A sensor design method and application for detecting butyric acid odor gas in livestock and poultry breeding

Abstract

The application discloses a kind of detection of livestock and poultry breeding butyric acid malodorous gas sensor design method and application, comprising: carbon ball is mixed with deionized water and ultrasonic, then add zinc acetate dihydrate to obtain carbon ball mixture, then carbon ball mixture is placed in the stainless steel reaction kettle lined with polytetrafluoroethylene and placed in oven to obtain mixture C; supernatant is removed, mixture D is obtained, centrifugal washing and drying, placed in muffle furnace and calcined, to obtain zinc oxide nanospheres;Zinc oxide nanospheres are placed in muffle furnace and calcined under 4.8% hydrogen argon mixed atmosphere to obtain zinc oxide nanospheres loaded with zinc nanoparticles, the prepared zinc oxide nanospheres loaded with zinc nanoparticles are dispersed in ethanol, then drop-coated on flat plate electrode using a pipette gun, dried, and finally welded on the sensor using a precision electric welder, for detection of livestock and poultry breeding butyric acid malodorous gas, response is rapid and sensitivity is high.

Description

Technical Field

[0001] This invention relates to the field of gas detection sensor technology, specifically to a sensor design method and application for detecting butyric acid odorous gas from livestock and poultry farming. Background Technology

[0002] Odor-laden gases from livestock and poultry farming are primarily generated from livestock and poultry feces and respiration. These gases are not only harmful to the livestock themselves, potentially causing symptoms such as respiratory distress, loss of appetite, and stunted growth, but also pose risks to the environment and human health. While the detection of odor-laden gases such as hydrogen sulfide and trimethylamine is widely used, the detection of volatile fatty acids, particularly butyric acid, is rarely employed. Therefore, utilizing high-performance gas sensors for real-time monitoring of butyric acid in production and living environments is crucial.

[0003] Among all types of gas sensors, semiconductor gas sensors are the most widely used and commercially available. The principle is that the gas-sensitive material itself exhibits different voltage changes in different gases. When a resistive semiconductor gas sensor is exposed to a target gas, the gas-sensitive material reacts with the target gas, causing a drastic change in the material's resistance, which in turn causes a voltage change across it. The magnitude of this resistance change is related to the concentration of the target gas in the environment. This type of sensor has advantages such as simple circuitry, ease of manufacturing, simple operation, low cost, and easy integration. Among many gas-sensitive materials, metal-oxide-semiconductor (MOS) possesses excellent physicochemical properties and a unique structure, exhibiting significantly superior gas-sensing performance compared to other sensors. It can provide a wider detection range, higher sensitivity, good stability, and shorter response / recovery time. However, MOS sensors also suffer from a discrepancy between response value and response / recovery time. To address this issue, gas sensor performance can be improved by synthesizing special morphologies, doping with noble metals, or forming heterojunctions. However, these methods often cannot comprehensively solve all problems. Therefore, it is of great significance to study a low-cost, high-response, and short-response / recovery gas sensor.

[0004] In recent years, zinc oxide (ZnO), as a wide-bandgap semiconductor metal oxide, has not only exhibited excellent electrical properties but also superior gas-sensing characteristics, showing broad application prospects in optoelectronic devices, sensors, solar cells, and gas-sensitive devices. Based on this, this invention designs a sensor suitable for detecting butyric acid-laden odorous gases from livestock and poultry farming using a zinc oxide semiconductor material modified with metallic zinc, achieving highly sensitive detection of butyric acid gas. Summary of the Invention

[0005] The purpose of this invention is to provide a sensor design method and application for detecting butyric acid odorous gas from livestock and poultry farming, so as to solve the problems mentioned above.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A sensor design method for detecting butyric acid odorous gas from livestock and poultry farming includes the following steps:

[0008] Step 1: Take 0.3-0.5g of carbon spheres and mix with 70-100ml of deionized water, sonicate for 0.8-1.2h, then add 0.428-0.713g of zinc acetate dihydrate to obtain a carbon sphere mixture, and sonicate and magnetically stir it. Then place the carbon sphere mixture in a stainless steel reactor lined with polytetrafluoroethylene, and place the reactor in an oven at 180-190℃ for 5-7h to obtain mixture C.

[0009] Step 2: Remove the supernatant from mixture C to obtain mixture D. Disperse mixture D ultrasonically and wash it by centrifugation with ethanol. Place the centrifuged and washed mixture D in an oven to dry it. Place the dried mixture D in a muffle furnace to calcine it to obtain zinc oxide nanospheres.

[0010] Step 3: Place the zinc oxide nanospheres in a muffle furnace and calcine them at a rate of 2℃ / min to raise the temperature to 200℃ in a hydrogen-argon mixed atmosphere of 4.8%-5.2% for 0.9-1.2h, and keep the temperature at 200℃ to obtain zinc oxide nanospheres loaded with zinc nanoparticles.

[0011] Step 4: Disperse the prepared zinc oxide nanospheres loaded with zinc nanoparticles in ethanol, then drop them onto a flat electrode using a pipette, dry the flat electrode in a 60-80℃ drying oven, and finally weld it onto the sensor using a precision welding machine.

[0012] As a further aspect of the present invention: in step one, the ultrasonic time of the carbon ball mixture is 20-30 min; then the carbon ball mixture is placed on a magnetic stirrer and magnetically stirred at a speed of 1000-1200 r / min for 1-1.2 h.

[0013] As a further aspect of the present invention: in step two, the ultrasonic dispersion time of mixture D is 12-18 min, and the mixture is centrifuged and washed with ethanol in a centrifuge at a speed of 8000-9000 r / min for 4-6 min.

[0014] As a further aspect of the present invention: in step two, the mixture D is centrifuged and washed 2-4 times.

[0015] As a further aspect of the present invention: in step two, the mixture D after centrifugation and washing is placed in an oven at 75-85°C for 5-7 hours to react.

[0016] As a further aspect of the present invention: the method for preparing the carbon spheres is as follows:

[0017] S1: Weigh 7-8g of anhydrous glucose and dissolve it completely in 70-80ml of deionized water to obtain a glucose solution. Then place the glucose solution in a stainless steel reactor lined with polytetrafluoroethylene and place the reactor in an oven at 160-200℃ for 6-7 hours to obtain mixture A.

[0018] S2: Remove the supernatant from mixture A to obtain mixture B. Wash mixture B by centrifugation with ethanol. Place the washed mixture B in an oven for drying reaction to obtain carbon balls.

[0019] As a further aspect of the present invention: in step S2, mixture B is washed with ethanol and centrifuged for 4-6 minutes in a centrifuge at a speed of 8000-9000 r / min.

[0020] As a further aspect of the present invention: in step S2, the mixture B after centrifugation and washing is placed in an oven at 75-85°C and reacted for 5-7 hours.

[0021] As a further aspect of the present invention: the application of a sensor for detecting butyric acid odorous gas from livestock and poultry farming, used for gas-sensitive testing.

[0022] The beneficial effects of this invention are:

[0023] In this invention, zinc oxide nanospheres are prepared and then reduced in a hydrogen-argon mixed atmosphere to obtain zinc oxide nanospheres loaded with zinc nanoparticles. These nanospheres have a large surface area, which can increase the contact area between the gas and the material during the detection process and effectively improve the sensitivity of gas detection.

[0024] Secondly, the zinc oxide nanospheres loaded with zinc nanoparticles have the characteristics of uniform size and good dispersion. When designed and prepared as gas-sensitive materials for butyric acid sensors and used for the detection of butyric acid odor gas in livestock and poultry farming, they have a rapid response and high sensitivity.

[0025] In addition, zinc oxide nanospheres were prepared and then reduced in a hydrogen-argon mixed atmosphere to obtain zinc oxide nanospheres loaded with zinc nanoparticles. Then, gas-sensitive materials for butyric acid sensors were designed and prepared, and finally, a sensor for butyric acid odor gas was obtained. The entire preparation process does not require special equipment, the process is simple and easy to operate, and the production cost of the entire process is effectively reduced. Attached Figure Description

[0026] The invention will now be further described with reference to the accompanying drawings.

[0027] Figure 1 This is a gas-sensing test Response(Rgas / Ra ir)-T ime(s) curve of the sensor in this invention at a working temperature of 250℃ for different concentrations of butyric acid;

[0028] Figure 2 These are scanning electron microscope images of carbon spheres from this invention;

[0029] Figure 3 In the middle (a) and (b), respectively, are scanning electron microscope (SEM) images of zinc oxide nanospheres without zinc nanoparticles and zinc oxide nanospheres loaded with zinc nanoparticles provided by the present invention;

[0030] Figure 4 These are the X-ray diffraction patterns of zinc oxide nanospheres without zinc nanoparticles and zinc oxide nanospheres with zinc nanoparticles provided by this invention. Detailed Implementation

[0031] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] Please see Figures 1-4 As shown, the present invention provides the following embodiments:

[0033] Example 1

[0034] A sensor design method for detecting butyric acid odorous gas from livestock and poultry farming includes the following steps:

[0035] M1: Weigh 7g of anhydrous glucose and dissolve it completely in 70ml of deionized water to obtain a glucose solution. Then place the glucose solution in a stainless steel reactor lined with polytetrafluoroethylene and place the reactor in an oven at 160℃ for 6 hours to obtain mixture A.

[0036] M2: Remove the supernatant from mixture A to obtain mixture B. Wash mixture B with ethanol and centrifuge at 8000 r / min for 4 min, repeating the centrifugation wash three times. Place the washed mixture B in an oven at 75℃ to dry for 5 h to obtain carbon spheres; Figure 2 As shown;

[0037] M3: Mix 0.3g of carbon balls with 70ml of deionized water, sonicate for 0.8h, then add 0.428g of zinc acetate dihydrate to obtain a carbon ball mixture. The sonication time of the carbon ball mixture is 20min. Then place the carbon ball mixture on a magnetic stirrer and stir magnetically at 1000r / min for 1h. Then place the carbon ball mixture in a stainless steel reactor lined with polytetrafluoroethylene and place the reactor in an oven at 180℃ for 5h to obtain mixture C.

[0038] M4: Remove the supernatant from mixture C to obtain mixture D. Disperse mixture D ultrasonically for 12 min, and wash it with ethanol in a centrifuge at 8000 r / min for 4 min. Repeat the centrifugation and washing twice. Place the washed mixture D in an oven at 75℃ to dry for 5 h. Place the dried mixture D in a muffle furnace for calcination to obtain zinc oxide nanospheres.

[0039] M5: Zinc oxide nanospheres were placed in a muffle furnace and calcined at 200°C for 0.9 h under a 4.8% hydrogen-argon mixed atmosphere, with the furnace temperature increased to 200°C at a rate of 2°C / min, to obtain zinc oxide nanospheres loaded with zinc nanoparticles. Figure 3 The scanning electron microscope image shown in (b) is as follows: Figure 3 Image (a) shows a scanning electron microscope image of zinc oxide nanospheres without zinc nanoparticles.

[0040] Zinc oxide nanospheres loaded with zinc nanoparticles were prepared by reducing them in a hydrogen-argon mixed atmosphere. Then, gas-sensitive materials for butyric acid sensors were designed and prepared, and finally, a sensor for butyric acid odor gas was obtained. The entire preparation process does not require special equipment, the process is simple and easy to operate, and the production cost of the entire process is effectively reduced.

[0041] M6: The prepared zinc oxide nanospheres loaded with zinc nanoparticles were dispersed in ethanol, then dropped onto a flat plate electrode using a pipette, and then the flat plate electrode was dried in a 60°C drying oven. Finally, it was welded onto the sensor using a precision welding machine.

[0042] Zinc oxide nanospheres loaded with zinc nanoparticles have a large surface area, which can increase the contact area between gas and material during detection and effectively improve the sensitivity of gas detection.

[0043] Figure 4The middle image shows the X-ray diffraction (XRD) patterns of zinc oxide nanospheres without zinc nanoparticles and zinc oxide nanospheres with zinc nanoparticles. The upper image shows the XRD pattern of zinc oxide nanospheres with zinc nanoparticles, and the lower image shows the XRD pattern of zinc oxide nanospheres without zinc nanoparticles.

[0044] Figure 1 The figure shows the Response (Rgas / Ra ir)-Time(s) curves of the designed sensor at an operating temperature of 250℃ for gas sensing of butyric acid of different concentrations. In the figure, the upper curve is the test curve of zinc oxide nanospheres loaded with zinc nanoparticles, and the lower curve is the test curve of zinc oxide nanospheres without zinc nanoparticles.

[0045] Example 2

[0046] A sensor design method for detecting butyric acid odorous gas from livestock and poultry farming includes the following steps:

[0047] M1: Weigh 8g of anhydrous glucose and dissolve it completely in 80ml of deionized water to obtain a glucose solution. Then place the glucose solution in a stainless steel reactor lined with polytetrafluoroethylene and place the reactor in an oven at 200℃ for 7h to obtain mixture A.

[0048] M2: Remove the supernatant from mixture A to obtain mixture B. Wash mixture B with ethanol and centrifuge at 9000 r / min for 6 min, repeating the centrifugation wash 5 times. Place the washed mixture B in an oven at 85℃ to dry for 7 h to obtain carbon spheres; Figure 2 As shown;

[0049] M3: Mix 0.5g of carbon balls with 100ml of deionized water and sonicate for 1.2h. Then add 0.713g of zinc acetate dihydrate to obtain a carbon ball mixture. Sonicate the carbon ball mixture for 30min. Then place the carbon ball mixture on a magnetic stirrer and stir at 1200r / min for 1.2h. Then place the carbon ball mixture in a stainless steel reactor lined with polytetrafluoroethylene and place the reactor in an oven at 190℃ for 7h to obtain mixture C.

[0050] M4: Remove the supernatant from mixture C to obtain mixture D. Disperse mixture D ultrasonically for 18 min, and wash it with ethanol in a centrifuge at 9000 r / min for 6 min. Repeat the centrifugation washing 4 times. Place the centrifuged and washed mixture D in an oven at 85℃ to dry for 7 h. Place the dried mixture D in a muffle furnace for calcination to obtain zinc oxide nanospheres.

[0051] M5: Zinc oxide nanospheres were placed in a muffle furnace and calcined at 200°C for 1.2 hours under a 5.2% hydrogen-argon mixed atmosphere, with the furnace temperature increased to 200°C at a rate of 2°C / min, to obtain zinc oxide nanospheres loaded with zinc nanoparticles. Figure 3 The scanning electron microscope image shown in (b) is as follows: Figure 3 Image (a) shows a scanning electron microscope image of zinc oxide nanospheres without zinc nanoparticles.

[0052] M6: The prepared zinc oxide nanospheres loaded with zinc nanoparticles were dispersed in ethanol, then drop-coated onto a flat electrode using a pipette, and then dried in an 80°C drying oven. Finally, they were welded onto the sensor using a precision welding machine.

[0053] By preparing zinc oxide nanospheres and then reducing them in a hydrogen-argon mixed atmosphere, zinc oxide nanospheres loaded with zinc nanoparticles are obtained. These nanospheres have a large surface area, which can increase the contact area between the gas and the material during the detection process and effectively improve the sensitivity of gas detection.

[0054] Secondly, the zinc oxide nanospheres loaded with zinc nanoparticles have the characteristics of uniform size and good dispersion. When designed and prepared as gas-sensitive materials for butyric acid sensors and used for the detection of butyric acid odor gas in livestock and poultry farming, they have a rapid response and high sensitivity.

[0055] In addition, zinc oxide nanospheres were prepared and then reduced in a hydrogen-argon mixed atmosphere to obtain zinc oxide nanospheres loaded with zinc nanoparticles. Then, gas-sensitive materials for butyric acid sensors were designed and prepared, and finally, a sensor for butyric acid odor gas was obtained. The entire preparation process does not require special equipment, the process is simple and easy to operate, and the production cost of the entire process is effectively reduced.

[0056] Example 3

[0057] An application of a sensor for detecting butyric acid odorous gas from livestock and poultry farming is presented. This sensor is used for gas-sensitive testing and can achieve high-sensitivity detection of butyric acid gas. Zinc oxide nanospheres are prepared using zinc metal ions as a precursor, and after modification with zinc metal ions and calcination under hydrogen and argon atmospheres, zinc oxide nanospheres with uniform size and good dispersion are prepared. The gas sensor developed based on the above sensitive material has excellent sensing response to butyric acid gas.

[0058] The foregoing has provided a detailed description of one embodiment of the present invention, but this description is merely a preferred embodiment and should not be construed as limiting the scope of the invention. All equivalent variations and modifications made within the scope of the claims of this invention should still fall within the patent coverage of this invention.

Claims

1. A sensor design method for detecting butyric acid odorous gas from livestock and poultry farming, characterized in that, Includes the following steps: Step 1: Take 0.3-0.5g of carbon balls and mix with 70-100ml of deionized water, sonicate for 0.8-1.2h, then add 0.428-0.713g of zinc acetate dihydrate to obtain a carbon ball mixture, and sonicate and magnetically stir it. Then place the carbon ball mixture in a stainless steel reactor lined with polytetrafluoroethylene, and place the reactor in an oven at 180-190℃ for 5-7h to obtain mixture C. Step 2: Remove the supernatant from mixture C to obtain mixture D. Disperse mixture D ultrasonically and wash it by centrifugation with ethanol. Place the centrifuged and washed mixture D in an oven to dry it. Place the dried mixture D in a muffle furnace to calcine it to obtain zinc oxide nanospheres. Step 3: Place the zinc oxide nanospheres in a muffle furnace and, under a hydrogen-argon mixed atmosphere, raise the temperature inside the muffle furnace to 200°C at a heating rate of 2°C / min, and maintain the temperature at 200°C for calcining the zinc oxide nanospheres for 0.9-1.2 hours to obtain zinc oxide nanospheres loaded with zinc nanoparticles. Step 4: Disperse the prepared zinc oxide nanospheres loaded with zinc nanoparticles in ethanol, then drop them onto a flat electrode using a pipette, dry the flat electrode in a 60-80℃ drying oven, and finally weld it onto the sensor using a precision welding machine.

2. The sensor design method for detecting butyric acid odor gas from livestock and poultry farming according to claim 1, characterized in that, In step one, the ultrasonic time for the carbon ball mixture is 20-30 minutes; then the carbon ball mixture is placed on a magnetic stirrer and magnetically stirred at a speed of 1000-1200 r / min for 1-1.2 hours.

3. The sensor design method for detecting butyric acid odor gas from livestock and poultry farming according to claim 1, characterized in that, In step two, the ultrasonic dispersion time of mixture D is 12-18 min, and the mixture is centrifuged and washed with ethanol in a centrifuge at a speed of 8000-9000 r / min for 4-6 min.

4. The sensor design method for detecting butyric acid odor gas from livestock and poultry farming according to claim 3, characterized in that, In step two, mixture D is centrifuged and washed 2-4 times.

5. The sensor design method for detecting butyric acid odor gas from livestock and poultry farming according to claim 3, characterized in that, In step two, the mixture D after centrifugation and washing is placed in an oven at 75-85℃ for drying reaction for 5-7 hours.

6. The sensor design method for detecting butyric acid odor gas from livestock and poultry farming according to claim 1, characterized in that, The carbon spheres are prepared by: S1: Weigh 7-8g of anhydrous glucose and dissolve it completely in 70-80ml of deionized water to obtain a glucose solution. Then place the glucose solution in a stainless steel reactor lined with polytetrafluoroethylene and place the reactor in an oven at 160-200℃ for 6-7 hours to obtain mixture A. S2: Remove the supernatant from mixture A to obtain mixture B. Wash mixture B by centrifugation with ethanol. Place the washed mixture B in an oven for drying reaction to obtain carbon balls.

7. The sensor design method for detecting butyric acid odor gas from livestock and poultry farming according to claim 6, characterized in that, In step S2, mixture B is washed with ethanol and centrifuged for 4-6 minutes in a centrifuge at a speed of 8000-9000 r / min.

8. A sensor design method for detecting butyric acid odorous gas from livestock and poultry farming according to claim 6, characterized in that, In step S2, the mixture B, after centrifugation and washing, is placed in an oven at 75-85°C and reacted for 5-7 hours.

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