CN112824331B - Modified biological membrane carrier and preparation method and application thereof - Google Patents
Modified biological membrane carrier and preparation method and application thereof Download PDFInfo
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- CN112824331B CN112824331B CN201911148629.XA CN201911148629A CN112824331B CN 112824331 B CN112824331 B CN 112824331B CN 201911148629 A CN201911148629 A CN 201911148629A CN 112824331 B CN112824331 B CN 112824331B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/108—Immobilising gels, polymers or the like
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/109—Characterized by the shape
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention belongs to the technical field of biomembrane carriers, and particularly relates to a modified biomembrane carrier and a preparation method and application thereof. The invention provides a preparation method of a modified biological carrier, which comprises the following steps: sequentially carrying out first heat preservation and second heat preservation on carbon fibers to obtain the modified biological membrane carrier; the temperature of the first heat preservation is 150-250 ℃; the temperature of the second heat preservation is 250-650 ℃. According to the preparation method provided by the invention, the resin slurry on the surface of the carbon fiber can be decomposed by the first heat-preservation stage treatment, so that the use of a large amount of organic solvent for soaking, washing and removing the slurry is avoided, and the production expansion is facilitated; and the second heat preservation stage promotes the oxidation and the loss of the carbon fiber, so that the modification of the carbon fiber is realized. The experiment effect shows that the biomass of carbon fiber in unit mass of the aerobic unit can reach 10-12 g/g and the biomass of carbon fiber in unit mass of the anoxic unit can reach 3-5 g/g after the modified biomembrane carrier provided by the invention runs for a long time.
Description
Technical Field
The invention belongs to the technical field of biomembrane carriers, and particularly relates to a modified biomembrane carrier and a preparation method and application thereof.
Background
The biomembrane method is one of the main methods for sewage treatment, has stronger adaptability to the change of the quality and the quantity of sewage, generates less sludge, has no sludge bulking problem, particularly has better treatment effect on low-concentration sewage, and is widely applied to the treatment of urban sewage and industrial wastewater. Biofilms are the basis for biofilm processes. Whereas the generation and growth of biofilms is not independent of the use of carrier materials. The water treatment biomembrane carrier is a medium required in the process of fixing biological cells and enzymes by a biomembrane method in the secondary biological treatment of urban sewage and industrial wastewater, and is positioned in a bioreactor or a biochemical pool at a biochemical stage, namely a biological filler commonly referred to in the industry; the biofilm carrier has a key role in the biofilm process.
In the 90 s of the 20 th century, japanese scholars have begun to develop researches on purifying natural water bodies by using carbon fibers as biomembrane carriers, but the carbon fibers are expensive and have high use cost, so that the development of the application of the carbon fibers is limited. With the increase of the localization degree of the carbon fiber, the price of the carbon fiber is reduced, and the price of the home-made carbon fiber is only 1/2 of that of the imported product. More and more scholars in China develop research work of the carbon fiber biomembrane carrier in water treatment, and particularly modify carbon fiber materials to obtain better biocompatibility.
The existing technology for modifying carbon fiber materials mainly comprises electrochemical modification, wet modification (including acidic oxidation and alkaline oxidation), cation loading, chemical grafting and other modification technologies, the modification technologies firstly use ethanol or acetone to soak carbon fiber products, wash off resin slurry on the fiber surface, modify the carbon fiber after drying, and generate a large amount of organic solvents in the modification process, so that the modification cost is increased, pollution is easy to generate, the industrial popularization is not facilitated, and the application of modified carbon fibers in the field of biomembrane carriers is limited.
Disclosure of Invention
In view of this, the invention aims to provide a modified biomembrane carrier, which has good removal effect on COD and ammonia nitrogen in sewage; the invention also provides a preparation method of the modified biomembrane carrier, which has low cost, is simple and easy to operate and does not produce secondary pollution; the invention also provides an application of the modified biomembrane carrier.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a modified biological carrier, which comprises the following steps:
sequentially carrying out first heat preservation and second heat preservation on the carbon fiber to obtain a modified biomembrane carrier;
the temperature of the first heat preservation is 150-250 ℃; the temperature of the second heat preservation is 250-650 ℃.
Preferably, the carbon fibers include one or more of polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, viscose-based carbon fibers, and lignin-fiber-based carbon fibers.
Preferably, the first heat preservation time is 5-15 min.
Preferably, the time of the second heat preservation is 30-180 min.
Preferably, the atmosphere of the first heat preservation and the second heat preservation is an oxygen-containing atmosphere.
The invention also provides the modified biomembrane carrier prepared by the preparation method in the technical scheme.
The invention also provides application of the modified biomembrane carrier prepared by the preparation method in the technical scheme in the field of water treatment.
Preferably, the modified biofilm carrier is applied to an anoxic unit and/or an aerobic unit of a water treatment process.
Preferably, in the anoxic unit and the aerobic unit, the filling density of the modified biomembrane carrier is independently 100-1000 g/m 3 。
Preferably, the water flow mode in the anoxic unit and the aerobic unit is an upward flow water inlet and outlet mode.
The invention provides a preparation method of a modified biological carrier, which comprises the following steps: sequentially carrying out first heat preservation and second heat preservation on carbon fibers to obtain the modified biological membrane carrier; the temperature of the first heat preservation is 150-250 ℃; the temperature of the second heat preservation is 250-650 ℃. By adopting the preparation method provided by the invention, the carbon fiber can be processed only by two sections of different process conditions in the same equipment, the resin slurry on the surface of the carbon fiber can be decomposed by the first heat preservation stage, the use of a large amount of organic solvent for soaking, washing and removing the slurry is avoided, the process is simplified compared with the existing modification method, and the expanded production is facilitated; the second heat preservation stage promotes the oxidation of the carbon fibers, increases the number of oxygen-containing groups on the surfaces of the carbon fibers, improves the hydrophilicity of the modified biomembrane carrier, has better biocompatibility and is beneficial to improving the efficiency of bioadsorption and fixation; meanwhile, the carbon fibers have certain loss due to burning through the second heat preservation, so that more grooves and defects are generated on the surfaces of the carbon fibers, the roughness of the surfaces of the carbon fibers is improved, the attachment area of organisms is increased, and the fixation growth of a biological film on a modified biological film carrier is facilitated; in addition, the second heat preservation is beneficial to reducing the modulus of the carbon fiber and the deformation of the modified biomembrane carrier under the slight scouring force of water flow, so that the modified biomembrane carrier can be dispersed to a greater extent, more biomembrane carriers are contacted with organisms, the utilization rate of the modified biomembrane carrier is improved, a larger net-shaped biological system is formed, and higher biofilm formation amount can be obtained.
The experimental effect shows that the preparation method of the modified biomembrane carrier provided by the invention can realize the desizing of the carbon fiber without adopting an organic reagent, thereby avoiding the environmental pollution; when the obtained modified biomembrane carrier is used for water treatment, compared with the carbon fiber carrier of other existing modification processes, the modified biomembrane carrier prepared by the invention can obtain higher biological fixation amount in the same time, the biomass of carbon fiber per unit mass of an aerobic unit can reach 10-12 g/g after long-time operation, and the biomass of carbon fiber per unit mass of an anoxic unit can reach 3-5 g/g.
Drawings
FIG. 1 is a photograph showing the biofilm formation of the modified biofilm carriers obtained in example 3 of the present invention for 60 days;
FIG. 2 is an SEM image of a carbon fiber of comparative example 1 of the present invention;
FIG. 3 is an SEM photograph of a modified biofilm carrier obtained in example 1 of the present invention;
FIG. 4 is a photograph showing the biofilm formation of the modified biofilm carrier 72h obtained in example 1 of the present invention;
FIG. 5 is a photograph showing the biofilm formation of the biofilm carrier 72h in comparative example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a modified biological carrier, which comprises the following steps:
sequentially carrying out first heat preservation and second heat preservation on carbon fibers to obtain the modified biological membrane carrier; the temperature of the first heat preservation is 150-250 ℃; the temperature of the second heat preservation is 250-650 ℃.
The carbon fiber is subjected to first heat preservation to obtain the desized carbon fiber.
In the present invention, the carbon fiber preferably includes one or more of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, viscose-based carbon fiber, and lignin-fiber-based carbon fiber. The source of the carbon fiber is not particularly limited in the present invention, and any source known to those skilled in the art may be used, specifically, commercially available. In the present invention, the carbon fiber is preferably a carbon fiber which has not been subjected to surface desizing.
In the present invention, the atmosphere of the first heat preservation is preferably an oxygen-containing atmosphere, specifically, such as air. In the invention, the temperature of the first heat preservation is 150-250 ℃, preferably 170-230 ℃, and more preferably 190-210 ℃; the time is preferably 5 to 15min, more preferably 7 to 13min, and still more preferably 9 to 11min. The first heat preservation temperature is preferably obtained by heating; the heating rate is preferably 5 to 20 ℃/min, more preferably 7 to 17 ℃/min, and still more preferably 10 to 15 ℃/min. In the invention, the resin slurry on the surface of the carbon fiber can be decomposed by the first heat preservation, so that the use of a large amount of organic solvent for soaking, washing and removing the slurry is avoided, the process is simplified compared with the existing modification method, and the expanded production is facilitated.
After the desized carbon fiber is obtained, the modified biomembrane carrier is obtained by carrying out second heat preservation on the desized carbon fiber.
In the present invention, the atmosphere of the second keeping warm is preferably an oxygen-containing atmosphere, specifically, such as air. In the invention, the temperature of the second heat preservation is 250-650 ℃, preferably 270-600 ℃, and more preferably 300-550 ℃; the time is preferably 30 to 180min, more preferably 50 to 160min, and still more preferably 80 to 130min. The second heat preservation temperature is preferably obtained by heating; the heating rate is preferably 5 to 15 ℃/min, more preferably 7 to 13 ℃/min, and still more preferably 9 to 11 ℃/min. In the invention, the second heat preservation can promote the oxidation of the carbon fiber, increase the number of oxygen-containing groups on the surface of the carbon fiber, and improve the hydrophilicity of the modified biomembrane carrier, so that the modified biomembrane carrier has better biocompatibility and is beneficial to improving the efficiency of bioadsorption and fixation; meanwhile, the carbon fibers have certain loss due to burning through the second heat preservation, so that more grooves and defects are generated on the surfaces of the carbon fibers, the roughness of the surfaces of the carbon fibers is improved, the attachment area of organisms is increased, and the fixation growth of a biological film on a modified biological film carrier is facilitated; in addition, the second heat preservation is beneficial to reducing the carbon fiber modulus, the modified biological membrane carrier is beneficial to being deformed under the small scouring force of water flow, the modified biological membrane carrier can be dispersed to a greater degree, more biological membrane carriers are in contact with organisms, the utilization rate of the modified biological membrane carrier is improved, a larger net-shaped biological system is formed, and therefore a higher membrane hanging amount can be obtained.
After the second incubation, the present invention preferably further comprises cooling the resulting product. In the present invention, the cooling is preferably furnace cooling.
The invention also provides the modified biomembrane carrier prepared by the preparation method in the technical scheme. The modified biological membrane carrier provided by the invention has rough surface and obvious defects and stripping.
The invention also provides application of the modified biomembrane carrier prepared by the preparation method in the technical scheme in the field of water treatment.
In the present invention, the modified biofilm carrier is preferably applied to an anoxic unit and/or an aerobic unit of a water treatment process. In the present invention, the packing density of the modified biofilm carrier in the anoxic unit and the aerobic unit is independently preferably 100 to 1000g/m 3 More preferably 200 to 900g/m 3 More preferably 300 to 750g/m 3 . In the present invention, the water flow pattern in the anoxic unit and the aerobic unit is preferably an upward flow water inlet and outlet pattern.
As the preferable application of the invention, the specific application mode of the modified biological membrane carrier in the field of water treatment provided by the invention is as follows:
in the invention, from the water inlet direction to the water outlet direction, the water treatment system comprises a phosphorus removal unit, an anoxic unit and an aerobic unit which are sequentially arranged. The present invention preferably provides flexible combinations of the elements of the treatment system based on water treatment needs. In the invention, when the water to be treated only has biochemical oxygen demand and ammonia nitrogen removal requirement, the treatment system for water treatment preferably comprises an aerobic unit separately; when the water to be treated has the requirements for removing biochemical oxygen demand, ammonia nitrogen and total nitrogen, the treatment system for water treatment preferably comprises an anoxic unit and an aerobic unit; when the water to be treated has the removal requirements of biochemical oxygen demand, ammonia nitrogen, total nitrogen and total phosphorus, the treatment system for water treatment preferably comprises a phosphorus removal unit, an anoxic unit and an aerobic unit.
In the present invention, the flocculating agent in the phosphorus removal unit is preferably an iron containing solution; the mass concentration of the iron-containing solution is preferably 1 to 40%, more preferably 5 to 35%, and still more preferably 10 to 30%. In the invention, the flocculation time of the phosphorus removal unit is preferably 0.2-1 h, more preferably 0.3-0.8 h, and still more preferably 0.4-0.6 h.
In the present invention, the packing density of the modified biofilm carrier in the anoxic unit is preferably 100 to 1000g/m 3 More preferably 200 to 900g/m 3 More preferably 300 to 750g/m 3 . In the present invention, the temperature of the anoxic unit is preferably 20 to 40 ℃, more preferably 23 to 38 ℃, and still more preferably 25 to 35 ℃; the concentration of dissolved oxygen of the anoxic unit is preferably less than or equal to 0.5mg/L, more preferably 0.01-0.45 mg/L, and still more preferably 0.05-0.4 mg/L. In the present invention, the hydraulic retention time in the anoxic unit is preferably 6 to 30 hours, more preferably 7 to 25 hours, and still more preferably 8 to 20 hours. In the invention, the water to be treated preferably flows in and out in an upward direction in the water outlet mode of the anoxic unit.
In the present invention, the packing density of the modified biofilm carriers in the aerobic unit is preferably 100 to 1000g/m 3 More preferably 200 to 900g/m 3 More preferably 300 to 750g/m 3 . In the present invention, the temperature of the aerobic unit is preferably 15 to 35 ℃, more preferably 18 to 32 ℃, still more preferably 20 to 30 ℃. In the present invention, the concentration of dissolved oxygen in the aerobic unit is preferably 2 to 7mg/L, more preferably 3 to 6mg/L. In the present invention, the hydraulic retention time in the aerobic unit is preferably 6 to 30 hours, more preferably 7 to 25 hours, and still more preferably 8 to 20 hours. In the invention, part of effluent obtained by the aerobic unit treatment is preferably refluxed to the anoxic unit, and the reflux ratio of the reflux is preferably 0.5-4. In the invention, the water to be treated preferably flows in and out in an upward direction in the water outlet mode of the aerobic unit.
The water treatment system of the invention does not need to be provided with a water outlet precipitation unit, namely, the treatment system has good SS (suspended solids) removal effect, and can directly discharge water after being treated by the aerobic unit.
The treatment system containing the modified biomembrane carrier provided by the invention has strong adaptability to water quality, and can quickly adapt to working conditions to reach the water quality target; when the device runs stably, the sludge production of the aerobic unit is small, back washing is not needed, and sludge backflow is not needed. The treatment system provided by the invention is used for water treatment, the process is simple and easy to implement, the treatment cost is low, and water can be discharged without precipitation.
In order to further illustrate the present invention, the following examples are given to describe the modified biofilm carriers and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The raw material carbon fiber used in this example was purchased from Jiangsu and was a polyacrylonitrile-based carbon fiber.
Placing the carbon fiber in a high-temperature furnace, heating to 200 ℃ at a heating rate of 10 ℃/min, and preserving heat for 10min at 200 ℃ to obtain desized carbon fiber; and (3) the obtained desized carbon fiber is heated to 350 ℃ at the heating rate of 8 ℃/min without equipment conversion, is kept at 350 ℃ for 3 hours, and is cooled along with the furnace to obtain the modified biomembrane carrier.
Application example 1
The source of the water to be treated in the application example is the confluent domestic sewage of a sewage plant in a certain town of Beijing, and the water quality detection result is as follows: COD 60-130 mg/L, NH 3 -N 10～30mg/L，TN 12～32mg/L，TP 2.5～3.5mg/L，SS 25～45mg/L。
In the water treatment system, the setting and treatment process of each unit is as follows:
a phosphorus removal unit: feCl with the mass concentration of 10% 3 The solution (calculated by Fe) is used as a flocculating agent, and the ratio of the flocculating agent to the water to be treated is 75ppm; after flocculation is carried out for 0.5h, the obtained effluent enters an anoxic unit;
an anoxic unit: the modified biomembrane carrier obtained in example 1 is used for filling, and the filling density is 300g/m 3 Controlling the concentration of dissolved oxygen in the anoxic unit to be less than or equal to 0.5mg/L and the temperature to be 22-30 ℃; an upward flow water inlet and outlet mode is adopted, the hydraulic retention time is 8 hours, and the obtained outlet water enters an aerobic unit;
an aerobic unit: the modified biomembrane carrier obtained in example 1 is used for filling, and the filling density is 350g/m 3 Controlling the concentration of dissolved oxygen in the aerobic unit to be 2-7 mg/L and the temperature to be 22-30 ℃; an upward flow water inlet and outlet mode is adopted, the hydraulic retention time is 8 hours, the obtained water outlet part flows back to the anoxic unit, the reflux ratio is 2.5, and the residual water is directly discharged without precipitation; the treatment system operates stably to obtain the final effluent discharged by the aerobic unit.
COD content detection is carried out according to a dichromate method in HJ828-2017, ammonia nitrogen content detection is carried out according to a Nashin reagent spectrophotometry method in HJ535-2009, total phosphorus content detection is carried out according to an ammonium molybdate spectrophotometry method in GB11893-1989, total nitrogen content detection is carried out according to an alkaline potassium persulfate digestion ultraviolet spectrophotometry method in HJ636-2012, SS content detection is carried out according to a gravimetric method in GB11901-89, and final effluent is detected, wherein the detection results are as follows: COD 15-20 mg/L, NH 3 0.3 to 0.9mg/L of N, 5 to 16mg/L of TN, 0.3 to 0.5mg/L of TP, and 1 to 4mg/L of SS, according to detectionAnd obtaining final effluent which meets the first-grade B water quality requirement.
Application example 2
The source of the water to be treated in the application example is rural domestic sewage in certain places in Guangdong, and the water quality detection result is as follows: COD 70-150 mg/L, NH 3 ～N 10-25mg/L，SS 25-55mg/L。
The sewage is used for crop irrigation after being treated, the total phosphorus and total nitrogen treatment requirement is avoided, and the aerobic unit is applied; in the water treatment system, the setting and treatment process of the aerobic unit is as follows:
an aerobic unit: the modified biomembrane carrier obtained in example 1 is used for filling, and the filling density is 400g/m 3 Controlling the concentration of dissolved oxygen in the aerobic unit to be 2-7 mg/L and the temperature to be 15-35 ℃; an upward flow water inlet and outlet mode is adopted, the hydraulic retention time is 10 hours, and the outlet water is directly discharged without precipitation to obtain the final outlet water.
According to the detection method of the application example 1, the final effluent is detected, and the detection result is as follows: COD<20mg/L，NH 3 -N<0.5mg/L，SS<5mg/L。
Example 2
The raw material carbon fiber used in this example was purchased from Zhejiang and was a polyacrylonitrile-based carbon fiber.
Placing the carbon fiber in a high-temperature furnace, heating to 150 ℃ at the heating rate of 12 ℃/min, and preserving the heat for 15min at the temperature of 150 ℃ to obtain desized carbon fiber; and (3) the obtained desized carbon fiber is heated to 400 ℃ at the heating rate of 10 ℃/min without equipment conversion, is kept at the temperature of 400 ℃ for 2.5 hours, and is cooled along with the furnace to obtain the modified biomembrane carrier.
Application example 3
The source of the water to be treated in the application example is domestic sewage in a certain suburb area of Beijing, and the water quality detection result is as follows: COD 150-300 mg/L, NH 3 -N 20～50mg/L，TN 30～60mg/L，SS 45～100mg/L。
In the water treatment system, the setting and treatment process of each unit is as follows:
an anoxic unit: the modified biomembrane carrier obtained in example 2 is used for filling, and the filling density is 500g/m 3 Controlling the anoxic unitThe concentration of dissolved oxygen in the solution is less than or equal to 0.5mg/L, and the temperature is 18-28 ℃; an upward flow water inlet and outlet mode is adopted, the hydraulic retention time is 12 hours, and the obtained outlet water enters an aerobic unit;
an aerobic unit: the modified biomembrane carrier obtained in example 1 is used for filling, and the filling density is 400g/m 3 Controlling the concentration of dissolved oxygen in the aerobic unit to be 2-7 mg/L and the temperature to be 18-28 ℃; an upward flow water inlet and outlet mode is adopted, the hydraulic retention time is 12 hours, the obtained water outlet part flows back to the anoxic unit, the reflux ratio is 3, and the residual water is directly discharged without precipitation; the treatment system operates stably to obtain the final effluent discharged by the aerobic unit.
According to the detection method of the application example 1, the final effluent is detected, and the detection result is as follows: COD 25-40 mg/L, NH 3 -N 0.5～1mg/L，TN 8～20mg/L，SS 2～6mg/L。
After stable operation for 60 days, the biofilm hanging biomass of the modified biofilm carrier in the aerobic unit in the application example is 9-11 g/1g of the modified biofilm carrier; and taking out the modified biomembrane carrier in the aerobic unit, observing the biofilm-hanging shape of the biomembrane carrier, and observing the picture as shown in figure 1. As can be seen from FIG. 1, after the modified biofilm carrier provided by the invention stably runs for a period of time under appropriate process conditions, only a single fiber bundle can form a thick biofilm, and a large number of zoogloea are attached to form a rich microbial system.
Example 3
The raw carbon fiber used in this example was purchased from Shandong and was pitch-based carbon fiber.
Placing the carbon fiber in a high-temperature furnace, heating to 180 ℃ at a heating rate of 11 ℃/min, and preserving heat for 10min at 180 ℃ to obtain desized carbon fiber; and (3) the obtained desized carbon fiber is heated to 500 ℃ at the heating rate of 9 ℃/min without equipment conversion, is kept at the temperature of 500 ℃ for 1.0h, is cooled along with the furnace, and the modified biomembrane carrier is obtained.
Application example 4
The source of the water to be treated in the application example is the effluent of a septic tank in a certain ecological agricultural park, and the water quality detection result is as follows: COD 100-180 mg/L, NH 3 -N 20～40mg/L，TN25～45mg/L，TP 6～10mg/L，SS 25～50mg/L。
In the water treatment system, the setting and treatment process of each unit is as follows:
an anoxic unit: the modified biomembrane carrier obtained in example 3 is used for filling, and the filling density is 380g/m 3 Controlling the concentration of dissolved oxygen in the anoxic unit to be less than or equal to 0.5mg/L and the temperature to be 18-30 ℃; an upward flow water inlet and outlet mode is adopted, the hydraulic retention time is 12 hours, and the obtained outlet water enters an aerobic unit;
an aerobic unit: the modified biomembrane carrier obtained in example 3 is used for filling, and the filling density is 350g/m 3 Controlling the concentration of dissolved oxygen in the aerobic unit to be 2-7 mg/L and the temperature to be 18-30 ℃; an upward flow water inlet and outlet mode is adopted, the hydraulic retention time is 12 hours, the obtained effluent part flows back to the anoxic unit, the reflux ratio is 2.0, and the residual effluent is directly discharged without precipitation; the treatment system operates stably to obtain the final effluent discharged by the aerobic unit.
According to the detection method of the application example 1, the final effluent is detected, and the detection result is as follows: COD 20-35 mg/L, NH 3 -N0.5～1mg/L，TN10～18mg/L，SS 1～4mg/L。
Comparative example 1
The raw material carbon fiber in example 1 was used as the biofilm carrier of this comparative example.
Comparative example 2
Carrying out a liquid-phase oxidation method on the same raw carbon fiber as that in example 1 to obtain a modified carbon fiber;
wherein, the liquid phase oxidation process comprises the following steps: soaking carbon fibers in ethanol for desizing, cleaning residual organic matters with pure water after desizing, and placing the carbon fibers after desizing in 40wt.% of H 2 SO 4 And (3) reacting the carbon fiber in the solution at 85 ℃ for 2h, taking out the carbon fiber after the reaction is finished, washing the acid liquor with pure water, and drying to obtain the liquid-phase oxidation modified carbon fiber.
Comparative example 3
Carrying out an electrochemical salt method on the same raw carbon fiber as that in the example 1 to obtain a modified carbon fiber;
wherein, the electrochemical salt method processComprises the following steps: soaking carbon fiber in acetone for desizing, and cleaning residual organic matters with pure water after desizing. Taking carbon fiber after pulp removal as an anode and graphite as a cathode, and taking 1.3mol/L (NH) 4 ) 2 HPO 4 And electrolyzing the solution serving as an electrolyte for 120s under the condition of 4V, taking out the carbon fiber after the reaction is finished, washing the carbon fiber with pure water, and drying to obtain the electrochemical salt method modified carbon fiber.
Comparative example 4
Carrying out an electrochemical acid method on the same raw carbon fiber as that in example 1 to obtain a modified carbon fiber;
the electrochemical acid method comprises the following steps: boiling and soaking the carbon fiber for desizing, and cleaning the residual organic matters of the carbon fiber after desizing by using pure water. Taking carbon fiber after pulp removal as an anode and graphite as a cathode, and taking H of 0.5mol/L 2 SO 4 And (3) electrolyzing the solution serving as an electrolyte for 120s under the condition of 4V voltage, taking out the carbon fiber after the reaction is finished, washing the acid liquor with pure water, and drying to obtain the electrochemical acid method modified carbon fiber.
Comparative example 5
Carrying out a non-oxidizing atmosphere modification method on the same raw carbon fiber as that in example 1 to obtain a modified carbon fiber;
wherein, the non-oxidizing atmosphere modification method comprises the following processes: desizing carbon fiber with ethanol, cleaning residual organic matter with pure water, oven drying, placing in an atmosphere furnace, introducing CO 2 Reacting the gas at 750 ℃ for 1h, and taking out the carbon fiber after the reaction is finished and cooled to obtain the non-oxidizing atmosphere modified carbon fiber.
Test example 1
The scanning electron microscope test is carried out on the comparative example 1, and the obtained SEM image is shown in figure 2; the scanning electron microscope test was carried out on example 1, and the SEM image obtained is shown in FIG. 3. As can be seen from fig. 2 and 3, the modified biofilm carrier carbon fiber provided in example 1 has obvious defects and peeling on the surface, and the surface is rougher compared with the unmodified carbon fiber provided in comparative example 1, which is beneficial to biofilm formation.
Test example 2
The modulus of the modified biomembrane carrier obtained in example 1, the carbon fiber obtained in comparative example 1 and the modified carbon fibers obtained in comparative examples 2 to 5 were tested according to the tensile property test method of GB/T3362-2005 carbon fiber multifilament, and the test results are shown in Table 1.
TABLE 1 results of modulus test in example 1 and comparative examples 1 to 5
| Sample (I) | Modulus of elasticity/GPa |
| Example 1 | 54.23 |
| Comparative example 1 | 91.85 |
| Comparative example 2 | 73.52 |
| Comparative example 3 | 87.05 |
| Comparative example 4 | 78.83 |
| Comparative example 5 | / |
As can be seen from table 1, the modified biofilm carriers provided by the present invention have a smaller modulus. The smaller the modulus, the more easy the deformation is under the slight scouring force of water flow, the more dispersed the fiber can be made, and more fiber is contacted with the organism, therefore, the modified biomembrane carrier provided by the invention can obviously improve the utilization rate of the carbon fiber, form a larger net-shaped biological system, and obtain higher biofilm formation amount; in addition, the lower modulus is favorable for the carbon fiber to present better flow state under the rivers disturbance, and the biomembrane is difficult to be washed away by rivers, and biomembrane fastness degree is better.
Test example 3
And (3) performing a biofilm formation test on the modified biomembrane carrier obtained in the example 1, the carbon fiber obtained in the comparative example 1 and the modified carbon fibers obtained in the comparative examples 2-5, wherein the specific experimental conditions of the biofilm formation test are as follows: 0.5g/L of activated sludge, prepared COD 300mg/L, NH 3 Hanging the membrane in 0.8L solution of-N10 mg/L, TP mg/L, controlling the dissolved oxygen to be 2-4mg/L, taking out after 72h, calculating the membrane hanging biomass, and showing the membrane hanging test result in table 2.
TABLE 2 results of the biofilm formation test in example 1 and comparative examples 1 to 5
| Sample (I) | Biofilm formation amount g biomass/1 g carrier |
| Example 1 | 0.51 |
| Comparative example 1 | 0.17 |
| Comparative example 2 | 0.38 |
| Comparative example 3 | 0.28 |
| Comparative example 4 | 0.30 |
| Comparative example 5 | 0.25 |
As can be seen from Table 2, the modified biofilm carrier provided by the invention has the optimal biofilm formation effect.
Taking out the modified biomembrane carrier obtained after 72h of biofilm formation test of the modified biomembrane carrier obtained in the example 1, observing the biofilm formation of the biomembrane carrier, and the observation photo is shown in figure 4; the carrier obtained after 72h of biofilm formation test of the carbon fiber in the comparative example 1 is taken out, the biofilm formation is observed, and the observation picture is shown in figure 5. As can be seen from fig. 4 and 5, the modified biofilm carrier fiber provided by the present invention is more easily dispersed in water, and compared with the bulk form of the unmodified carbon fiber, the modified biofilm carrier provided by the present invention has a significant hypha form, and therefore, has a higher biofilm formation amount.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The preparation method of the modified biomembrane carrier is characterized by comprising the following steps:
sequentially carrying out first heat preservation and second heat preservation on carbon fibers to obtain the modified biological membrane carrier;
the temperature of the first heat preservation is 150-250 ℃; the temperature of the second heat preservation is 250-650 ℃;
and the atmosphere of the first heat preservation and the second heat preservation is oxygen-containing atmosphere.
2. The method of claim 1, wherein the carbon fibers comprise one or more of polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, viscose-based carbon fibers, and lignin-fiber-based carbon fibers.
3. The method according to claim 1, wherein the first temperature is maintained for 5 to 15min.
4. The method according to claim 1, wherein the second temperature is maintained for 30 to 180min.
5. The modified biofilm carrier prepared by the preparation method of any one of claims 1 to 4.
6. Use of the modified biofilm carrier of claim 5 in the field of water treatment.
7. The use according to claim 6, wherein the modified biofilm carrier is used in an anoxic and/or aerobic unit of a water treatment process.
8. The use according to claim 7, wherein the modified biofilm carriers independently have a packing density of 100 to 1000g/m in the anoxic and aerobic units 3 。
9. Use according to claim 7 or 8, wherein the water flow pattern in the anoxic and aerobic units is an upward flow in and out water pattern.
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| CN101544449A (en) * | 2009-05-14 | 2009-09-30 | 北京化工大学 | Application of carbon-fiber biofilm carrier in wastewater treatment |
| CN103058356A (en) * | 2012-12-06 | 2013-04-24 | 武汉环天禹生物环保科技有限公司 | Method of surface modification for environmentally-friendly carbon fibers |
| CN104437376A (en) * | 2014-11-27 | 2015-03-25 | 环境保护部南京环境科学研究所 | Activated carbon fiber modification method, water treatment filter device and application of water treatment filter device |
| CN104803471A (en) * | 2015-04-14 | 2015-07-29 | 北京化工大学常州先进材料研究院 | Excellent and efficient carbon fiber biofilm carrier modification method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101544449A (en) * | 2009-05-14 | 2009-09-30 | 北京化工大学 | Application of carbon-fiber biofilm carrier in wastewater treatment |
| CN103058356A (en) * | 2012-12-06 | 2013-04-24 | 武汉环天禹生物环保科技有限公司 | Method of surface modification for environmentally-friendly carbon fibers |
| CN104437376A (en) * | 2014-11-27 | 2015-03-25 | 环境保护部南京环境科学研究所 | Activated carbon fiber modification method, water treatment filter device and application of water treatment filter device |
| CN104803471A (en) * | 2015-04-14 | 2015-07-29 | 北京化工大学常州先进材料研究院 | Excellent and efficient carbon fiber biofilm carrier modification method |
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