CN110818476A - Micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer and preparation method thereof - Google Patents
Micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer and a preparation method thereof. The coated slow/controlled release fertilizer consists of a composite coating material and a fertilizer, wherein the composite coating material consists of a carrier and a coating agent, and the composite coated slow/controlled release fertilizer contains 70-90% of granular fertilizer and 10-30% of the composite coating material. The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is green and environment-friendly, can greatly prolong the nutrient release period of the fertilizer, improve the utilization rate of the fertilizer, reduce the application amount of the fertilizer and reduce the cost.
Description
Technical Field
The invention relates to the technical field of agricultural slow/controlled release fertilizers, in particular to a micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer and a preparation method thereof.
Background
The fertilizer is an important guarantee for increasing the yield of grains, and the contribution rate of the fertilizer to the grain yield in the world is 50 percent. China is the country with the most fertilizers in the world, but the fertilizer utilization rate in China is generally low at present. According to statistics, the season utilization rate of the fertilizer is about 30% -35% of nitrogen, about 10% -20% of phosphorus and about 35% -50% of potassium, wherein the loss of nitrogen fertilizer is the most serious. The loss of nutrients accelerates the eutrophication and ecological imbalance of lakes and aggravates the environmental pollution. Therefore, the improvement of the fertilizer utilization rate is of great significance.
The utilization rate and utilization efficiency of the fertilizer are related to the natural environment required by the growth of crops such as soil, water, air temperature, illumination and the like, the photosynthesis performance of the crops and whether the fertilizer requirement rules of the applied fertilizer and the crops at different stages of growth are synchronous or not; and also in relation to many factors that may be lost in the soil during transport of fertilizer nutrients, such as fixation, gasification, leaching, runoff, etc. In order to improve the utilization rate and utilization efficiency of the fertilizer and achieve the purpose of increasing both production and income, Chinese technologists vigorously develop the fertilizer production and also vigorously strengthen the farmland management, establish balanced fertilization theories of formula fertilization, soil testing fertilization, plant breaking fertilization and the like, and make due contribution to the agricultural production development. However, the data of the relationship between the development of chemical fertilizers and the increase of the fertilizing amount and the grain growth rate show that the utilization rate and the utilization efficiency of the fertilizers are not improved but reduced. The key point is that the balanced fertilization principle and technology are disconnected from the actual production. The method is characterized in that the soil testing and fertilizing technologies are relatively lagged behind in the production process of farmers, and balanced fertilization is difficult to achieve, and the method is related to related technical factors such as slow release/controlled release fertilizers and soil testing and fertilizing which are products without balanced fertilization in the true sense.
The slow release/controlled release fertilizer is characterized in that on one hand, the fertilizer nutrients can be slowly released through some regulation measures, so that the losses of fixation, gasification, leaching, runoff and the like of the fertilizer are reduced, the pollution of the fertilizer to the air and water resource environment is reduced, and the supply time of the fertilizer to the crop nutrients is prolonged; meanwhile, the release rate of the fertilizer can be effectively controlled to be matched with the nutrient absorption rule of crops in different growth periods as far as possible. The utilization rate of the fertilizer is improved by more than 30 percent, so that the utilization rate and the utilization efficiency of the fertilizer can be obviously improved, and the aims of reducing the fertilization cost, reducing the environmental pollution, increasing the yield and the efficiency, improving the income of farmers and realizing the maximum social benefit and the economic benefit as much as possible are fulfilled.
At present, the slow/controlled release fertilizer in China mainly comprises urea aldehyde, sulfur coating, resin coating, fertilizer coating, natural zeolite coating, biochemical inhibitor adding and other types of slow/controlled release fertilizers. However, due to different requirements of natural environments such as climate, soil structure, paddy field, dry land and the like and agricultural and forest crops, the coating material, the coating method and the process still have a larger research and development space. Patent No. CN201310322277.1 discloses a modified trench oil coating material and application thereof in coating slow/controlled release fertilizers. The modified illegal cooking oil coating material comprises the following components in percentage by mass: 30-70% of illegal cooking oil, 20-65% of hydroxy acrylate, 0.5-5% of catalyst, 0.1-1% of polymerization inhibitor and 1-5% of crosslinking agent.
Disclosure of Invention
The invention aims to provide a micro-nano porous silicon-aluminum composite coating material coated slow/controlled release fertilizer, which can remarkably improve the slow/controlled release capability of large, medium and trace element fertilizers such as N, P, K, CA, Mg, Si, S, Zn, Mo, B and the like after the composite coated slow/controlled release material is used, reduce the losses of fixation, gasification, leaching, runoff and the like of the fertilizers, reduce the pollution of the fertilizers to the air and water resource environments and prolong the supply time of the fertilizers to crop nutrients; the release rate of the fertilizer can be effectively controlled to be matched with the nutrient absorption rule of crops in different growth periods as far as possible, and the utilization rate and the utilization efficiency of the fertilizer are improved; secondly, the fertilizer can adsorb the nutrients such as nitrogen, oxygen, water and the like in the air which are necessary for crops; but also can improve soil microcirculation, achieve the purposes of preserving water and fertilizer, improving soil and benefiting the growth of crops.
In order to achieve the purpose, the invention adopts the following technical scheme:
the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer consists of a composite coating material and a fertilizer, wherein the composite coating material consists of a carrier and a coating agent, and the mass ratio of the composite coating material to the fertilizer is 1-3: 7-9; the mass ratio of the carrier to the coating agent is 1:1.
The carrier consists of 70-90 wt% of micro-nano 3A/4A/5A type molecular sieve and 10-30 wt% of modified micro-nano 3A/4A/5A type molecular sieve.
The fertilizer comprises a controlled-release nitrogen, phosphorus and potassium single-nutrient fertilizer; the fertilizer is a compound fertilizer of nitrogen, phosphorus and potassium and a special fertilizer for paddy rice, wherein the compound fertilizer is a compound fertilizer of nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum, and the large and medium trace elements are mixed, wherein the grain diameter of fertilizer particles is 2-6 mm.
The coating agent is egg white, pig blood, cattle blood and gelatin; tung oil, pine oil, dextrin, and chitosan.
The micro-nano 3A/4A/5A type molecular sieve is modified by the following steps;
(1) according to the weight portion, 35-90 portions of silane coupling agent are dispersed in 200 portions of 100-plus-one ethanol and 200 portions of 100-plus-one monosaccharide water for hydrolysis for 30-60min, the mass ratio of the ethanol to the monosaccharide water is 1-2:1-2, then 100 portions of micro-nano 3A/4A/5A type molecular sieve are added, sodium hydroxide solution is added, the concentration of the sodium hydroxide solution is 30-60%, and the pH value of the mixed solution is 10-12; dipping for 1-3 hours, taking out the micro-nano 3A/4A/5A type molecular sieve, drying for 24 hours at room temperature, then drying for 1 hour at 50 ℃, and finally heating to 150 ℃ and drying for 2 hours;
(2) adding 10-30 parts of pore-expanding agent into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (1), and then heating and expanding pores at the temperature of 200-300 ℃;
(3) performing acid treatment on the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (2) by using a mixed solution of 200 parts of citric acid and 200 parts of diammonium hydrogen citrate, soaking for 10-30min, activating for 1-2 min by high fire at the high fire temperature of 300-500 ℃, naturally cooling, and repeating the operation for 1-2 times;
(4) adding 10-30 parts of carbon disulfide solution into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (3), treating for 2-4h by using ultrasonic waves with the ultrasonic power of 120 + 200W, washing and drying to obtain the modified micro-nano 3A/4A/5A type molecular sieve;
the carbon disulfide concentration is 300-500mgS/m3The solvent of the carbon disulfide is ethanol.
The silane coupling agent is a vinyl triethoxy silane coupling agent.
The pore-expanding agent is one or a mixture of more of mesitylene TMB, a long-chain polymer template agent, sodium polyacrylate, sesbania powder, a starch derivative or carbon black.
The monosaccharide water is one or more of glucose, ribose or fructose.
The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared by the following steps:
① according to the weight portion, 70 to 90 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 5-15 parts of coating agent by weight in a spraying manner and uniformly mixing with the fertilizer, wherein the atomizing pressure of a nozzle is 0.05-0.35PA, the pressure of compressed air is 0.4-0.8PA, and the flow rate is controlled at 400ml-
1500ml/h；
③, adding 5-15 parts by weight of 70-90% micro-nano 3A/4A/5A type molecular sieve and 10-30% modified micro-nano 3A/4A/5A type molecular sieve, and uniformly mixing;
④, naturally airing at room temperature or drying at 60-100 ℃ to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer.
The carrier modified micro-nano 3A/4A/5A molecular sieve prepared by the method can adjust the characteristics of the modified micro-nano 3A/4A/5A molecular sieve such as aperture and the like according to different fertilizers and different crops to be applied, so that the sustained and controlled release performance can meet the requirements of the crops on different fertilizer requirements at different times; the special controlled release fertilizer used on other agricultural and forestry crops such as cotton, corn, tobacco, vegetables, nursery stocks and the like related to the patent right is additionally patented. The modified micro-nano 3A/4A/5A type molecular sieve is prepared by using monosaccharide water and a silane coupling agent in a production process, any coating agent of egg white, pig blood, bovine blood, gelatin animal protein, tung oil, pine oil vegetable oil ester, dextrin and a chitosan adhesive is added into the modified micro-nano 3A/4A/5A type molecular sieve, so that double slow-release coating of nutrients is realized, the nutrients are not easy to lose, the fertilizer effect is more durable, the requirements of crops on growth in various stages can be met, the fertilizer is non-toxic and harmless to soil, a certain sterilization and anticorrosion effect is realized, the harm of bacteria to root crops can be reduced, a good growth environment is created for the growth of the plants, and the yield and the quality of the crops are improved.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1:
the micro-nano 3A/4A/5A type molecular sieve is modified by the following steps;
dispersing 35 parts of silane coupling agent in 150 parts of ethanol and 150 parts of monosaccharide water according to the weight part ratio of 1:1, hydrolyzing for 60min, adding 100 parts of micro-nano 3A/4A/5A type molecular sieve, adding sodium hydroxide solution with the concentration of 60% to ensure that the pH of the mixed solution is 10, soaking for 3 hours, taking out the micro-nano 3A/4A/5A type molecular sieve, drying for 24 hours at room temperature, then drying for 1 hour at 50 ℃, and finally heating to 150 ℃ and drying for 2 hours;
(2) adding 30 parts of pore-expanding agent into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (1), and then heating and expanding pores at the temperature of 300 ℃;
(3) performing acid treatment on the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (2) by using a mixed solution of 200 parts of citric acid and 200 parts of diammonium hydrogen citrate, soaking for 30min, then activating for 2 minutes by high fire at the temperature of 300 ℃, then naturally cooling, and repeating the operation for 2 times;
(4) adding 10-30 parts of carbon disulfide solution into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment of the step (3), treating for 2-4h by using ultrasonic waves with the ultrasonic power of 200W, washing and drying to obtain the modified micro-nano 3A/4A/5A type molecular sieve;
the concentration of the carbon disulfide is 500mgS/m3The solvent is ethanol;
the pore-expanding agent is mesitylene (TMB);
the monosaccharide water is glucose;
the fertilizer comprises a controlled-release nitrogen, phosphorus and potassium single-nutrient fertilizer; the fertilizer is a compound fertilizer of nitrogen, phosphorus and potassium and a special fertilizer for paddy rice, wherein the compound fertilizer is a compound fertilizer of nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum, and large and medium trace elements are mixed, wherein the particle size of fertilizer particles is 6 mm;
the coating agent is egg white.
The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared by the following steps:
① according to the weight portion, 70 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 15 parts by weight of coating agent and fertilizer in a spraying manner, stirring and mixing uniformly, wherein the pressure of the spray head for atomization is 0.35PA, the pressure of compressed air is 0.8PA, and the flow rate is controlled at 1500 ml/h;
③, adding 15 parts by weight of 70% micro-nano 3A/4A/5A type molecular sieve and 30% modified micro-nano 3A/4A/5A type molecular sieve, and uniformly mixing;
④ and naturally airing at room temperature or drying at 100 ℃ to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer.
The improvement rate of the rice yield and the biological yield of the applied micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer compared with the non-coated fertilizer is measured, and the results are shown in table 2 according to the qualified requirement of the industry standard HG/T3931-2007 on the nutrient release rate of the slow/controlled release fertilizer.
The controlled release performance of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer prepared in the embodiment is measured by a water immersion method, and the distilled water absorption rate of the fertilizer is 500 times of that of a water retention layer of the fertilizer measured at 25 ℃.
Example 2:
the micro-nano 3A/4A/5A type molecular sieve is modified by the following steps;
(1) according to the weight portion, 90 portions of silane coupling agent are dispersed in a mixed solution of 100 portions of ethanol and 100 portions of monosaccharide water for hydrolysis for 60min, the mass ratio of the ethanol to the monosaccharide water is 1:1, then 100 portions of micro-nano 3A/4A/5A type molecular sieve are added, and sodium hydroxide solution is added, the concentration of the sodium hydroxide solution is 30%, so that the pH value of the mixed solution is 11; soaking for 1 hour, taking out the micro-nano 3A/4A/5A type molecular sieve, drying for 24 hours at room temperature, then drying for 1 hour at 50 ℃, and finally heating to 150 ℃ and drying for 2 hours;
(2) adding 30 parts of pore-expanding agent into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (1), and then heating and expanding pores at the temperature of 200 ℃;
(3) performing acid treatment on the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (2) by using a mixed solution of 100 parts of citric acid and 100 parts of diammonium hydrogen citrate, soaking for 20min, then activating for 2 minutes by high fire at the temperature of 400 ℃, then naturally cooling, and repeating the operation for 2 times;
(4) adding 20 parts of carbon disulfide solution into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment of the step (3), treating for 2 hours by using ultrasonic waves with the ultrasonic power of 200W, washing and drying to obtain the modified micro-nano 3A/4A/5A type molecular sieve;
the concentration of the carbon disulfide is 300mgS/m3The solvent is ethanol;
the pore-expanding agent is a long-chain polymer template agent;
the monosaccharide water is ribose;
the fertilizer comprises a controlled-release nitrogen, phosphorus and potassium single-nutrient fertilizer; the fertilizer is a compound fertilizer of nitrogen, phosphorus and potassium and a special fertilizer for paddy rice, wherein the compound fertilizer is a compound fertilizer of nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum, and large and medium trace elements are mixed, wherein the grain diameter of fertilizer particles is 4 mm;
the coating agent is tung oil.
The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared by the following steps:
① according to the weight portion, 90 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 5 parts by weight of coating agent and fertilizer in a spraying manner, stirring and mixing uniformly, wherein the pressure of the spray head for atomization is 0.35PA, the pressure of compressed air is 0.8PA, and the flow rate is controlled at 1000 ml/h;
③, adding 5 parts by weight of 90% micro-nano 3A/4A/5A type molecular sieve and 10% modified micro-nano 3A/4A/5A type molecular sieve, and uniformly mixing;
④, naturally airing at room temperature or drying at 100 ℃ to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer;
the improvement rate of the rice yield and the biological yield of the applied micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer compared with the non-coated fertilizer is measured, and the results are shown in table 2 according to the qualified requirement of the industry standard HG/T3931-2007 on the nutrient release rate of the slow/controlled release fertilizer.
The controlled release performance of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer prepared by the embodiment is measured by a water immersion method, and the distilled water absorption rate of the fertilizer is 450 times of that of a water retention layer of the fertilizer measured at 25 ℃.
Example 3:
the micro-nano 3A/4A/5A type molecular sieve is modified by the following steps;
(1) according to the weight portion, 80 portions of silane coupling agent are dispersed in 100 portions of ethanol and 200 portions of monosaccharide water for 30min of hydrolysis, the mass ratio of the ethanol to the monosaccharide water is 1:2, then 100 portions of micro-nano 3A/4A/5A type molecular sieve are added, sodium hydroxide solution is added, the concentration of the sodium hydroxide solution is 30% -60%, and the pH value of the mixed solution is 12; soaking for 1 hour, taking out the micro-nano 3A/4A/5A type molecular sieve, drying for 24 hours at room temperature, then drying for 1 hour at 50 ℃, and finally heating to 150 ℃ and drying for 2 hours;
(2) adding 30 parts of pore-expanding agent into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (1), and then heating and expanding pores at the temperature of 200 ℃;
(3) performing acid treatment on the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (2) by using a mixed solution of 200 parts of citric acid and 200 parts of diammonium hydrogen citrate, soaking for 30min, then activating for 1 min by high fire, wherein the temperature of the high fire is 450 ℃, then naturally cooling, and repeating the operation for 1-2 times;
(4) adding 30 parts of carbon disulfide solution into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment of the step (3), treating for 4 hours by using ultrasonic waves with the ultrasonic power of 120W, washing and drying to obtain a modified micro-nano 3A/4A/5A type molecular sieve;
the concentration of the carbon disulfide is 400mgS/m3The solvent is ethanol;
the pore-expanding agent is sodium polyacrylate;
the monosaccharide water is fructose;
the fertilizer comprises a controlled-release nitrogen, phosphorus and potassium single-nutrient fertilizer; the fertilizer is a compound fertilizer of nitrogen, phosphorus and potassium and a special fertilizer for paddy rice, wherein the compound fertilizer is a compound fertilizer of nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum, and large and medium trace elements are mixed, wherein the grain diameter of fertilizer particles is 4 mm;
the coating agent is chitosan;
the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared by the following steps:
① according to the weight portion, 90 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 5 parts by weight of coating agent and fertilizer in a spraying manner, stirring and mixing uniformly, wherein the pressure of the spray head for atomization is 0.35PA, the pressure of compressed air is 0.6PA, and the flow rate is controlled at 1500 ml/h;
③, adding 5 parts by weight of 80% micro-nano 3A/4A/5A type molecular sieve and 20% modified micro-nano 3A/4A/5A type molecular sieve, and uniformly mixing;
④ and naturally airing at room temperature to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer.
The improvement rate of the rice yield and the biological yield of the applied micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer compared with the non-coated fertilizer is measured, and the results are shown in table 2 according to the qualified requirement of the industry standard HG/T3931-2007 on the nutrient release rate of the slow/controlled release fertilizer.
The controlled release performance of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer prepared in the embodiment is measured by a water immersion method, and the distilled water absorption rate of the fertilizer is 470 times of that of a water retention layer of the fertilizer measured at 25 ℃.
Example 4
The micro-nano 3A/4A/5A type molecular sieve is modified by the following steps;
(1) according to the weight portion, 70 portions of silane coupling agent are dispersed in 200 portions of ethanol and 100 portions of monosaccharide water for hydrolysis for 50min, the mass ratio of the ethanol to the monosaccharide water is 2:1, then 100 portions of micro-nano 3A/4A/5A type molecular sieve are added, and sodium hydroxide solution is added, the concentration of the sodium hydroxide solution is 60%, so that the pH value of the mixed solution is 10; soaking for 1 hour, taking out the micro-nano 3A/4A/5A type molecular sieve, drying for 24 hours at room temperature, then drying for 1 hour at 50 ℃, and finally heating to 150 ℃ and drying for 2 hours;
(2) adding 10 parts of pore-expanding agent into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (1), and then heating and expanding pores at the temperature of 300 ℃;
(3) performing acid treatment on the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (2) by using a mixed solution of 100 parts of citric acid and 100 parts of diammonium hydrogen citrate, soaking for 30min, then activating for 2 minutes by microwave high fire at the high fire temperature of 500 ℃, then naturally cooling, and repeating the operation for 1 time;
(4) adding 15 parts of carbon disulfide solution into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment of the step (3), treating for 2 hours by using ultrasonic waves with the ultrasonic power of 160W, washing and drying to obtain the modified micro-nano 3A/4A/5A type molecular sieve;
the concentration of the carbon disulfide is 350mgS/m3The solvent is ethanol;
the pore-expanding agent is a long-chain polymer template agent;
the monosaccharide water is ribose;
the fertilizer comprises a controlled-release nitrogen, phosphorus and potassium single-nutrient fertilizer; the fertilizer is a compound fertilizer of nitrogen, phosphorus and potassium and a special fertilizer for paddy rice, wherein the compound fertilizer is a compound fertilizer of nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum, and large and medium trace elements are mixed, wherein the particle size of fertilizer particles is 6 mm;
the coating agent is pine oil;
the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared by the following steps:
① according to the weight portion, 90 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 5 parts by weight of coating agent and fertilizer in a spraying manner, stirring and mixing uniformly, wherein the pressure of the spray head for atomization is 0.35PA, the pressure of compressed air is 0.4PA, and the flow rate is controlled at 1000 ml/h;
③, adding 5 parts by weight of 90% micro-nano 3A/4A/5A type molecular sieve and 10% modified micro-nano 3A/4A/5A type molecular sieve, and uniformly mixing;
④ and naturally airing at room temperature or drying at 100 ℃ to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer.
The improvement rate of the rice yield and the biological yield of the applied micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer compared with the non-coated fertilizer is measured, and the results are shown in table 2 according to the qualified requirement of the industry standard HG/T3931-2007 on the nutrient release rate of the slow/controlled release fertilizer.
The controlled release performance of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer prepared in the embodiment is measured by a water immersion method, and the distilled water absorption rate of the fertilizer is 440 times of that of a water retention layer of the fertilizer measured at 25 ℃.
Example 5
The micro-nano 3A/4A/5A type molecular sieve is modified by the following steps;
(1) dispersing 40 parts of silane coupling agent in 200 parts of mixed solution of ethanol and 200 parts of monosaccharide water according to the weight part ratio, hydrolyzing for 45min, wherein the mass ratio of the ethanol to the monosaccharide water is 1:1, then adding 100 parts of micro-nano 3A/4A/5A type molecular sieve, and then adding sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 60%, and the pH value of the mixed solution is 11; dipping for 3 hours, taking out the micro-nano 3A/4A/5A type molecular sieve, drying for 24 hours at room temperature, then drying for 1 hour at 50 ℃, and finally heating to 150 ℃ and drying for 2 hours;
(2) adding 25 parts of pore-expanding agent into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (1), and then heating and expanding pores at the temperature of 200 ℃;
(3) performing acid treatment on the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (2) by using a mixed solution of 200 parts of citric acid and 200 parts of diammonium hydrogen citrate, soaking for 30min, then activating for 2 min by high fire,
the high fire temperature is 500 ℃, then natural cooling is carried out, and the operation is repeated for 1 time;
(4) adding 30 parts of carbon disulfide solution into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment of the step (3), treating for 3 hours by using ultrasonic waves with the ultrasonic power of 180W, washing and drying to obtain the modified micro-nano 3A/4A/5A type molecular sieve;
the concentration of the carbon disulfide is 500mgS/m3The solvent is ethanol.
The pore-expanding agent is carbon black;
the monosaccharide water is fructose;
the fertilizer comprises a controlled-release nitrogen, phosphorus and potassium single-nutrient fertilizer; the fertilizer is a compound fertilizer of nitrogen, phosphorus and potassium and a special fertilizer for paddy rice, wherein the compound fertilizer is a compound fertilizer of nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum, and large and medium trace elements are mixed, wherein the grain diameter of fertilizer particles is 5 mm;
the coating agent is chitosan;
the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared by the following steps:
① according to the weight portion, 80 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 10 parts by weight of coating agent in a spraying manner, and uniformly mixing with the fertilizer under the conditions that the pressure of the spray head is 0.05PA, the pressure of the compressed air is 0.4PA, and the flow rate is controlled at 400 mlml/h;
③, adding 10 parts by weight of 85% micro-nano 3A/4A/5A type molecular sieve and 15% modified micro-nano 3A/4A/5A type molecular sieve, and uniformly mixing;
④ and naturally airing at room temperature or drying at 100 ℃ to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer.
The improvement rate of the rice yield and the biological yield of the applied micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer compared with the non-coated fertilizer is measured, and the results are shown in table 2 according to the qualified requirement of the industry standard HG/T3931-2007 on the nutrient release rate of the slow/controlled release fertilizer.
The controlled release performance of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer prepared in the embodiment is measured by a water immersion method, and the distilled water absorption rate of the fertilizer is 500 times of that of a water retention layer of the fertilizer measured at 25 ℃.
Example 6
The micro-nano 3A/4A/5A type molecular sieve is modified by the following steps;
(1) according to the weight portion, 70 portions of silane coupling agent are dispersed in 100 portions of ethanol and 150 portions of monosaccharide water to be hydrolyzed for 40min, the mass ratio of the ethanol to the monosaccharide water is 1:1.5, then 100 portions of micro-nano 3A/4A/5A type molecular sieve are added, and sodium hydroxide solution is added, the concentration of the sodium hydroxide solution is 60%, so that the pH value of the mixed solution is 10; dipping for 3 hours, taking out the micro-nano 3A/4A/5A type molecular sieve, drying for 24 hours at room temperature, then drying for 1 hour at 50 ℃, and finally heating to 150 ℃ and drying for 2 hours;
(2) adding 15 parts of pore-expanding agent into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (1), and then heating and expanding pores at the temperature of 200 ℃;
(3) performing acid treatment on the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (2) by using a mixed solution of 100 parts of citric acid and 150 parts of diammonium hydrogen citrate, soaking for 10min, then activating for 2 minutes by high fire at the temperature of 400 ℃, then naturally cooling, and repeating the operation for 1 time;
(4) adding 30 parts of carbon disulfide solution into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment of the step (3), treating for 3 hours by using ultrasonic waves with the ultrasonic power of 150W, washing and drying to obtain the modified micro-nano 3A/4A/5A type molecular sieve;
the concentration of the carbon disulfide is 450mgS/m3The solvent is ethanol;
the pore-expanding agent is sodium polyacrylate;
the monosaccharide water is glucose;
the fertilizer comprises a controlled-release nitrogen, phosphorus and potassium single-nutrient fertilizer; the fertilizer is a compound fertilizer of nitrogen, phosphorus and potassium and a special fertilizer for paddy rice, wherein the compound fertilizer is a compound fertilizer of nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum, and large and medium trace elements are mixed, wherein the grain diameter of fertilizer particles is 2 mm;
the coating agent is tung oil.
The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared by the following steps:
① according to the weight portion, 90 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 5 parts by weight of coating agent and fertilizer in a spraying manner, stirring and mixing uniformly, wherein the pressure of the spray head for atomization is 0.05PA, the pressure of compressed air is 0.8PA, and the flow rate is 1500 ml/h;
③, adding 5 parts by weight of 70% micro-nano 3A/4A/5A type molecular sieve and 30% modified micro-nano 3A/4A/5A type molecular sieve, and uniformly mixing;
④ and naturally airing at room temperature or drying at 100 ℃ to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer.
The improvement rate of the rice yield and the biological yield of the applied micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer compared with the non-coated fertilizer is measured, and the results are shown in table 2 according to the qualified requirement of the industry standard HG/T3931-2007 on the nutrient release rate of the slow/controlled release fertilizer.
The controlled release performance of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer prepared in the embodiment is measured by a water immersion method, and the distilled water absorption rate of the fertilizer is 460 times that of the water retention layer of the fertilizer measured at 25 ℃.
Comparative example 1: the following procedure is different from example 6, and the rest is the same as example 6
The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared by the following steps:
① according to the weight portion, 90 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 5 parts by weight of coating agent and fertilizer in a spraying manner, stirring and mixing uniformly, wherein the pressure of the spray head for atomization is 0.05PA, the pressure of compressed air is 0.8PA, and the flow rate is 1500 ml/h;
③, adding 5 parts by weight of micro-nano 3A/4A/5A type molecular sieve with the weight percentage of 40% and 60% of modified micro-nano 3A/4A/5A type molecular sieve, and uniformly mixing;
④ and naturally airing at room temperature or drying at 100 ℃ to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer.
The improvement rate of the rice yield and the biological yield of the applied micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer compared with the non-coated fertilizer is measured, and the results are shown in table 2 according to the qualified requirement of the industry standard HG/T3931-2007 on the nutrient release rate of the slow/controlled release fertilizer.
The controlled release performance of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer prepared in the embodiment is measured by a water immersion method, and the distilled water absorption rate of the fertilizer is 320 times that of a water retention layer of the fertilizer measured at 25 ℃.
Comparative example 2: the micro-nano 3A/4A/5A type molecular sieve is not modified, and the steps are as follows;
the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared by the following steps:
① according to the weight portion, 90 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 5 parts by weight of coating agent and fertilizer in a spraying manner, stirring and mixing uniformly, wherein the pressure of the spray head for atomization is 0.05PA, the pressure of compressed air is 0.8PA, and the flow rate is 1500 ml/h;
③ adding 5 parts by weight of 100% micro-nano 3A/4A/5A type molecular sieve, and mixing;
④ and naturally airing at room temperature or drying at 100 ℃ to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer.
The fertilizer comprises a controlled-release nitrogen, phosphorus and potassium single-nutrient fertilizer; the fertilizer is a compound fertilizer of nitrogen, phosphorus and potassium and a special fertilizer for paddy rice, wherein the compound fertilizer is a compound fertilizer of nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum, and large and medium trace elements are mixed, wherein the grain diameter of fertilizer particles is 2 mm;
the coating agent is tung oil.
The improvement rate of the rice yield and the biological yield of the applied micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer compared with the non-coated fertilizer is measured, and the results are shown in table 2 according to the qualified requirement of the industry standard HG/T3931-2007 on the nutrient release rate of the slow/controlled release fertilizer.
The controlled release performance of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer prepared by the embodiment is measured by a water immersion method, the dissolution rate is 0.7% at the initial stage, and the controlled release period is 135 days. The rate of absorbing distilled water was 350 times as high as the water-retaining layer thereof, as measured at 25 ℃.
Comparative example 3: the coated controlled-release fertilizer is prepared according to the patent number CN201310322277.1
The improvement rate of the rice yield and the biological yield of the slow controlled release fertilizer prepared by applying the patent compared with the rice yield and the biological yield of a non-coated fertilizer is measured according to the qualified requirement of the industry standard HG/T3931-2007 on the nutrient release rate of the slow controlled release fertilizer, and the result is shown in Table 2.
The controlled release performance of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer prepared in the embodiment is measured by a water immersion method, and the distilled water absorption rate of the fertilizer is 300 times of that of a water retention layer of the fertilizer measured at 25 ℃.
Experimental example 1: under the condition that the fertilizer application nutrient consumption per mu is equal, applying modified micro-nano 4A molecular sieve coated slow/controlled release nitrogen, phosphorus and potassium single-nutrient fertilizer, modified micro-nano 5A molecular sieve coated slow/controlled release nitrogen, phosphorus and potassium compound fertilizer, modified micro-nano 3A molecular sieve coated slow/controlled release nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum large and medium trace element compound rice special fertilizer, and measuring the yield improvement rate, the biological yield improvement rate, the nitrogen fertilizer absorption utilization rate improvement rate, the water retention improvement rate and the like of rice by taking a comparative example 3 as a reference, wherein the results are shown in the following table;
TABLE 1
TABLE 2
It can be seen from the example 6 and the comparative examples 1-2 that the slow/controlled release performance of the micro-nano composite coated slow/controlled release fertilizer is reduced and the utilization rate of the fertilizer is reduced without or with the modified micro-nano 3A/4A/5A type molecular sieve, and the rice yield and the biological yield of the applied micro-nano composite coated slow/controlled release fertilizer are both obviously improved compared with the non-coated fertilizer, which indicates that the coated slow/controlled release fertilizer has less loss and pollution to the water source environment, high utilization rate and utilization efficiency, and the slow/controlled release effect of the fertilizer can be effectively improved.
In the early period, the nutrients in the examples 1 to 6 are released slowly, the nutrients in the comparative examples 1 to 3 are released quickly, the nutrient release rate of the examples 1 to 6 reaches the highest within 60 to 80 days, and the slow/controlled release fertilizers in the examples 1 to 6 still release the nutrients within 140 days, but the nutrients in the comparative examples 1 to 3 are not released basically, so that the nutrient release period of the fertilizers is greatly prolonged, the utilization rate of the fertilizers is improved, the application amount of the fertilizers is reduced, and the cost is reduced.
And the fertilizer release rule is basically synchronous with the growth rule of crops, the fertilizer efficiency is long, the fertilizer supply is stable, the requirements of normal growth and development of the hybrid rice in one season on large and medium trace element fertilizers can be effectively met, the effective spike number is obviously increased, the maturing rate is improved, the yield is increased, and the effect of protecting the environment is achieved.
Claims (10)
1. The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is characterized in that: the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer consists of a composite coating material and a fertilizer, wherein the composite coating material consists of a carrier and a coating agent, and the mass ratio of the composite coating material to the fertilizer is 1-3: 7-9; the mass ratio of the carrier to the coating agent is 1:1.
2. The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer of claim 1, characterized in that:
the carrier consists of 70-90% of micro-nano 3A/4A/5A type molecular sieve and 10-30% of modified micro-nano 3A/4A/5A type molecular sieve in percentage by weight.
3. The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer of claim 1, wherein the fertilizer comprises a slow/controlled release nitrogen, phosphorus and potassium single nutrient fertilizer; the fertilizer is a compound fertilizer of nitrogen, phosphorus and potassium and a special fertilizer for paddy rice, wherein the compound fertilizer is a compound fertilizer of nitrogen, phosphorus, potassium, calcium, magnesium, silicon, sulfur, zinc, boron and molybdenum, and the large and medium trace elements are mixed, wherein the grain diameter of fertilizer particles is 2-6 mm.
4. The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer of claim 1, characterized in that:
the coating agent is egg white, pig blood, cattle blood and gelatin; tung oil, pine oil, dextrin, and chitosan.
5. The preparation method of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer as claimed in claims 1-4, characterized in that 10-30% of the modified micro-nano 3A/4A/5A type molecular sieve is modified by the following steps;
(1) according to the weight portion, 35-90 portions of silane coupling agent are dispersed in 200 portions of 100-plus-one ethanol and 200 portions of 100-plus-one monosaccharide water for hydrolysis for 30-60min, the mass ratio of the ethanol to the monosaccharide water is 1-2:1-2, then 100 portions of micro-nano 3A/4A/5A type molecular sieve are added, sodium hydroxide solution is added, the concentration of the sodium hydroxide solution is 30-60%, and the pH value of the mixed solution is 10-12; soaking for 1-3 hours, taking out the micro-nano 3A/4A/5A type molecular sieve, drying for 24 hours at room temperature, then drying for 1 hour at 50 ℃, and finally heating to 150 ℃ and drying for 2 hours;
(2) adding 10-30 parts of pore-expanding agent into the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (1), and then heating and expanding pores at the temperature of 200-300 ℃;
(3) performing acid treatment on the micro-nano 3A/4A/5A type molecular sieve obtained after the treatment in the step (2) by using a mixed solution of 200 parts of citric acid and 200 parts of diammonium hydrogen citrate, soaking for 10-30min, taking out, activating for 1-2 min by high fire at the temperature of 300-500 ℃, naturally cooling, and repeating the operation for 1-2 times;
(4) and (4) adding 10-30 parts of carbon disulfide solution into the micro-nano 3A/4A/5A molecular sieve obtained after the treatment in the step (3), treating for 2-4h by using ultrasonic waves with the ultrasonic power of 120 + 200W, washing and drying to obtain the modified micro-nano 3A/4A/5A molecular sieve.
6. The micro-nano porous silicon-aluminum material composite coating slow/control system of claim 5The fertilizer release is characterized in that: the carbon disulfide concentration in the step (4) is 300-500mgS/m3The solvent of the carbon disulfide is ethanol.
7. The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer of claim 5, characterized in that: the silane coupling agent is a vinyl triethoxy silane coupling agent.
8. The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer of claim 5, characterized in that: the pore-expanding agent is one or a mixture of more of mesitylene (TMB), a long-chain polymer template agent, sodium polyacrylate, sesbania powder, a starch derivative or carbon black.
9. The micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer of claim 5, characterized in that: the monosaccharide water is one or more of glucose, ribose or fructose.
10. The preparation method of the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer as claimed in claims 1-9, characterized in that the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer is prepared according to the following steps:
① according to the weight portion, 70 to 90 portions of granulated fertilizer by weight portion is put into the mixer, and the mixer is started to stir;
② adding 5-15 parts of coating agent by weight in a spraying manner, and uniformly mixing with the fertilizer under the conditions of nozzle atomization pressure of 0.05-0.35PA, compressed air pressure of 0.4-0.8PA and flow rate of 400-1500 ml/h;
③, adding 70-90% of micro-nano 3A/4A/5A type molecular sieve and 10-30% of modified micro-nano 3A/4A/5A type molecular sieve in parts by weight, and uniformly mixing;
④, naturally airing at room temperature or drying at 60-100 ℃ to obtain the micro-nano porous silicon-aluminum material composite coated slow/controlled release fertilizer.
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