CN111359435A - Graphene-based photocatalytic bioreactor for sterilization and ammonia removal of farm - Google Patents
Graphene-based photocatalytic bioreactor for sterilization and ammonia removal of farm Download PDFInfo
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- CN111359435A CN111359435A CN202010362487.3A CN202010362487A CN111359435A CN 111359435 A CN111359435 A CN 111359435A CN 202010362487 A CN202010362487 A CN 202010362487A CN 111359435 A CN111359435 A CN 111359435A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
- A61L9/18—Radiation
- A61L9/20—Ultraviolet radiation
- A61L9/205—Ultraviolet radiation using a photocatalyst or photosensitiser
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
- A61L2209/10—Apparatus features
- A61L2209/11—Apparatus for controlling air treatment
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
- A61L2209/10—Apparatus features
- A61L2209/14—Filtering means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B01D2257/00—Components to be removed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0266—Other waste gases from animal farms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to a graphene-based photocatalytic bioreactor for sterilizing and removing ammonia in a farm, which comprises a reactor box body, and an air filtering component, a composite ultraviolet component and a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier which are arranged in the reactor box body; the reactor box body is a box body with openings at the left end and the right end, and the left air inlet and the right air outlet are arranged; the reactor box body is characterized in that a plurality of concave mounting grooves are formed in the inner wall of the reactor box body, and a first-stage air filtering component, a composite ultraviolet light source component, a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier and a second-stage air filtering component are sequentially mounted from left to right. Selection of UV185‑254nmVacuum ultraviolet lamp and UVC254nmUltraviolet lamp, self-made LedUV365nm‑400nmAn ultraviolet lamp as a composite light source of the photocatalytic bioreactor; preparing a Mn type Graphene-based nano titanium dioxide photocatalytic reaction carrier, wherein the composite material comprises 40 wt% of C, 30 wt% of Graphene and MnOX20%、TiO210 percent. The test result proves that: the activity of the photocatalyst for degrading pollutants is obviously superior to that of a pure semiconductor by 40 percent.
Description
Technical Field
The invention relates to the technical field of sterilization and ammonia removal of medium-scale farms, in particular to a graphene-based photocatalytic bioreactor for sterilization and ammonia removal of farms.
Background
Two major problems facing livestock farms are: biological pollution and environmental protection. The regulations on pollution prevention and control of livestock and poultry scale breeding, which are implemented in 1 month and 1 day in 2014, make relevant legal provisions on pollution prevention and control of livestock and poultry breeding. At present, a certain part of livestock and poultry farms adopt a relatively extensive management mode, after malodorous gases, dust, microorganisms and the like generated by the livestock and poultry farms are discharged into the atmosphere, the malodorous gases, the dust, the microorganisms and the like are diffused and diluted by atmospheric air flow and absorbed by ground vegetation and soil, so that the environment is damaged, and meanwhile, complaints of 'malodor disturbs people' are continuous, so that the construction of a harmonious society is influenced.
Microbial contamination: in the interior of a chicken farm, chicken bodies are pollution sources, pathogenic bacteria can survive in soil, excrement and dust for a plurality of months, and a large amount of viruses and microorganisms are exposed in the air and continuously reproduce to cause serious pollution to the chicken house. Chicken escherichia coli is a common opportunistic pathogen and is directly present in chickens, so that pathogenic bacteria multiply in chickens to cause disease. In recent years, the colibacillosis of chickens is continuously spread and diffused in chicken farms, the morbidity and the mortality are high, and in addition, the colibacillosis is easy to generate drug resistance, so that the treatment cost is increased, and huge economic loss is caused to farmers.
Among the gaseous pollutants in the farm, ammonia gas is the most harmful to livestock and poultry, and hydrogen sulfide gas is the most toxic. The ammonia gas is mainly generated by decomposing ammonia-containing organic matters such as excrement, feed and the like. Ammonia gas stimulates respiratory tract mucous membrane to destroy its protective action, so that animals and human are susceptible to various respiratory tract diseases, the disease resistance of animal organisms is reduced, respiratory tract inflammation is caused, and pulmonary edema is caused seriously.
The ecological environment of a farm must be improved to realize the continuous development of animal husbandry, the source control of biological pollution and environmental pollution is enhanced, and the win-win situation of the development of animal husbandry and environmental protection is realized.
The prior sterilization technology at home and abroad and the existing problems are as follows: the methods currently used in the world for sterilization are mainly ozone methods or ultraviolet methods. TiO22The photocatalysis technology is a new environmental management technology and becomes a green technology and an environment-friendly technology. With nano TiO2Processes for the catalytic oxidation of gaseous pollutants for catalysts have received extensive attention in the last 10 years. Halogenated aliphatic hydrocarbon, halogenated aromatic hydrocarbon, organic acid, dye, nitrohydrocarbon, substituted aniline, polycyclic aromatic hydrocarbon, heterocyclic compound, amine, hydrocarbon, phenol, surfactant, pesticide and the like can be found to effectively carry out photocatalytic reaction, detoxify and decolor, generate inorganic micromolecule substances and finally eliminate the pollution to the environment. TiO22An important aspect of the application of photocatalytic degradation of organic pollutants is TiO2And (5) carrying out photocatalytic sterilization. TiO22The photocatalyst can not only kill bacteria, but also decompose toxic compounds released by the bacteria. I.e. TiO2The photocatalyst not only can reduce the vitality of bacteria, but also can attack bacteria and outer cells. Penetrate cell membrane and destroy cell membrane structure, so as to kill bacteria thoroughly and has important effect on decomposing and eliminating microbial residue.
In China, the main methods for disinfection and disease control mainly depend on chemical disinfectants and antibiotics, and for ammonia gas removal include a water curtain method, activated carbon adsorption and a photo-oxidation technology based on activated carbon adsorption.
Problems with photocatalytic bioreactors: the photocatalytic reactor can be classified into an artificial light source such as ultraviolet light and a natural light source such as a solar photocatalytic reactor according to the difference of the light source. Ubiquitous: the utilization rate of natural visible light is low, and the catalytic oxidation efficiency is low due to the limitation of ultraviolet light sources. Foreign studies have shown that photocatalytic bioreactors with various light source configurations have been used to photodegrade organic pollutants with some success and experience.
With the continuous development and research of high-efficiency multifunctional integrated photocatalytic reactors, photocatalytic bioreactors have become multifunctional integrated high-efficiency purification devices for sterilizing and killing viruses, eliminating pathogens and residual toxins of organic pollutants, degrading ammonia gas and the like.
The inhibition performance of graphene on bacterial viruses: graphene is a nano material with antibacterial property and good biocompatibility, and can destroy cell membranes through contact cutting effect and also can destroy cell membranes and kill bacteria through large-scale direct extraction of phospholipid molecules on the cell membranes.
The research shows that: the graphene and the derivatives thereof have excellent antibacterial performance when acted with bacteria, and only have weak cytotoxicity when acted with cells or organisms. Graphene is also an ideal carrier of antibacterial active substances, and has great potential in developing novel antibacterial materials.
The adsorption performance of graphene on ammonia gas is as follows: the first study on the adsorption properties of graphene was by Schedin et al, who found that graphene was resistant to NH3、NO2CO and H2O has strong adsorbability, and graphene can be desorbed by adopting ultraviolet irradiation; they also performed multiple adsorption and desorption experiments to confirm that graphene was not poisoned. Huang et al simulated the intrinsic graphene pair of CO and O by using a method based on the first type principle of density functional2、N2、NO、NO2、CO2And NH3The research shows that the graphene only acts on NH3Has stronger adsorbability.
Spongy graphene prepared from Chinese academy of sciences metal and capable of reacting with NH3Has very strong adsorbability.
Although intrinsic graphene has very high electron mobility and a large specific surface area, intrinsic graphene can only exhibit strong adsorption performance to a very small number of molecules and atoms due to limitations of its structure and chemical properties. Therefore, vacancy graphene and doped graphene are the main research directions for the adsorption performance of graphene, and meanwhile, in practical application, an effective method for desorption at normal temperature needs to be solved.
Nano TiO22Photocatalytic pair of NH3Removing effect: in recent years, scholars at home and abroad will use nano TiO2Introduction of photocatalytic technology into animal husbandry field for NH3The purification is carried out, the effect is ideal and no secondary pollution is caused. Nano TiO22The principle of the photocatalysis technology is TiO2The surface is irradiated by UV ultraviolet light to generate electron-hole pairs, and high-activity OH free radicals, NH3Contact TiO2A series of oxidation-reduction reactions can occur on the surface and degrade into H2O、N2And the like; the technology is used for the first time in a pigsty by the veterinarian system Guarno and the like of Milan university in Italy in 2008, the effect is good, Costa and the like treat ammonia gas in the pigsty by the same method, and Xuxin and the like develop chicken coop air purification equipment by adopting activated carbon adsorption, photocatalysis and ozone coupling technologies. But these techniques are very inefficient in photocatalytic oxidation.
The root cause of low efficiency of traditional photocatalytic oxidation is as follows:
no. 1, the wavelength and the illumination of the light source are not matched with the response range of the catalyst. Nano TiO22The light wave below 387nm is received, the domestic vacuum ultraviolet lamp can only achieve 254nm power at present, Philips can achieve 365nm, but the light power is insufficient, the requirement of photocatalysis illumination cannot be met, and therefore the photoelectric conversion efficiency is low.
No. 2, the catalyst carrier material has no adsorbability and can not enrich pollutants. Although the activated carbon has a certain pollutant enrichment effect by taking the activated carbon as an adsorption carrier, the activated carbon has a large resistance value, a carrier drift speed is low, and an electron-hole pair recombination probability is accelerated, so that the oxidation-reduction reaction efficiency is low directly. Meanwhile, the activated carbon has low effectiveness of adsorbing microorganisms. The treatment efficiency in the actual engineering is about 50%.
Photocatalytic bioreactors have urgently needed to solve the core problems: TiO22The photocatalytic oxidation is applied to the water pollution treatment, but few photocatalytic bioreactors are involved. At present, the research is mainly carried out in the countries such as the United states, Canada, Spain and the like, and the design and the manufacture of the high-efficiency photocatalytic bioreactor carry out the degradation of pollution by solar light and artificial light on a certain scaleThe important links of things. Foreign studies have shown that photocatalytic reactors with various wavelength light source structures have been used in research on photodegradation of organic wastes and actual wastewater treatment, and have achieved some success and experience. In order to improve the photocatalytic efficiency of a photocatalytic bioreactor, the key point of applying a photocatalytic technology to large-scale industrial production is to research the light source system, the reactor structure, the catalyst photosensitivity and other aspects.
Disclosure of Invention
Based on the antibacterial and bacteriostatic performance of graphene, the unique adsorption efficiency on ammonia gas and the excellent conductivity of graphene, the problem of accumulation of excited electrons on the surface of a photocatalyst in a photocatalytic reaction is better solved through a forming method of a graphene-based composite material, the excited electron-hole composite reaction is effectively inhibited, the forbidden bandwidth is reduced to a certain extent, the fermi level relative position of the photocatalytic material is changed, the relative positions of a conduction band and a valence band of the photocatalytic material are indirectly adjusted, and the application range of the photocatalytic material in the catalytic reaction is expanded. Through typical tests, prototype tests and field trials, on the basis of continuous summarization and adjustment, the designed photocatalytic bioreactor is a high-efficiency purification device integrating multiple functions of sterilization, virus killing, pathogen elimination, gaseous pollutants, residual toxins and the like. In order to prevent the transmission and diffusion of pathogens, prevent the outbreak of animal diseases, reduce various chemical disinfectants (especially antibiotic medicines) and maintain the ecological balance of beneficial microbial communities.
The graphene-based photocatalytic bioreactor for sterilizing and removing ammonia in a farm comprises a reactor box body, and an air filtering component, a composite ultraviolet component and a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier which are arranged in the reactor box body; the reactor box body is a box body with openings at the left end and the right end, an air inlet is arranged at the opening at the left end, and an air outlet is arranged at the opening at the right end; the reactor box body is characterized in that a plurality of concave mounting grooves are formed in the inner wall of the reactor box body, and a first-stage air filtering component, a composite ultraviolet light source component, a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier and a second-stage air filtering component are sequentially mounted from left to right.
The first-stage air filtering component is assembled in the metal frame after being overlapped by the primary filter cotton and the medium-density non-woven fabric, and metal protecting nets are arranged on the surfaces of two sides of the frame.
The second-stage air filtering component is assembled in the metal frame after the primary-effect non-woven fabric and the medium-density non-woven fabric are stacked, and metal protective nets are arranged on the surfaces of two sides of the metal frame.
Plant's sterilization removes ammonia graphite alkene base photocatalysis bioreactor, still includes external control box, inside ECU control module that sets up of control box and by its connection control's button, display and on-off control circuit, button and display setting are on the panel of control box, through control button input control signal, show running state through the display.
The switch control circuit is connected with a composite ultraviolet light source component power supply in the reactor box body through a circuit, controls the switch and automatically executes power-off protection and overload protection.
The front of box is provided with the chamber door of switch, conveniently opens each part of installation, maintenance box internally mounted. The bottom of the box body is provided with the roller, so that the box body can be conveniently moved in a field.
The composite ultraviolet light source component comprises a deep ultraviolet vacuum ultraviolet lamp, a UVC, a UVB wave band vacuum ultraviolet lamp and a UVled ultraviolet lamp, and the ultraviolet wavelength range is finally determined through multiple tests to be as follows: 185nm-254nm, 254nm and 365nm-400 nm. By vacuum UV lamps185nm-254nm、UVC254nmAnd Leduv365nm-400nmThe ultraviolet lamps are arranged side by side and fixedly assembled in the metal frame.
The Mn-containing Graphene-based nano titanium dioxide photocatalytic carrier is prepared from Graphene/MnOX/TiO2The composite material is made into a plate structure and fixedly assembled in a metal frame, wherein Graphene/MnO isX/TiO2The raw materials of the composite material comprise 40% of C, 30% of Graphene and MnO according to the weight ratioX20%、TiO 210 percent. The core function of the graphene is as follows: when TiO is present2After photon energy is absorbed, valence band electrons are excited to transit to a conduction band, and the excited electrons flow into a graphene lamellar structure, just because graphene has excellent propertiesGood conductivity, the excited electrons will not gather around the photocatalytic material, and the experiment verifies: graphene and TiO2The most important synergistic effect is that in the photoelectric conversion and photocatalytic pollutant degradation processes, the photoproduction electron-hole separation of the semiconductor is promoted, so that the recombination probability of holes and electrons is reduced. The interaction between graphene and Ti-O-C chemical bond changes TiO2Original forbidden band width, TiO2Shows greater photochemical activity in the visible region, thereby increasing TiO2The utilization rate of visible light. Experiments also find that the graphene lamellar structure has huge specific surface area and conjugated structure, can adsorb a large amount of pollutants, provides an ideal reaction site for photocatalytic reaction, and is favorable for improving the reaction efficiency.
The Graphene/MnOX/TiO2The preparation method of the composite material comprises the following steps: firstly, preparing graphene by adopting an ultrasonic stripping method. Raw materials: graphite oxide powder, ultrasonic equipment: GBS-SCP pilot model (power 3000W, operating frequency 20 KHz), solvent: dissolving graphite oxide powder in N-methylpyrrolidone, ultrasonically stripping (6 h), centrifuging (45min rotation speed 1000r/min), and taking an upper layer suspension; and (4) performing secondary ultrasonic treatment and centrifugation, then taking the upper suspension, and centrifuging again (5min rotating speed of 30000r/min), wherein the rest precipitate is Graphene oxide (Graphene). The second step is that: according to the weight ratio of 2: 3: 4 taking MnOXSoaking the Graphene and the base C for 6-8h, stirring, rolling and pressing for molding, drying, and calcining at normal temperature and normal pressure at low temperature to prepare Graphene/MnOX(ii) a The third step: soaking Graphene/MnO in nano titanium dioxide dispersion liquidxDrying for 10 min, and ultraviolet curing to obtain Graphene/MnOX/TiO2A photocatalytic carrier.
Photocatalytic sterilization: the graphene-based photocatalytic bioreactor for sterilizing and removing ammonia in a farm is compounded by adopting various technical means. Firstly, the method comprises the following steps: ozone generated by vacuum ultraviolet light 185 nanometer waves through air has stronger sterilization capability under the coordination of 254 nanometer waves, and surplus ozone is absorbed by the Mn type ozone oxidation catalyst and is converted into peroxide species to play a sterilization role; secondly, the method comprises the following steps: the 254nm ultraviolet wave energy ionizes air to form negative ions and also plays a role in inhibitingThe function of bacteria production; thirdly, the method comprises the following steps: illumination of TiO2Active groups with strong oxidizing property are generated on the surface, and are combined with bacterial cells in a direct or indirect mode, so that the active groups have the effect of inhibiting or killing microorganisms. And moreover, the graphene can effectively enhance the catalytic effect of the semiconductor under the action of ultraviolet light and visible light, so that the sterilization effect field of the graphene-based/graphene oxide-based composite material is obviously improved. Typical experiments: Graphene/TiO2The film can eliminate 99.9 percent of colibacillus under the irradiation of sunlight and is relatively pure TiO2For thin films, Graphene/TiO2The antibacterial activity of the film is remarkably improved, and the graphene sheet layer is still stable after the light inactivates bacteria.
Ultraviolet visible absorption spectrum test and analysis: as can be seen from fig. 11, graphene oxide reaches a maximum absorption peak at 245 nm; titanium dioxide is about 400 nm; the titanium dioxide is loaded on the graphene oxide, the absorption boundary of the composite material is prolonged to about 450nm, the red shift is obviously generated in a long wavelength region, and the addition of the graphene oxide is fully proved to widen TiO2The energy band improves the utilization efficiency of the light energy.
Inventive selection of UV185-254nmVacuum ultraviolet lamp and UVC254nmUltraviolet lamp, self-made LedUV365nm-400nmThe ultraviolet lamp is a composite light source of the photocatalytic bioreactor.
The test result proves that: the activity of the Mn-containing graphene-based nano titanium dioxide photocatalytic carrier in photocatalytic degradation of pollutants is obviously superior to that of a pure semiconductor by 40%.
The purification process of the graphene-based photocatalytic bioreactor for sterilizing and removing ammonia in the farm comprises the following steps: toxic and harmful gases in a farm firstly enter a first-stage air filtering component to be filtered, enter a composite ultraviolet light component to be subjected to catalytic ozone oxidation under the conditions of deep ultraviolet light and ultraviolet light, and then are subjected to ultraviolet light or nano TiO under visible light by virtue of a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier2A photocatalytic oxidation process; finally, the purified clean air is returned to the farm by the fan after being filtered by the second-stage air filtering component, and the ECU control module controls the whole system to operateThe line state.
Plant's sterilization removes ammonia graphite alkene base photocatalysis bioreactor adopts the composite wavelength light source, cooperates neotype Mn type graphite alkene base nanometer titanium dioxide photocatalysis carrier that contains, has realized that photocatalysis disinfects, harmful substance adsorption's multiple functions, has improved photocatalysis efficiency, and reinforcing adsorption effect can more effectual disinfecting, get rid of the ammonia.
Drawings
FIG. 1 is a schematic view of a photobioreactor configuration;
FIG. 2 is a diagram of a photobioreactor in-situ layout;
FIG. 3 is a schematic view of the internal structure of the photobioreactor;
FIG. 4 is a schematic view of a first stage air filter assembly;
FIG. 5 is a schematic view of a composite UV assembly;
FIG. 6 is a schematic structural diagram of a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier;
FIG. 7 is a schematic diagram of an electrical structure of the ECU control module;
FIG. 8 is a sample sterilization and purification test report
FIG. 9 is a sterilization rate detection report data;
FIG. 10 is an air purification efficiency test report data;
FIG. 11 is a UV-VIS absorption spectrum of GO, TiO2 and TiO2/GO composite.
Detailed description of the preferred embodiments
The invention is further described with reference to the following specific embodiments and the accompanying drawings. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
Example (b): the graphene-based photocatalytic bioreactor for antibacterial and ammonia removal in chicken farms is composed of a reactor box body 1, an air filtering component, a composite ultraviolet light component and a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier, wherein the air filtering component, the composite ultraviolet light component and the Mn-containing graphene-based nano titanium dioxide photocatalytic carrier are installed in the reactor box body 1.
As shown in fig. 1 and fig. 3, a reactor box 1 is a box with a structure with openings at the left and right ends, an air inlet 2 is arranged at the opening at the left end, and an air outlet 3 is arranged at the opening at the right end; the reactor box body is characterized in that a plurality of concave mounting grooves 14 are formed in the inner wall of the reactor box body 1, a first-stage air filtering component 4, a composite ultraviolet light source component 5, a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier 6, a second-stage air filtering component 7 and a control box 8 are sequentially mounted from left to right. The front surface of the box body 1 is divided into three independently openable and closable box doors 12 which are provided with locks, and the bottom of the box body 1 is provided with sliding rollers 13.
As shown in fig. 4, the first stage air filter assembly 4 is assembled in a rectangular metal frame 41 by overlapping a primary filter cotton 43 and a medium-density non-woven fabric 44, and metal guard nets 42 are disposed on both side surfaces of the frame.
The composite ultraviolet light source assembly 5 comprises deep ultraviolet vacuum ultraviolet lamp, UVC, UVB band vacuum ultraviolet lamp and UV Led ultraviolet lamp, as shown in FIG. 5, and is composed of vacuum ultraviolet lamp (UV lamp)185nm-254nm) 52 ultraviolet lamp (uvc)254nm）53， Leduv365nm-400nmThe uv lamps 54 are arranged side by side and fixedly mounted in the lamp frame 51. The lamp frame 51 is a rectangular metal frame, and mounting holes are provided in the horizontal frame to insert and fix the lamp through the mounting holes.
As shown in FIG. 6, the Mn-containing Graphene-based nano-titanium dioxide photocatalytic carrier 6 is prepared from Graphene/MnOX/TiO2The composite material is made into a plate-type structure 62 and fixedly assembled in a rectangular metal frame 61, and metal protective nets 63 are arranged on the surfaces of two sides of the frame. Wherein Graphene/MnOX/TiO2The raw materials of the composite material comprise 40% of C, 30% of Graphene and MnO according to weight ratioX20%、TiO 210%。
The Graphene/MnOX/TiO2The preparation method of the composite material comprises the following steps: firstly, preparing graphene by adopting an ultrasonic stripping method. Raw materials: graphite oxide powder, ultrasonic equipment: GBS-SCP pilot model (power 3000W, operating frequency 20 KHz), solvent: dissolving graphite oxide powder in N-methylpyrrolidone, ultrasonically stripping (6 h), centrifuging (45min rotation speed 1000r/min), and taking an upper layer suspension; and (4) performing secondary ultrasonic treatment and centrifugation, then taking the upper suspension, and centrifuging again (5min rotating speed of 30000r/min), wherein the rest precipitate is Graphene oxide (Graphene). First, theStep two: according to the weight ratio of 2: 3: 4 taking MnOXSoaking the Graphene and the base C for 6-8h, stirring, rolling and pressing for molding, drying, and calcining at normal temperature and normal pressure at low temperature to prepare Graphene/MnOX(ii) a The third step: soaking Graphene/MnO in nano titanium dioxide dispersion liquidxDrying for 10 min, and ultraviolet curing to obtain Graphene/MnOX/TiO2A photocatalytic carrier.
And the second-stage air filtering component 7 is assembled in a rectangular metal frame after being overlapped by the primary-effect non-woven fabric and the medium-density non-woven fabric, and the surfaces of two sides of the metal frame are provided with metal protecting nets which have the same structure as the first-stage air filtering component 4.
The external control box 8 is used as an electric appliance controller, an ECU control module is arranged in the external control box, as shown in fig. 7, the ECU module is connected with a control button, a display and a switch control circuit, the button and the display are arranged on a panel of the control box 8, a control signal is input through the control button, and the running state is displayed through the display. The switch control circuit is connected with a lamp power supply of the composite ultraviolet light source component 5 in the reactor box body 1 through a circuit, controls the switch and automatically executes power-off protection and overload protection.
As shown in fig. 2, the reactor box 1 is installed outside the henhouse 9, the exhaust air of the henhouse 9 is connected to the air inlet 2 of the reactor box 1 through the pipeline 10, enters the reactor box for purification treatment, the purified air returns to the farm through the exhaust outlet 3 and the pipeline 11, and the purification process is as follows: poisonous and harmful gas in the chicken house firstly enters a first-stage air filtering component to be filtered, enters a composite ultraviolet light component to perform catalytic ozone oxidation process under the conditions of deep ultraviolet light and ultraviolet light, and then passes through a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier to perform nano TiO under the conditions of ultraviolet light or visible light2A photocatalytic oxidation process; and finally, the purified clean air is returned to the henhouse by the fan after being filtered by the second-stage air filtering component, and the whole system is controlled to operate by the ECU control module and displays the operating state.
The test report of the prototype, as shown in fig. 8, 9 and 10, was tested by the southern eastern province microbiological analysis and detection center, and the sterilization rate: 99.12 percent of white staphylococcus and 97.86 percent of escherichia coli; purification efficiency: 88.2 percent of ammonia gas and 80.3 percent of volatile micromolecular organic formaldehyde.
Practical cases of the prototype: the removal rate of malodorous gases (hydrogen sulfide and ammonia gas) is more than 93 percent after being tried by a certain pig farm in Bazhou city, Hebei province; after the animal waste water is tried out by a certain animal treatment center treatment workshop and a sewage treatment workshop in the province of Shandong, the odor can not be smelled after the animal waste water is started for 10 minutes.
Through tests, the desorption time of the Mn-containing graphene-based nano titanium dioxide photocatalytic carrier under sunlight is 27 s.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention shall be covered by the claims of the present invention.
Claims (5)
1. The graphene-based photocatalytic bioreactor for sterilizing and removing ammonia in a farm is characterized by comprising a reactor box body (1), and an air filtering component, a composite ultraviolet component and a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier which are arranged in the reactor box body; the reactor box body (1) is a box body with openings at the left end and the right end, an air inlet (2) is arranged at the opening at the left end, and an air outlet (3) is arranged at the opening at the right end; the inner wall of the reactor box body (1) is provided with a plurality of concave mounting grooves (14), and a first-stage air filtering component (4), a composite ultraviolet light source component (5), a Mn-containing graphene-based nano titanium dioxide photocatalytic carrier (6) and a second-stage air filtering component (7) are sequentially mounted from left to right;
the first-stage air filtering component (4) is assembled in a metal frame after primary filter cotton and medium-density non-woven fabrics are superposed, and metal protective nets are arranged on the surfaces of two sides of the frame;
the composite ultraviolet light source component (5) is composed of a vacuum ultraviolet lamp UV185nm-254nm（52）、UVC254nmUV lamp (53) and led uv365nm-400nmThe ultraviolet lamps (54) are arranged side by side and fixedly assembled in the metal frame;
the Mn-containing Graphene-based nano titanium dioxide photocatalytic carrier (6) is prepared from Graphene/MnOX/TiO2The composite material is made into a plate structure and fixedly assembled in a metal frame, wherein Graphene/MnO isX/TiO2The raw materials of the composite material comprise C40%, Graphene30% and MnO according to weight ratioX20%、TiO210%。
And the second-stage air filtering component (7) is assembled in the metal frame after the primary-effect non-woven fabric and the medium-density non-woven fabric are superposed, and metal protective nets are arranged on the surfaces of two sides of the metal frame.
2. The Graphene-based photocatalytic bioreactor for sterilization and ammonia removal in a farm according to claim 1, wherein the Graphene/MnO isX/TiO2The preparation method of the composite material comprises the following steps: firstly, preparing graphene by adopting an ultrasonic stripping method, wherein the raw materials are as follows: graphite oxide powder, ultrasonic equipment: GBS-SCP pilot model (power 3000W, operating frequency 20 KHz), solvent: dissolving graphite oxide powder in N-methylpyrrolidone, ultrasonically stripping for 6h, centrifuging (45min rotation speed 1000r/min), and taking an upper layer suspension; and (4) performing secondary ultrasonic treatment and centrifugation, then centrifuging the upper suspension for 5 times (the min rotating speed is 30000r/min), and obtaining the remaining precipitate which is Graphene oxide (Graphene). The second step is that: according to the weight ratio of 2: 3: 4 taking MnOXSoaking the Graphene and the base C for 6-8h, stirring, rolling and pressing for molding, drying, and calcining at normal temperature and normal pressure at low temperature to prepare Graphene/MnOX(ii) a The third step: soaking Graphene/MnO in nano titanium dioxide dispersion liquidxDrying for 10 min, and ultraviolet curing to obtain Graphene/MnOX/TiO2A photocatalytic carrier.
3. The graphene-based photocatalytic bioreactor for sterilization and ammonia removal in a farm according to claim 1, further comprising an externally connected control box (8), wherein an ECU control module, buttons connected and controlled by the ECU control module, a display and a switch control circuit are arranged in the control box (8), the buttons and the display are arranged on a panel of the control box (8), control signals are input through the control buttons, and the display displays the operation state; the switch control circuit is connected with a power supply of the composite ultraviolet light source component (5) in the reactor box body (1) through a circuit, controls the switch and automatically executes power-off protection and overload protection.
4. The graphene-based photocatalytic bioreactor for sterilization and ammonia removal in a farm according to claim 1, characterized in that the front surface of the box body (1) is provided with a box door (12) which can be opened and closed.
5. The graphene-based photocatalytic bioreactor for sterilization and ammonia removal in a farm according to claim 1, characterized in that rollers (13) are arranged at the bottom of the box body (1).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4205773A1 (en) * | 2021-12-28 | 2023-07-05 | Hyundai Mobis Co., Ltd. | Vehicle sterilizing apparatus and cockpit module having the same |
| US20230321587A1 (en) * | 2022-04-07 | 2023-10-12 | The United States Of America, As Represented By The Secretary Of Agriculture | System for removing ammonia, dust and pathogens from air within an animal rearing/sheltering facility |
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2020
- 2020-04-30 CN CN202010362487.3A patent/CN111359435A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4205773A1 (en) * | 2021-12-28 | 2023-07-05 | Hyundai Mobis Co., Ltd. | Vehicle sterilizing apparatus and cockpit module having the same |
| US20230321587A1 (en) * | 2022-04-07 | 2023-10-12 | The United States Of America, As Represented By The Secretary Of Agriculture | System for removing ammonia, dust and pathogens from air within an animal rearing/sheltering facility |
| US11986768B2 (en) * | 2022-04-07 | 2024-05-21 | The United States Of America, As Represented By The Secretary Of Agriculture | System for removing ammonia, dust and pathogens from air within an animal rearing/sheltering facility |
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