded and cultured at room temperature, and then concentrated for later use. Firstly, adding a mixed solution of sodium alginate and polyvinyl alcohol serving as fixing agents for mixing, and adding a cross-linking agent after mixing to change the molecular structure of the mixture so as to enable the mixture to be firmer; adding the prepared concentrated algae solution into the cross-linked fixing agent, and performing constant volume; after the volume is fixed, the fixing agent added with the algae liquid is further crosslinked, so that the fixing agent is fully mixed and connected with the algae liquid.
The immobilized microcapsule algae membrane is prepared by the following method: firstly, coating a layer of polyvinyl alcohol with the concentration of 15% on a flat plate, and drying for 24 hours at low temperature; then coating a layer of cross-linking agent (glutaraldehyde) with concentration of 4%, finally pouring the prepared mixed algae liquid on a flat plate for single-side cross-linking fixation, and spraying fixing agent (CaCl) on the other side2And boric acid mixed solution) for shaping, and mixingAnd the film covered on the flat plate is taken down after the edge is simply corrected.
Clamping the prepared immobilized microcapsule algae membrane 82 by two membrane clamping plates 81 with liquid through holes 82 to obtain an immobilized microcapsule algae membrane assembly 8, and inserting the immobilized microcapsule algae membrane assembly 8 into the immobilized microcapsule algae membrane fixing groove 6 to ensure that the immobilized microcapsule algae membrane assembly is arranged on an immobilized microcapsule algae membrane bracket; starting the fan 1, opening the control valve 2 and the branch pipe control valve 3, and finally aerating through the aeration component 1 through the air supply pipeline 5.
The device is arranged in a simulated sewage tank, and the volume of sewage in the sewage tank is 2m3The initial ammonia nitrogen concentration is 102mg/L, and the total phosphorus concentration is 25 mg/L. After the device operates and purifies the water body for 3 days, the ammonia nitrogen removal rate reaches over 70 percent, and the total phosphorus removal rate reaches over 75 percent; the ammonia nitrogen removal rate reaches more than 95 percent in 10 days, and the total phosphorus removal rate reaches more than 95 percent. The device is proved to have better removal effect.
Observing the fixed microcapsule algae membrane leakage condition during the purification process. Chlorophyll is not detected in the initial water body, but is not detected in the final water body basically, which indicates that the algae basically do not leak, the fixing effect of the fixing agent is good, and the risk of secondary pollution is eliminated.
Example 2
Fishing the micro-capsule algae solution, performing expansion culture in an indoor algae culture device, and concentrating for later use. Firstly, adding a mixed solution of sodium alginate and polyvinyl alcohol serving as fixing agents for mixing, and adding a cross-linking agent after mixing to change the molecular structure of the mixture so as to enable the mixture to be firmer; adding the prepared concentrated algae solution into the cross-linked fixing agent, and performing constant volume; after the volume is fixed, the fixing agent added with the algae liquid is further crosslinked, so that the fixing agent is fully mixed and connected with the algae liquid.
The immobilized microcapsule algae membrane is prepared by the following method: firstly, coating a layer of polyvinyl alcohol with the concentration of 10% on a flat plate, and drying for 24 hours at low temperature; then coating a layer of cross-linking agent (glutaraldehyde) with concentration of 4%, finally pouring the prepared mixed algae liquid on a flat plate for single-side cross-linking fixation, and spraying fixing agent (CaCl) on the other side2And boric acid mixed solution) intoAnd (5) shaping, namely simply correcting the edge of the film covered on the flat plate and then taking down the film.
Clamping the prepared immobilized microcapsule algae membrane 83 by two membrane clamping plates 81 with liquid through holes 82 to obtain an immobilized microcapsule algae membrane assembly 8, and inserting the immobilized microcapsule algae membrane assembly 8 into the immobilized microcapsule algae membrane fixing groove 6 to enable the immobilized microcapsule algae membrane assembly to be arranged on an immobilized microcapsule algae membrane bracket; starting the fan 1, opening the control valve 2 and the branch pipe control valve 3, and finally aerating through the aeration component 1 through the air supply pipeline 5.
The device is arranged in Nanjing Jian 37050The Duozhao in a certain branchia in the area, the river is about 10 meters long, the initial ammonia nitrogen concentration is 35.3mg/L, and the total phosphorus concentration is 4.6 mg/L. After the device operates and purifies the water body for 3 days, the ammonia nitrogen removal rate reaches more than 50 percent, and the total phosphorus removal rate reaches more than 50 percent; the ammonia nitrogen removal rate reaches more than 60 percent in 10 days, and the total phosphorus removal rate reaches more than 65 percent. The device is proved to have better removal effect.
Observing the fixed microcapsule algae membrane leakage condition during the purification process. Chlorophyll is not detected in the initial water body, but is not detected in the final water body basically, which indicates that the algae basically do not leak, the fixing effect of the fixing agent is good, and the risk of secondary pollution is eliminated.
Example 3
Fishing the micro-capsule algae solution, performing expansion culture in an indoor algae culture device, and concentrating for later use. Firstly, adding a mixed solution of 3 percent (w/v) of sodium alginate serving as a fixing agent and 9 percent (w/v) of polyvinyl alcohol for mixing, adding a cross-linking agent after mixing, and changing the molecular structure of the cross-linking agent to be firmer; adding the prepared concentrated algae solution into the cross-linked fixing agent, and performing constant volume; after the volume is fixed, the fixing agent added with the algae liquid is further crosslinked for 10 hours, so that the fixing agent and the algae liquid are fully mixed and connected. Uniformly pouring the fully crosslinked mixed solution into a template, drying for 4-24 hours for shaping (shaping the external form), demolding, and placing the demolded immobilized microcapsule algae membrane into CaCl2And carrying out secondary shaping (inner structure shaping) in the boric acid mixed solution, and finishing the shaped immobilized microalgae membrane. Two membrane clamping plates 81 with holes with the diameter of 5mm densely distributed on the upper surfacesThe resulting microalgae membrane 83 is clamped, as shown in fig. 2. The membrane module covered with the immobilized micro-capsule algae membrane is manufactured.
Simply correcting the edge of the membrane covered on the membrane component, and then inserting the immobilized microcapsule algae membrane component into the immobilized microcapsule algae membrane fixing groove 6 to ensure that the immobilized microcapsule algae membrane component is installed on the immobilized microcapsule algae membrane bracket; starting the fan 1, opening the control valve 2 and the branch pipe control valve 3, and finally aerating through the aeration component 1 through the air supply pipeline 5.
The device is arranged in a certain branchia creek in Maanshan, the river course is about 10 meters long, the initial ammonia nitrogen concentration is 35.3mg/L, and the total phosphorus concentration is 4.6 mg/L. After the device is operated to purify the water body for 3 days, the ammonia nitrogen removal rate reaches 67.2 percent, and the total phosphorus removal rate reaches more than 50 percent; the ammonia nitrogen removal rate reaches 71.3 percent in 10 days, and the total phosphorus removal rate reaches about 65 percent. The device is proved to have better removal effect.
Observing the fixed microcapsule algae membrane leakage condition during the purification process. Chlorophyll is not detected in the initial water body, but is not detected in the final water body basically, which indicates that the algae basically do not leak, the fixing effect of the fixing agent is good, and the risk of secondary pollution is eliminated.
Example 4
Fishing the micro-capsule algae solution, performing expansion culture in an indoor algae culture device, and concentrating for later use. Firstly, adding a mixed solution of 3 percent (w/v) of sodium alginate serving as a fixing agent and 9 percent (w/v) of polyvinyl alcohol for mixing, adding a cross-linking agent after mixing, and changing the molecular structure of the cross-linking agent to be firmer; adding the prepared concentrated algae solution into the cross-linked fixing agent, and performing constant volume; after the volume is fixed, the fixing agent added with the algae liquid is further crosslinked for 10-12 hours, so that the fixing agent and the algae liquid are fully mixed and connected. Uniformly pouring the fully crosslinked mixed solution into a template, drying for 4-24 hours for shaping (shaping the external form), demolding, and placing the demolded immobilized microcapsule algae membrane into CaCl2And carrying out secondary shaping (inner structure shaping) in the boric acid mixed solution, and finishing the shaped immobilized microalgae membrane.
In this embodiment, the membrane clamping plate 81 of the immobilized microalgae membrane is a stainless steel plate, the length and width of the two pieces are both 1 meter, and a hollow strip 82 with the width of 5mm is arranged on the membrane clamping plate, as shown in fig. 3. The microalgae membrane 83 can be in full contact with the water body to be treated, and the two sides of the microalgae membrane are in contact. The membrane module covered with the immobilized microcapsule algae membrane is manufactured by fastening the membrane module by using the buckle 84.
Simply correcting the edge of the membrane covered on the membrane component, and then inserting the immobilized microcapsule algae membrane component into the immobilized microcapsule algae membrane fixing groove 6 to ensure that the immobilized microcapsule algae membrane component is installed on the immobilized microcapsule algae membrane bracket; starting the fan 1, opening the control valve 2 and the branch pipe control valve 3, and finally aerating through the aeration component 1 through the air supply pipeline 5.
The device is arranged in a certain branchia creek in Maanshan, the river course is about 10 meters long, the initial ammonia nitrogen concentration is 35.3mg/L, and the total phosphorus concentration is 4.6 mg/L. After the device operates and purifies the water body for 3 days, the ammonia nitrogen removal rate reaches more than 60 percent, and the total phosphorus removal rate reaches more than 50 percent; the ammonia nitrogen removal rate reaches 65% in 10 days, and the total phosphorus removal rate reaches more than 60%. The device is proved to have better removal effect.
Observing the fixed microcapsule algae membrane leakage condition during the purification process. Chlorophyll is not detected in the initial water body, but is not detected in the final water body basically, which indicates that the algae basically do not leak, the fixing effect of the fixing agent is good, and the risk of secondary pollution is eliminated.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (5)
1. An adsorption membrane system utilizing immobilized microcystis is characterized in that: the system at least comprises: the device comprises a bracket, a plurality of immobilized microcapsule algae membrane assemblies are arranged on the bracket at intervals, and an aeration device is arranged between every two adjacent immobilized microcapsule algae membrane assemblies;
the immobilized microcapsule algae membrane assembly comprises a membrane clamping plate for clamping a microcapsule algae membrane, and a plurality of liquid through holes are formed in the membrane clamping plate; the microcapsule algae membrane is prepared by the following method:
41) brushing a polyvinyl alcohol coating on the flat plate, wherein the concentration of the polyvinyl alcohol is 8-15%;
42) then putting the mixture into an oven to be dried at 40-50 ℃ until the coating is completely dried;
43) brushing a layer of cross-linking agent on the surface of the polyvinyl alcohol coating;
44) uniformly pouring the micro-capsule algae liquid mixed with the fixing agent and the cross-linking agent onto the polyvinyl alcohol coating layer brushed with the cross-linking agent prepared in the step 43);
45) fixing the single side of the micro-capsule algae solution on the polyvinyl alcohol coating by using a shaping solution, and then taking down the micro-capsule algae solution from the flat plate;
the shaping solution is a mixed solution of calcium chloride and boric acid, wherein the content of the calcium chloride is 1-3% (w/v), and the content of the boric acid mixed solution is 2-5% (w/v).
2. The immobilized microencapsulated algae adsorptive membrane system of claim 1, wherein: the microcapsule algae liquid is prepared by the following method:
21) centrifuging the microcystis obtained by the salvage or culture method and then concentrating for later use;
22) preparing a fixing agent: preparing a mixed solution of sodium alginate and polyvinyl alcohol;
23) adding a cross-linking agent into the prepared mixed solution;
24) adding the concentrated algae solution into the cross-linked fixing agent, and performing constant volume;
25) after the volume is fixed, the fixing agent added with the algae liquid is further crosslinked, so that the fixing agent is fully mixed and connected with the algae liquid.
3. The immobilized microencapsulated algae adsorptive membrane system of claim 2, wherein: the volume ratio of the fixing agent to the micro-capsule algae liquid in the step 21) is 30:1-1000: 1.
4. The immobilized microencapsulated algae adsorptive membrane system of claim 1, wherein: the aeration device is connected with the fan through a gas supply pipeline to work together.
5. A preparation method of an immobilized microcapsule algae membrane is characterized by comprising the following steps:
91) brushing a polyvinyl alcohol coating on the flat plate, wherein the concentration of the polyvinyl alcohol is 8-15%; the flat plate is an anti-corrosion plate with certain strength, and the anti-corrosion plate is an organic glass plate, a toughened glass plate or a stainless steel plate;
92) then putting the mixture into an oven to be dried at 40-50 ℃ until the coating is completely dried;
93) brushing a layer of cross-linking agent on the surface of the polyvinyl alcohol coating;
94) uniformly pouring the micro-capsule algae liquid on the polyvinyl alcohol coating which is brushed with the cross-linking agent and is prepared in the step 93);
95) fixing the single side of the micro-capsule algae solution on the polyvinyl alcohol coating by using a shaping solution, and then taking down the micro-capsule algae solution from the flat plate;
the shaping solution is a mixed solution of calcium chloride and boric acid, wherein the content of the calcium chloride is 1-3% (w/v), and the content of the boric acid mixed solution is 2-5% (w/v).
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