CN110540284B

CN110540284B - Photocatalytic coupling microorganism water body restoration device and preparation method of sponge carrier

Info

Publication number: CN110540284B
Application number: CN201910840121.XA
Authority: CN
Inventors: 俞亚楠; 张焕军; 李轶; 刘哲豪; 杨柳
Original assignee: Hohai University HHU
Current assignee: Hohai University HHU
Priority date: 2019-09-06
Filing date: 2019-09-06
Publication date: 2021-09-07
Anticipated expiration: 2039-09-06
Also published as: CN110540284A

Abstract

The invention discloses a photocatalytic coupling microorganism water body restoration device and a preparation method of a sponge carrier. The device applies the photocatalysis coupling microbiological method to the in-situ restoration of the water body, effectively combines the advantages of photocatalysis and biodegradation of pollutants, has reasonable structural design, can adjust the height along with the change of the water level, is easy to install, and is an economic, energy-saving, environment-friendly and convenient water body restoration device.

Description

Photocatalytic coupling microorganism water body restoration device and preparation method of sponge carrier

Technical Field

The invention relates to the technical field of water environment protection and water ecological restoration, in particular to a photocatalytic coupling microorganism water restoration device and a preparation method of a sponge carrier.

Background

With the continuous deepening of industrialization, environmental problems are increasingly prominent, and the healthy development of human society is seriously hindered, wherein the problem of water pollution is particularly serious. Generally, pollutants in water are mainly removed by conventional physical, physicochemical, biochemical and membrane methods. The traditional physical treatment process comprises a screening method, a precipitation method, a filtration method, a floating method, an air floatation method and the like, but the treatment method mainly removes suspended solid pollutants in the sewage and only can complete pretreatment in sewage treatment. The traditional physical and chemical treatment methods comprise neutralization, coagulation, extraction, electrolysis, oxidation reduction, ion exchange and the like, the treatment cost is high, and the added chemical reagent is easy to cause secondary pollution. The membrane methods used for separation, concentration and purification include microfiltration, ultrafiltration, nanofiltration, reverse osmosis, electrodialysis and the like, and the membrane component has high manufacturing cost, easy pollution and high energy consumption for system operation. Biochemical treatment methods such as an activated sludge method and a biofilm method are also one of the methods for effectively removing pollutants in water, but have certain limitations on water environment restoration due to insufficient stability, long time consumption, complex operation and management and even risk of causing pathogenic bacteria transmission.

The method for synchronously degrading pollutants by coupling photocatalysis with microorganisms as a novel sewage purification method can integrate the advantages of photocatalysis and biodegradation, has important application prospect, and is not applied to in-situ remediation of water. The microorganism and the photocatalytic material are loaded on the same carrier, so that the photocatalytic coupling biological membrane can degrade pollutants in the same reactor. The photocatalysis material outside the photocatalysis coupling microorganism carrier is excited by light, and the electron jumps to a conduction band, and the electron generated on the photocatalysis material can be transferred to the microorganism attached to the carrier due to the close coupling of the photocatalysis material and the microorganism in the system. Therefore, the microorganism and the photocatalysis close coupling system are utilized to reduce the pollutants in the water, the characteristics of photocatalysis and microorganism can be effectively combined, the photocatalysis efficiency is improved, the capability of degrading the pollutants by the microorganism is promoted, the integral purification and restoration effect is improved, and the method is a green, effective and safe water body restoration method.

Disclosure of Invention

Aiming at the defects of the traditional water body remediation method, the invention provides a device for performing water body remediation by using a method for synchronously degrading pollutants by using photocatalysis coupling microorganisms and a preparation method of a sponge carrier, which effectively combine the characteristics of photocatalysis and microorganisms, improve the photocatalysis efficiency, and promote the pollutant degrading capability of the microorganisms, thereby improving the overall purification and remediation effect.

The invention adopts the following technical scheme:

the utility model provides a little biological water prosthetic devices of photocatalysis coupling, includes bottom anchor assembly and a plurality of telescopic link, the detachable connection in telescopic link bottom is on bottom anchor assembly, and the sponge carrier is passed through the spring catch and is connected at the telescopic link top, and photocatalyst and microbial film are carried to the sponge carrier.

The device can be directly installed in water or used in cooperation with aeration equipment, an ecological floating bed and other devices, and is used for water body restoration.

Preferably, a plurality of threaded holes are formed in the bottom anchoring part, threads are machined at the bottom of each telescopic rod, and the bottom of each telescopic rod is in threaded connection with the threaded hole of the bottom anchoring part.

The sponge carriers are in strip shapes, and the strip-shaped sponge carriers are bound into a bundle shape through the soft ropes, tied on the spring buckles and connected with the telescopic rods through the spring buckles.

When the repairing device is placed under water, the sponge carrier is placed to be 5-10 cm below the water surface. The device can be directly installed in water or used in cooperation with aeration equipment, an ecological floating bed and other devices, and is used for water body restoration. The bundled sponge carriers are placed 5-10 cm below the water surface, and the number of the strip-shaped sponges is configured according to 5-20% of the area of the water body to be treated.

The preparation method of the sponge carrier loaded with the photocatalyst and the microbial film comprises the following steps:

step (1), preparing a photocatalyst; g-C₃N₄The material is prepared by burning dicyanodiamine in a muffle furnace for 2 hours at 550 ℃ under atmospheric pressure; after calcining, naturally cooling the sample to room temperature, taking out the sample from the furnace, and grinding the obtained yellow sample into powder in a mortar; 1g of TiO₂Dissolving in 50ml deionized water, adding 2g g-C₃N₄Stirring for 16h by using a magnetic stirrer; after stirring, drying the mixture at the temperature of 60 ℃, putting the dried sample into a muffle furnace, calcining for 1h to 450 ℃ under the atmospheric pressure condition, and raising the temperature at the rate of 15 ℃/min; after calcining and sintering, naturally cooling to room temperature, and grinding the obtained sample into powder;

step (2) adding TiO₂/g-C₃N₄Loading the composite material on a sponge carrier;

preparing a strip sponge carrier: cutting a polyurethane sponge with a porosity of 95 percent and a pore diameter of 100-300 mu m into strip-shaped sponges with the size of 25-30 cm multiplied by 3 cm;

20g of TiO₂/g-C₃N₄The powder was dissolved in a pure ethanol solution, and then 20mL of concentrated nitric acid was added. After 30min of ultrasonic vibration, adding the strip sponge, and then performing 30min of ultrasonic vibration; then, the mixture is put into an oven at 60 ℃ and stirred once every 30min until the liquid is fullPartial evaporation and concentration; finally, the unsupported TiO is₂/g-C₃N₄Removing powder, carrying out ultrasonic vibration on the loaded sponge carrier for 5min, and then washing with deionized water for 3 times;

and (3) culturing the biological membrane: and subpackaging the sponge carrier loaded with the material into a gauze, placing the sealed gauze into a frame convenient to fix, placing the gauze into a black and odorous river, and fixing the gauze at a position about 20cm below the water surface for in-situ culture for 90 days.

The invention has the beneficial effects that:

the device applies the photocatalysis coupling microbiological method to the in-situ restoration of the water body, effectively combines the advantages of photocatalysis and biodegradation of pollutants, has reasonable structural design, can adjust the height along with the change of the water level, is easy to install, and is an economic, energy-saving, environment-friendly and convenient water body restoration device.

Drawings

FIG. 1 is a schematic structural diagram of a photocatalytic coupling microorganism water restoration device according to the present invention;

FIG. 2 is an SEM image of an unsupported material sponge;

FIG. 3 is an SEM image of a sponge supporting a photocatalytic material;

FIG. 4 is an SEM image of a coupled biofilm sponge loaded with photocatalytic material;

FIG. 5 shows NO in water used in the experiment₃ ^-、NH₄ ⁺、Zn²⁺And Cu²⁺The change curve of (2).

Detailed Description

The device is further described with reference to the accompanying drawings and the detailed description. Example 1 is a process for preparing a sponge carrier material which plays a major repairing role in the present invention. Example 2 is a configuration and a specific application example of the present apparatus. Example 3 is an experimental example of the present apparatus.

Example 1

The preparation method of the sponge carrier (1) loaded with the photocatalyst and the microbial film comprises the following steps:

the photocatalyst in the step (1) is prepared according to the following proportion:

g-C₃N₄the preparation of (1): the g to C₃N₄The material is obtained by burning dicyandiamide in a muffle furnace for 2 hours at 550 ℃ and atmospheric pressure. After calcination, the sample was naturally cooled to room temperature and then taken out of the furnace, and the obtained yellow sample was ground into powder in a mortar.

TiO₂/g-C₃N₄The composite photocatalytic material is prepared according to the following proportion: 1g of TiO₂Dissolved in 50mL of deionized water, and 2g g-C was added₃N₄And stirring for 16h by using a magnetic stirrer. And after stirring, drying the mixture at the temperature of 60 ℃, putting the dried sample into a muffle furnace, calcining for 1h to 450 ℃ under the atmospheric pressure, and raising the temperature at the rate of 15 ℃/min. After the calcining and sintering, the sample is ground into powder after being naturally cooled to the room temperature.

TiO obtained in the step (2)₂/g-C₃N₄The composite material is loaded on the strip sponge according to the following proportion:

preparing a strip sponge carrier: the sponge with the porosity of 95% and the pore diameter of 100-300 mu m is cut into strips with the size of about 25-30 cm multiplied by 3cm, and an SEM image of the sponge without the loaded composite photocatalytic material is shown in an attached figure 2.

20g of TiO₂/g-C₃N₄The powder was dissolved in a pure ethanol solution, and then 20mL of concentrated nitric acid was added. And after 30min of ultrasonic vibration, adding the strip sponge, and then performing 30min of ultrasonic vibration. Then, the mixture was put into a furnace at 60 ℃ and stirred every 30min until the liquid was evaporated and concentrated. Finally, the unsupported TiO is₂/g-C₃N₄The powder was removed, the loaded sponge carrier was subjected to ultrasonic vibration for another 5min, and then washed 3 times with deionized water, and the SEM image of the loaded photocatalytic material sponge is shown in fig. 3.

And (3) culturing the biological membrane:

the sponge carrier loaded with the material is subpackaged into a gauze, the sealed gauze is placed into a frame convenient to fix and is placed into a black and odorous river, the frame is fixed at a position about 20cm below the water surface for in-situ culture for 90 days, and an SEM image of the sponge loaded with the photocatalytic material and coupled with the biological membrane is shown in figure 4.

Example 2

A photocatalysis coupling microorganism water body restoration device comprises a sponge carrier 1, a spring fastener 2, a soft rope 3, a telescopic rod 4, a screw fastener 5 and a bottom anchoring part 6. Bottom anchor assembly 6 is connected with sponge carrier 1 through

telescopic link

4, and 6 threaded recesses of evenly distributed on the anchor assembly of bottom are two rows of three columns distribution. The bottom of the telescopic rod 4 is provided with a screw rod fastener 5 matched with the thread so as to be fixed on a bottom anchoring piece 6. The height of the telescopic rod can be adjusted at will, and the telescopic rod can change along with the change of the river water level, so that the illumination condition of the photocatalytic material is met. The upper end of the telescopic rod 4 is evenly provided with a plurality of holes, and the spring buckle 2 can be hung at each hole. The sponge carrier is strip-shaped, a photocatalytic material and a biological membrane are loaded on the sponge carrier, 8 sponges are bound into a bundle shape through a soft rope 3, and the sponge carrier is tied on a spring buckle 2 and connected with a telescopic rod 4 through the spring buckle.

In the embodiment, the bottom anchoring part is of a cuboid structure, the length of the bottom anchoring part is 50-80 cm, the width of the bottom anchoring part is 40-50 cm, 6 threaded circular grooves are uniformly distributed in the upper part of the bottom anchoring part, the diameter of each groove is 6cm, the grooves are arranged in two rows and three columns, and a group is formed.

In this embodiment the telescopic link bottom have with screw thread assorted screw rod fastener, its diameter 6cm is unanimous with the recess diameter to fix on bottom anchor assembly, upper end evenly distributed has 4 apertures, and the aperture is about 1 ~ 2cm, and every aperture department can supply the snak link to hang.

The spring fastener is provided with a spring switch, is convenient to hang and is not easy to fall off, can be hung at small holes uniformly distributed at the upper end of the telescopic rod, and can tie the bundled sponge on the spring fastener through a soft rope.

The device can be directly installed in water or used in cooperation with aeration equipment, an ecological floating bed and other devices, and is used for water body restoration. The bundled sponge carriers are placed 5-10 cm below the water surface, and the number of the strip-shaped sponges is configured according to 5-20% of the area of the water body to be treated.

Experimental example 3

Connecting the telescopic rod with the bottom anchoring partForming a complete photocatalysis coupling microorganism water body restoration device. The device is placed in a rectangular water tank of a laboratory, a water collecting tank is arranged at the left end of the device to supply water for the water tank, and a water suction pump is arranged at the right end of the device to pump the water flowing out of the rectangular water tank back to the water collecting tank at the left side, so that a circulating system is formed. The upper part of the rectangular water tank is provided with a light source system to meet the illumination condition of the photocatalytic material. Collecting a water sample of the Jinchuan river in Nanjing, pouring the water sample into the rectangular water tank and the left water collecting tank, and adjusting the height of the sponge carrier through the telescopic rod to enable the sponge carrier to be located 5-10 cm below the water surface. And (3) taking an original water sample for detection before the experiment begins, and recording initial data. And then, turning on a water pump to circulate the water sample, and sampling and analyzing the water in the water tank every 4 hours for four times. NO in water for experiment₃ ^-、NH₄ ⁺、Zn²⁺And Cu²⁺The change curve is shown in figure 5, and the experimental result shows that the device has particularly obvious effect of removing nitrate, and NO is in a rectangular water tank₃ ^-The front and back concentrations are respectively 18.42mg/L and 10.11mg/L, the heavy metal ion can be removed to a certain extent, and Zn is²⁺And Cu²⁺The concentrations before the experiment were 3.82mg/L and 0.85mg/L, respectively, and the concentrations after the experiment were 2.19mg/L and 0.18mg/L, respectively.

The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. The non-illustrated parts referred to in the present invention are the same as or implemented by the prior art.

Claims

1. The utility model provides a little biological water prosthetic devices of photocatalysis coupling which characterized in that: the device comprises a bottom anchoring part and a plurality of telescopic rods, wherein a plurality of threaded holes are formed in the bottom anchoring part, threads are machined at the bottom of each telescopic rod, the bottom of each telescopic rod is connected in the threaded hole of the bottom anchoring part in a threaded manner, the top of each telescopic rod is connected with a sponge carrier through a spring buckle, and a photocatalyst and a microbial film are carried on the sponge carrier; the sponge carriers are in strip shapes, and a plurality of strip-shaped sponge carriers are bound into a bundle shape through soft ropes, tied on the spring buckles and connected with the telescopic rods through the spring buckles; when the repairing device is placed under water, the sponge carrier is placed to be 5-10 cm below the water surface;

step (1), preparing a photocatalyst; g-C₃N₄The material is prepared by burning dicyanodiamine in a muffle furnace for 2 hours at 550 ℃ under atmospheric pressure; after calcining, naturally cooling the sample to room temperature, taking out the sample from the furnace, and grinding the obtained yellow sample into powder in a mortar; 1g of TiO₂Dissolving in 50ml of deionized water, adding 2 gg-C₃N₄Stirring for 16h by using a magnetic stirrer; after stirring, drying the mixture at the temperature of 60 ℃, putting the dried sample into a muffle furnace, calcining for 1h to 450 ℃ under the atmospheric pressure condition, and raising the temperature at the rate of 15 ℃/min; after calcining and sintering, naturally cooling to room temperature, and grinding the obtained sample into powder;

preparing a strip sponge carrier: cutting a polyurethane sponge with the porosity of 95 percent and the pore diameter of 100-300 mu m into strip-shaped sponges with the size of 25-30 cm multiplied by 3 cm;

20g of TiO₂/g-C₃N₄Dissolving the powder into a pure ethanol solution, adding 20mL of concentrated nitric acid, performing ultrasonic vibration for 30min, adding the strip sponge, and performing ultrasonic vibration for 30 min; then, the mixture after ultrasonic vibration is placed in an oven at 60 ℃, and is stirred once every 30min until all the liquid is evaporated and concentrated; finally, the unsupported TiO is₂/g-C₃N₄Removing powder, carrying out ultrasonic vibration on the loaded sponge carrier for 5min, and then washing with deionized water for 3 times;

and (3) culturing the biological membrane: and (3) subpackaging the sponge carrier loaded with the material into a gauze, putting the sealed gauze into a frame convenient to fix, putting the gauze into a black and odorous river, and fixing the gauze at a position 20cm below the water surface for in-situ culture for 90 days.