TWI755969B - Use of oyster shells for controlling plant diseases - Google Patents

Abstract

The present invention discloses the use of oyster shells for preventing and treating plant diseases. The oyster shells are calcined under a predetermined calcining condition, so that the composition of the calcined oyster shells can be changed, so that the oyster shells can be used for the prevention and treatment of courgette bloom disease. The active ingredient of the composition, and at the same time can solve the pollution problem caused by waste oyster shells.

Description

Use of oyster shells for controlling plant diseases

The present invention relates to the second use of waste, especially the use of oyster shells for controlling plant diseases.

According to statistics, the oyster cultivation area in Taiwan accounts for more than 10,000 hectares, with an output value of 4.651 billion yuan and an average annual production volume of more than 180,000. mt. However, the prosperity of aquaculture and fishery has also resulted in a large amount of discarded shells, which account for 90% of the total weight of peony. If the shelling rate is calculated at 12%, the annual shell waste generated is as high as 160,000 metric tons. According to statistics In 2016, the waste of oyster shells reached 182,214 metric tons, and about 4 million metric tons were produced globally. In addition to taking up a lot of space and affecting local landscapes, discarded oyster shells also have negative impacts on the environment, such as the accumulation of heavy metals and stench caused by seawater pollution.

Since the main component of waste oyster shells is calcium carbonate, waste oyster shells are currently reused as fertilizers, paint coatings or roadbed additives, or as food additives to increase the shelf life, etc. In fact, although oyster shells are Shells serve many of the above-mentioned uses, however, most of the discarded oyster shells are still discarded arbitrarily due to the low utilization rate.

The main purpose of the present invention is to provide a use of oyster shells for preventing and treating plant diseases, which is a process of calcining oyster shells under a predetermined calcining condition, so that the composition of the calcined oyster shells is changed to contain a large amount of oxidized Calcium, and calcined oyster shells can be used as an active ingredient in a composition for preventing and treating succulent blooming disease, and at the same time, it can solve the problem of pollution caused by discarded oyster shells.

The reason is that, in order to achieve the above object, the present invention discloses a second use of oyster shell powder, which is to use oyster shell powder to prepare a composition for preventing and treating blooming disease, wherein the oyster shell powder is modified through a modified The procedure is obtained, and its main component is calcium oxide.

By providing an effective amount of the composition containing the oyster shell powder disclosed by the present invention to plants such as courgettes, the effect of preventing and treating the plants from being attacked by diseases or bacterial infections can be achieved. Specifically, the diseases are caused by Pseudoperonospora cubensis. Caused by dew fungus.

More specifically, the oyster shell powder is obtained by calcining the oyster shells at a calcining temperature above 850° C. for a predetermined period of time and then modifying them, and then powdering them.

In one embodiment of the present invention, the calcination temperature is above 850°C and below 1050°C, wherein, when the calcination temperature is 1050°C, the oyster shell powder can be made to contain a higher amount of calcium oxide.

In another embodiment of the present invention, the predetermined time is at least 1 hour, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours and the like.

In order to increase the convenience in use, in one embodiment of the present invention, the composition is prepared as an oyster shell powder solution, which is prepared by diluting the oyster shell powder 1000 to 6000 times, and, In order to achieve better disease control effect, the concentration of the oyster shell powder solution is above 117 ppm and below 1000 ppm, among which, when the concentration is 300-400 ppm, it has the best disease control effect.

The present invention discloses the use of an oyster shell for preventing and treating plant diseases. Specifically, the technical feature of the present invention is that the oyster shell is modified through a calcination process, and the modified oyster shell has a high amount of calcium oxide. , and can be used to make plants resistant to the invasion of Pseudoperonospora cubensis , not only can prevent plants from being infected by Pseudoperonospora cubensis and suffer from dew fungus, but also can persist on plants for long-term plant disease control; in addition, Since the oyster shells used in the present invention are wastes, the effects of environmental protection and pollution solving can also be achieved at the same time.

The "bacterial disease" disclosed in the present invention, the pathogen is Pseudoperonospora cubensis (Berkeley et Curtis) Rostow, which occurs in cucurbit crops, cruciferous crops, legume crops and other plants, such as courgette, loofah, cantaloupe, spinach, melon ,, gherkins, pumpkins, lettuce, shallots, etc.

Hereinafter, in order to verify the technical features and effects of the present invention, a number of examples will be given and the drawings will be described in detail as follows.

The discarded oyster shells used in the following examples were obtained from Changhua Wanggong Fishing Port, Chiayi County Yizhu Township and Tainan Xuejia District on the western coast of Taiwan.

The results of the following examples were analyzed by one-way analysis of variance (one-way ANOVA) using SAS 6.1 (SAS Institute, Inc., Cary, NC) software, and Fisher's least significant difference method was used. significant difference, LSD) for analysis and comparison (P = 0.05).

Example 1: Pre-treatment of oysters

After scrubbing, the oyster shells were immersed in bleaching water with a concentration of 1% sodium hypochlorite for 24 hours to remove their residues, and then washed with distilled water to remove the residual sodium hypochlorite. After drying, pulverize to obtain oyster powder. Part of the oyster powder is then subjected to nano-processing such as ball milling to obtain oyster powder.

Example 2; Thermogravimetric Analysis

The oyster powder and oyster powder were analyzed by thermogravimetric analyzer respectively, and the measurement temperature was raised from room temperature to 800 ° C. The results are shown in Figure 1.

As can be seen from the results of Fig. 1, when the temperature was heated to 600°C, the oyster powder and the oyster powder began to carry out thermal decomposition reaction, and changed from calcium carbonate to calcium oxide; when the temperature was nearly 750°C, the oyster powder and the oyster powder were The weight loss slowed down, and the weight loss rates were 54.77 % and 54.83 %, respectively, indicating that the nano-treatment had little effect on the weight loss rate.

Example 3: Preparation of oyster powder

The oyster powder was first removed from water at high temperature, and then calcined under different calcination conditions, and then subjected to nano-treatment such as ball milling to obtain oyster powder treated with different calcination conditions, as shown in Table 1.

Table 1: Various oyster powder samples and their calcination conditions Sample serial number Calcination temperature (°C) Calcination time (hours) Sample serial number Calcination temperature (°C) Calcination time (hours) C-650-1-BM 650 1 C-650-6-BM 650 6 C-750-1-BM 750 1 C-750-6-BM 750 6 C-850-1-BM 850 1 C-850-6-BM 850 6 C-950-1-BM 950 1 C-950-6-BM 950 6 C-1050-1-BM 1050 1 C-1050-6-BM 1050 6 C-850-1-BM 850 1 C-1050-1-BM 1050 1 C-850-2-BM 850 2 C-1050-2-BM 1050 2 C-850-3-BM 850 3 C-1050-3-BM 1050 3 C-850-4-BM 850 4 C-1050-4-BM 1500 4 C-850-6-BM 850 6 C-1050-6-BM 1050 6

Example 4: Elemental Analysis

The oyster powder obtained by different calcination conditions in Example 3 is analyzed with a high-resolution X-ray diffractometer, wherein the instrument uses a rotating anode copper target, and the scanning range of the oyster husk powder is 2θ=10-80°, and the scanning speed is 0.025° per second, the results are shown in Figure 2A and Figure 2B.

From the results in Figure 2A, it can be seen that the oyster powder calcined at 650°C and 750°C for 1 hour has obvious diffraction peaks at 23.02°, 29.38°, 35.96°, 39.42°, 43.16°, 47.52° and 48.54°. The radiation peaks correspond to the crystal planes (012), (104), (110), (113), (202), (024) and (116) of calcite in sequence, indicating that the material composition is still calcium carbonate; When treated at 850°C for 1 hour, some weak calcium oxide diffraction peaks began to appear, indicating that the calcination temperature of 850°C was the key temperature for the transformation of oyster powder from calcium carbonate to calcium oxide; the calcination temperature of 950°C and When treated at 1,050˚C for 1 hour, the diffraction peaks appeared at 32.20˚, 37.38˚, 53.88˚, 64.22˚ and 67.46˚, indicating that the material composition was completely transformed from calcium carbonate to calcium oxide after treatment at 950˚C. The sequence is (111), (200), (220), (311) and (222). Also, from the results in Fig. 2B, it can be seen that when the calcination time is increased to 6 hours, some calcium oxide diffraction peaks begin to appear at the calcination temperature of 750°C, while those treated at the calcination temperature of 850°C appear. The diffraction peak of calcium oxide is obvious and the diffraction peak of calcium carbonate is not obvious.

Further, the oyster powder was calcined at 850°C and 1050°C for different times, and then subjected to nano-processing respectively to obtain different oyster powders, and as described above, to analyze X The light diffractometer was used for analysis, and the results were shown in Fig. 3A and Fig. 3B.

It can be seen from the results in Figure 3A that although the calcination time is different, it can be found that the diffraction peaks of calcium carbonate and calcium oxide coexist, while the diffraction peak of calcium carbonate weakens with the prolongation of calcination time, and the calcium oxide increases accordingly. Calcium carbonate cannot be completely converted into calcium oxide due to the temperature limitation; and from the results in Figure 3B, it can be seen that the diffraction peaks of calcium oxide appear in each oyster powder, and it only takes 1 hour of calcination time to convert the components into oxide. calcium.

Combining the results of FIGS. 2A and 2B , it can be clearly seen that prolonging the calcination time helps to transform the calcium carbonate in the oyster shell powder into calcium oxide; and from the results of FIG. 3A and FIG. Under this condition, the time and efficiency of converting calcium carbonate into calcium oxide can be increased.

Example 5: Particle Size Analysis

0.008 g of the oyster powders obtained by different calcination treatments in Example 3 were added to 100 mL of deionized water, and analyzed by a dynamic light scattering particle size analyzer. The results are shown in Figure 4A and Figure 4B.

Further, the oyster powder was calcined at 850°C and 1050°C for different times, and then subjected to nano-treatment respectively to obtain different oyster powders, which were analyzed as described above. Results 5A and 5B,

It can be seen from the results in FIGS. 4A and 4B that although the particle size tends to decrease as the calcination temperature increases; and from the results in FIGS. 5A and 5B , it can be seen that the change of the calcination time will not change the particle size in principle, but the temperature At 1050°C, the particle size becomes smaller as the calcination time increases.

Example 6: Surface Potential Analysis

Take 0.01 g of the oyster powder obtained by different calcination treatments in Example 3, add 100 mL of 0.1 M NaClO4 (aq), adjust to the target pH value with 0.1 M HCl (aq) and 0.1 M NaOH, and transmit through dynamic light scattering. The particle size analyzer was used for analysis, and the results are shown in FIGS. 6A and 6B .

In addition, after the oyster powder was calcined at a temperature of 850°C and 1050°C for different times, the surface potential analysis of each oyster powder was performed as described above. The results are shown in Figures 7A and 7B.

6A and 6B show that the surface potential of the oyster powder obtained by different calcination treatments will decrease due to the increase of the pH value of the solution and the increase of hydroxide ions; and the results of FIGS. 6A and 6B are compared. It was found that the potential of calcination at 950 ˚C for 1 hour and 6 hours began to show a slow upward trend at pH 8, and then dropped sharply at pH 11.

7A and 7B, it can be seen that regardless of the temperature, at the same calcination temperature, the surface potential of the oyster powder will decrease with the increase of pH in principle, but when the pH value is 8-9, the oyster powder The surface potential will rise.

Example 7: Surface functional group test

After drying the oyster powder obtained by different calcination treatments in Example 3, it was analyzed by FTIR (Fourier-transform infrared spectroscopy). The results are shown in Figure 8A and Figure 8B.

Furthermore, the effects of different calcination times on the functional groups on the surface of oyster powder were analyzed at calcination temperatures of 850°C and 1050°C, respectively. The results are shown in Figures 9A and 9B.

From the results of Figure 8A and Figure 8B, it can be seen that the initial components of these oyster powders are all calcium carbonate, and have the same trend as the calcium carbonate map. C=O) stretches and bends, and 712 cm−1 represents the calcium-oxygen bond (Ca–O).

Fig. 9A shows the graph of calcium carbonate, and with the prolongation of calcination time, the penetration wave pattern also becomes slower, indicating that calcination makes the calcium carbonate component less; and Fig. 9B shows the graph of calcium oxide, showing that after 1050˚C After treatment, calcium carbonate can be converted into calcium oxide. ,

In addition, according to the results of FIG. 2 , FIG. 8A and FIG. 8B , in the example disclosed in the present invention, regardless of the calcination time (1 hour or 6 hours) of the oyster shell, the calcination temperature is 650°C, 750°C The analytical spectrum obtained at ˚C and 850˚C is similar to that of calcium carbonate, and after calcination at 950˚C and 1050˚C, its composition has been converted to calcium oxide, so the spectrum analysis is roughly the same as that of calcium oxide; in addition. At 3643 cm-1, it can be seen that the calcium oxide particles adsorb water in the air to form Ca(OH)2 and then bond with hydroxide (Ca-OH).

Example 8: Specific Surface Analysis

The oyster powder obtained by different calcination treatments in Example 3 was subjected to adsorption and desorption tests with nitrogen gas through a specific surface area analyzer, and the degassing condition was 305 °C for 4 hours, and the specific surface area (specific surface area), The pore volume and pore size are shown in Table 2.

From the results in Table 2, it can be seen that the specific surface area of the oyster powders processed by different calcinations is greater than 1 m ² /g, and with the increase of the calcination temperature, each oyster powder is converted from calcium carbonate to calcium oxide, so its specific surface area There is a decrease in the specific surface area. Among them, when the calcination temperature is 850˚C, the components in the oyster powder are calcium carbonate and calcium oxide coexist, so the specific surface area will be higher, but with the increase of calcination time, most of the calcium carbonate is converted into calcium oxide, Therefore, the specific surface area is significantly reduced. These results show that the amount of calcium carbonate converted to calcium oxide increases when the calcination treatment is performed at the same calcination temperature, thereby increasing the specific surface area.

In addition, the pore volumes of the oyster powders subjected to different calcination treatments are all low, about 0.005-0.015 cm ³ /g; comparing the pore volume with the specific surface area, it can be seen that when the specific surface area of the oyster powder is large, the pore volume is larger .

Table 2: Analysis results of specific surface area, pore volume and pore size of each oyster powder sample Sample serial number Specific surface area (m ² /g) Pore volume (cm ³ /g) Pore size (nm) C-650-1-BM 2.23 0.014 25.28 C-750-1-BM 2.85 0.014 18.94 C-850-1-BM 3.47 0.016 18.70 C-950-1-BM 1.52 0.007 18.39 C-1050-1-BM 2.65 0.015 22.92 C-650-6-BM 2.38 0.015 25.78 C-750-6-BM 2.72 0.013 19.83 C-850-6-BM 1.80 0.010 21.71 C-950-6-BM 1.33 0.007 19.74 C-1050-6-BM 1.76 0.008 18.16 C-850-2-BM 2.47 0.014 22.29 C850-3-BM 2.56 0.016 24.97 C-850-4-BM 2.17 0.012 22.30 C-1050-2-BM 1.65 0.008 20.00 C-1050-3-BM 1.13 0.005 19.00 C1050-4-BM 1.12 0.005 19.17

Example 9: Preparation of oyster calcined powder

The oyster shells were washed, pulverized and other procedures according to the content of Example 1, and calcined at 1050 ° C for 1 hour, and then the ball milling procedure was carried out to obtain C-1050-oyster powder.

Example 10: Evaluation of the effect of prevention and control of cucumis bloom (1)

Dilute 1 g/mL C-1050-oyster powder according to the following dilution ratios: after diluting 1000, 1500, 2000, 2500, 3000, 4000, 5000, 6000 times (concentrations are 1,000, 750, 500, 400, 333 , 200, 117 ppm), and then took 10 μL drops respectively on the cut leaves of courgette, and treated ten spots on each leaf, and then inoculated P. cubensis PC-001 20 sporangia /10 μL on the treated spots by drop inoculation method. Cyst suspension (the final concentration of C-1050-oyster powder solution is 500, 375, 250, 200, 166.5, 100, 58.5 ppm in sequence), and then placed in a growth chamber at 20°C and 12 hours of light, and the disease was observed after 7 days. The occurrence of plaques and the disease rate were calculated, and the control group was treated with sterile water. The evaluation results are shown in FIGS. 10 and 11 .

The results in Figure 10 and Figure 11 show that when the dilution ratio of C-1050-oyster powder solution is 1000 times, the disease incidence rate drops significantly to 10.0%, and with the increase of the dilution ratio of C-1050-oyster powder solution, the disease incidence rate does not change significantly. , however, when the dilution ratio of C-1050-oyster powder was increased to 5000 and 6000 times, the attack rate increased to 33.3%; this showed that there was no significant difference in the control effect when the dilution ratio of oyster powder was 1000-4000 times. -1050-Oyster powder diluted more than 5000 times will have a slight impact on the control effect of exposure to bacteria, and when the dilution ratio of C-1050-Oyster powder is between 1000-2500 times, you can see obvious inoculation spots on the back of the leaves , which means the inoculation concentration is too high.

10 and 11, it can be confirmed that the oyster shell calcined powder or its solution disclosed in the present invention can indeed have the purpose of preventing and treating succulent bloom disease, wherein, the preferred application concentration is 3000 times and 4000 times the dilution of the oyster shell calcined powder. times.

Example 11: Evaluation of the effect of preventing and treating courgette bloom (2)

The steps in this example are roughly the same as in Example 10, except that the concentrations of the diluted C-1050-oyster powder solution are 0.125, 0.25, 0.5, 1, and 2 mg/ml, respectively, and the C-1050 - 24 hours after the oyster powder solution was dropped on the cut leaves of courgette, P. cubensis PC-001 20 sporangia cyst suspension (104 sporangia/mL) was inoculated, and the disease rate was observed. The results are shown in Figure 12.

It can be seen from the results in FIG. 12 that the concentration of C-1050-oyster powder at 2 mg/ml can effectively protect the cut leaves of courgette from encountering courgette blooming disease for a long time. In other words, the calcined oyster shell powder or its solution disclosed in the present invention It can indeed have the purpose of preventing succulent bloom.

without

Figure 1 shows the results of thermogravimetric analysis of oyster powder and oyster powder, in which red is oyster powder and blue is oyster powder. FIG. 2A shows the results of XRD diffraction analysis of oyster powder obtained by calcining at different temperatures for 1 hour. Figure 2B shows the results of XRD diffraction analysis of oyster powder obtained by calcining at 850°C for different times. Figure 3A shows the results of XRD diffraction analysis of oyster powder obtained by calcining at 850°C for different times. Figure 3B shows the results of XRD diffraction analysis of oyster powder obtained by calcining at 1050°C for different times. FIG. 4A shows the results of particle size analysis of oyster powder obtained by calcining at different temperatures for 1 hour. FIG. 4B shows the results of particle size analysis of oyster powder obtained by calcining at different temperatures for 6 hours. Figure 5A shows the results of particle size analysis of oyster powder obtained by calcining at 850°C for different times. Figure 5B shows the results of particle size analysis of oyster powder obtained by calcining at 1050°C for different times. FIG. 6A shows the results of surface potential analysis of oyster powder obtained by calcining at different temperatures for 1 hour. FIG. 6B shows the results of surface potential analysis of oyster powder obtained by calcining at different temperatures for 6 hours. Figure 7A shows the results of surface potential analysis of oyster powder obtained by calcining at 850°C for different times. Figure 7B shows the results of surface potential analysis of oyster powder obtained by calcining at 1050°C for different times. Figure 8A shows the results of functional group analysis of oyster powder obtained by calcining at different temperatures for 1 hour. FIG. 8B shows the results of functional group analysis of oyster powder obtained by calcination at different temperatures for 6 hours. Figure 9A shows the results of functional group analysis of oyster powder obtained by calcining at 850°C for different times. Figure 9B shows the results of functional group analysis of oyster powder obtained by calcining at 1050°C for different times. Figure 10 is a photograph of observing the control effects of oyster calcined powder solutions with different concentrations on succulent bloom. Fig. 11 is the change of the incidence of succulent bloom disease with different concentrations of oyster calcined powder solution. Fig. 12 is a graph showing the change in the incidence of succulent showroom disease by pre-dropping different concentrations of oyster calcined powder solution.

without

Claims (6)

An oyster shell powder is used for preparing a composition for preventing and treating exposure to bloom disease, wherein the main component of the oyster shell powder is calcium oxide, and the oyster shell powder is prepared by calcining the oyster shells at a temperature of 850°C or higher. Obtained after calcination for at least 1 hour. The use according to claim 1, wherein the calcination temperature is 850°C or higher and 1050°C or lower. The use as claimed in claim 1, wherein the predetermined time does not exceed 6 hours. The use according to claim 1, wherein the composition is an oyster shell powder solution prepared by diluting the oyster shell powder 1000 to 6000 times. The use according to claim 4, wherein the concentration of the oyster shell powder solution is 117 ppm or more and 1000 ppm or less. The use according to claim 5, wherein the concentration of the oyster shell powder solution is 300-400 ppm.

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