CN107556062A - Quenched from flyash the method that water-soluble silicon prepares multiplex siliceous fertilizer - Google Patents

Abstract

A kind of method that water-soluble silicon prepares multiplex siliceous fertilizer of being quenched from flyash, flyash is added to the water, and is well mixed, is then added the concentrated sulfuric acid, under conditions of sealing after stirring reaction, is stacked storage, is carried out ageing reaction, obtain water soluble quick-acting siliceous fertilizer；Water soluble quick-acting siliceous fertilizer is crushed to the mesh of 100 mesh~200, adds ammonium salt, pH value is adjusted, obtains water-soluble quick-acting, the molten long-acting weak acid of Chinese holly, neutrality or alkalescent siliceous fertilizer；After weak acid, neutrality or alkalescent siliceous fertilizer are granulated with comminutor, the obtained quick-acting siliceous fertilizers of siliceous fertilizer particles with water dissolubility carry out coating, obtain multiplex siliceous fertilizer granule.Advantage is:Using flyash as raw material, cost is cheap, and the multiplex siliceous fertilizer granule of preparation both has immediate effect functional effect, there is long-acting controlled release N release rate again, make full use of that China's Industrial " three Waste " cost is low, and dosage is few, China's agricultural rises, and can increase income, and has good social benefit.

Description

Method for preparing multi-element silicon fertilizer by quenching water-soluble silicon from fly ash

technical field

The invention relates to a method for extracting water-soluble silicon from fly ash to prepare multi-element silicon fertilizer.

Background technique

my country is a big country in agricultural production, but the low utilization rate of fertilizers, insufficient and expensive medium and trace elements are the main problems at present. Silicon fertilizer, some in our country appear in the name of soil improver, calcium, magnesium, phosphate fertilizer and so on. The only silicon fertilizer industry standard NY/T797-2004. It is a silicon fertilizer with ironmaking slag, yellow phosphorus slag, potassium feldspar, sea ore, red mud, fly ash, etc. as the main raw materials, and available silicon (SiO ₂ ) as the main marked amount. Although there is no requirement for pH in the NY/T797-2004 standard, they are all alkaline-strongly alkaline. There are many alkaline "effective silicon fertilizer" products in my country, which are only suitable for acidic red soil, but acidic, weakly acidic, and weakly alkaline "water-soluble quick-acting silicon fertilizers" have not been found, especially quick-acting and long-acting silicon fertilizers that can be used in acid-base soils There is no record of fat.

Fly ash is the fine ash collected from the flue gas after coal combustion. Fly ash is the main solid waste discharged from coal-fired power plants. Due to the rapid development of our country and the rapid growth of electricity consumption, coal-fired power plants are still the main power source in our country. The annual production of "three wastes" fly ash is 100-200 million tons, and the total utilization rate is less than 50%. It is used in agriculture. of less than 10%. According to the data of China Urban and Rural Construction Fly Ash Utilization Technology Development Center, the annual output of fly ash in my country is about 100-200 million tons, and the overall utilization rate is less than 50%. The total storage capacity is 500 million to 1 billion tons, covering an area of 50 million to 200 million mu. Social problems that need to be solved urgently, especially in the coal resource-rich provinces around Beijing, Tianjin, and Hebei, Shanxi, Shaanxi, Inner Mongolia, the three northeastern provinces, Shandong, and Xinjiang.

Because the fly ash of power plants in China is basically a strong alkaline substance (individuals are weakly alkaline), its main constituent elements (oxides) are: SiO ₂ , CaO, Al ₂ O ₃ , TFeO (FeO+Fe ₂ O ₃ ), TiO ₂ , MgO, K ₂ O, NaO, SO ₃ , MnO, P ₂ O ₅ , Cl, etc., the order of their content is roughly arranged in this way. Practice has proved that its water solubility is poor and its viscosity is very low. Therefore, it is used in agricultural fertilizers as silicon fertilizers, the dosage is too large, the transportation cost is high, and it can only be applied to acidic soil, and it can be absorbed by plants only after being decomposed by some enzymes in the soil. The cost is high, the effect is slow, and the increase in production does not increase income.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method of extracting water-soluble silicon from fly ash to prepare multi-element silicon fertilizer, which uses fly ash as raw material, has low cost, high water-soluble silicon content, easy absorption by plants, and increased crop production and income. method.

Technical solution of the present invention is:

A method for extracting water-soluble silicon from fly ash to prepare multi-element silicon fertilizer, the specific steps are:

(1) Quench water-soluble silicon from fly ash

According to the parts by weight, add 100 parts of fly ash to 10 parts to 25 parts of water, mix well, then add 11 parts to 40 parts of concentrated sulfuric acid, stir and react under sealed conditions, the reaction temperature is 80 ° C ~ 250 ° C, the reaction The time is 5min-20min, stacked and stored for more than 24h, and the aging reaction is carried out to obtain the water-soluble quick-acting silicon fertilizer;

(2) Preparation of weak acid, neutral or weak alkaline silicon fertilizer

Pulverize the water-soluble quick-acting silicon fertilizer prepared in step (1) to 100-200 mesh, add ammonium salt, adjust the pH value, and obtain water-soluble quick-acting, citrate-soluble and long-acting weakly acidic, neutral or weakly alkaline silicon fertilizer;

(3) Granulation

After the weak acid, neutral or weakly alkaline silicon fertilizer prepared in step (2) is granulated with a granulator, the obtained silicon fertilizer granules are coated with the water-soluble quick-acting silicon fertilizer prepared in step (1), and the silicon fertilizer The mass ratio of the fertilizer granules to the water-soluble quick-acting silicon fertilizer is 1:0.003-1:0.005 to obtain multi-element silicon fertilizer granules.

Further, when the pH value is adjusted to alkaline in step (2), the ammonium salt is ammonium bicarbonate.

Further, when the pH value is adjusted to acidic or neutral in step (2), the ammonium salt is ammonium sulfate and ammonium bicarbonate.

Further, when granulating the weakly acidic, neutral or weakly alkaline silicon fertilizer, at least one of nitrogen fertilizer, phosphorus fertilizer, and medium and trace element fertilizer can also be added according to the nutrient requirement of the soil.

Further, the aging time of step (1) is 1 day to 30 days, and the longer the aging time, the higher the soluble silicon content.

Further, the stirring reaction temperature in step (1) is 120° C. to 180° C., the reaction time is 5 minutes, and the aging time is 1 day to 15 days.

Further, in step (1), the mass ratio of water to concentrated sulfuric acid is 1:1.1˜1:1.6.

Further, the mass percentage of silicon in the fly ash is 55%-65%, the mass percentage of calcium is 3%-8%, and the fineness of the fly ash is 100-200 mesh.

Further, the mass concentration of the concentrated sulfuric acid is 90%-96%.

Further, the pH value of the fly ash is 7.4-10.

Beneficial effects of the present invention:

(1) Using one of the industrial "three wastes" that seriously occupies land and pollutes the atmosphere, the fly ash of the power plant is used as the basic raw material, and the available silicon, calcium and other elements (water-insoluble citrate) required for plant growth contained in it are used State silicon, calcium and other elements) through chemical and physical reactions to obtain not only some water-soluble quick-acting silicon, calcium and other elements, but also some citrate-soluble silicon, calcium and other elements, becoming a product with both quick-acting effect and long-acting citrate-soluble effect Water-soluble quick-acting silicon fertilizer, without drying process, its water content can be controlled below 5%. The process is simple, safe, environmentally friendly, and pollution-free to meet the standard control indicators, improve the soil, provide beneficial elements to plants, and increase the utilization rate of N and P ₂ O ₅ , contributing to low-cost farmers' income and social benefits.

(2) The prepared multi-element silicon fertilizer granules not only have quick-acting functional effects, but also have long-acting, controlled-release N release rate effects, and make full use of my country's industrial "three wastes". The cost is low and the dosage is small. , and can increase income and create social benefits of "domestic" products.

detailed description

Example 1

(1) Quench water-soluble silicon from fly ash

Fly ash (the mass percentage content of silicon is 55%, the mass percentage content of calcium is 8%, the pH value is 7.4, and the fineness is 100 mesh) 100kg, H ₂ SO ₄ (mass concentration is 90%) 10kg and H ₂ O 11L, stirred and reacted at 120°C under sealed conditions, the reaction time was 20 minutes, stacked and stored for 24 hours;

A product with a water-soluble silicon content of 18 wt%, a pH of 4.05 and a water content of 5% was obtained. Explanation: In the case of 120°C, the chemical reaction and material change of 10 parts of H ₂ SO ₄ and 11 parts of H ₂ O are used to achieve the purpose of preliminary product indicators. The application effect is obvious on plants such as rice in saline-alkali land, and the dosage is 15%wt-20%wt of that of common effective silicon fertilizer.

(2) Preparation of weakly alkaline silicon fertilizer

The water-soluble quick-acting silicon fertilizer prepared in step (1) is pulverized to 100 mesh and weighed 70 kg, and 30 kg of ammonium bicarbonate is added to obtain a water-soluble quick-acting, citrate-soluble and long-acting weakly alkaline silicon fertilizer;

(3) Granulation

After the weakly alkaline silicon fertilizer prepared in step (2) is granulated with a granulator, the obtained silicon fertilizer particles are coated with the water-soluble quick-acting silicon fertilizer prepared in step (1), and 1 ton of silicon fertilizer particles uses 3 kg The water-soluble quick-acting silicon fertilizer is coated to obtain multi-element silicon fertilizer granules.

The product has an effective silicon content of 42%, water-soluble silicon accounts for more than 15% of the effective silicon content, ammonium nitrogen content of 5.0%, product pH value of 7.30, and water content of <5%; this product contains nitrogen in addition to silicon Rate changed from 22% to 50% ammonium nitrogen. No matter the saline-alkali soil in the north or the acidic red soil in the south are all products that can be used effectively, increase production and increase income. Its dosage is 1/5~1/6 of ordinary effective silicon fertilizer, the cost is 1/2~1/3 of effective silicon fertilizer, and the silicon content is 180%~220% of the standard "silicon fertilizer" index. The more important thing is that farmers increase income.

Example 2

(1) Quench water-soluble silicon from fly ash

Add 100kg of fly ash (the mass percentage of silicon is 60%, the mass percentage of calcium is 5%, and the fineness is 200 mesh) into 25kg of water, mix evenly, then add 35kg of 92% concentrated sulfuric acid, seal the Under the conditions of stirring reaction, the reaction temperature is 180 ° C, the reaction time is 5 minutes, stacked and stored for 240 hours, and the aging reaction is carried out to obtain a water-soluble quick-acting silicon fertilizer;

(2) Preparation of weakly alkaline silicon fertilizer

The water-soluble quick-acting silicon fertilizer prepared in step (1) is pulverized to 200 meshes and weighed 60 kg, and 40 kg of ammonium bicarbonate is added to obtain a water-soluble quick-acting, citrate-soluble and long-acting weakly alkaline silicon fertilizer;

(3) Granulation

After the weakly alkaline silicon fertilizer prepared in step (2) is granulated with a granulator, the obtained silicon fertilizer particles are coated with the water-soluble quick-acting silicon fertilizer prepared in step (1), and 1 ton of silicon fertilizer particles uses 5 kg The water-soluble quick-acting silicon fertilizer is coated to obtain multi-element silicon fertilizer granules.

The product has an effective silicon content of 36%, water-soluble silicon accounts for more than 15% of the available silicon, ammonium nitrogen content of 6.7%, product pH value of 7.5, and granules with a water content of <5%. The effective silicon content of this product is the standard "silicon fertilizer" index 165% to 180% of nitrogen, and also contains nitrogen rate> 50% ammonium nitrogen; this product is popular in northern my country.

Example 3

(1) Quench water-soluble silicon from fly ash

According to parts by weight, 100kg of fly ash (the mass percentage of silicon is 65%, the mass percentage of calcium is 3%, and the fineness is 150 mesh) is added into 25kg of water, mixed evenly, and then added 40kg of 96% Concentrated sulfuric acid was stirred and reacted under sealed conditions, the reaction temperature was 250°C, the reaction time was 5 minutes, stacked and stored for 30 days, and the aging reaction was carried out to obtain water-soluble quick-acting silicon fertilizer;

After the reaction, aging conditions and time are very important. Taking 30 days of aging as an example, it is manifested in three aspects: (1) pH value increases (acid oxygen release rate) by 2.2 to 4.5 times; (2) water content decreases (evaporation) 2.10% to 3.00%, the water-soluble silicon content increased by 2% to 8%;

(2) Preparation of neutral silicon fertilizer

The water-soluble quick-acting silicon fertilizer prepared in step (1) is pulverized to 150 mesh and weighed 50 kg, and 20 kg of ammonium sulfate and 30 kg of ammonium bicarbonate are added to obtain a water-soluble quick-acting, citrate-soluble and long-acting neutral silicon fertilizer;

(3) Granulation

After the neutral silicon fertilizer prepared in step (2) is granulated with a granulator, the obtained silicon fertilizer particles are coated with the water-soluble quick-acting silicon fertilizer prepared in step (1), and 1 ton of silicon fertilizer particles uses 4 kg of water-soluble The quick-acting silicon fertilizer is coated to obtain multi-element silicon fertilizer granules.

The effective silicon 30% of the product index is 150% of the standard "silicon fertilizer" index, the nitrogen content is 9% (the utilization rate of nitrogen in ammonium sulfate can be increased from 45% to 60%), and the pH value is 7, which is popular in both the north and the south of my country. The product.

Example 4

(1) Quench water-soluble silicon from fly ash

According to the parts by weight, add 100kg of fly ash to 15 parts of water, mix evenly, then add 20 parts of concentrated sulfuric acid, stir and react under sealed conditions, the reaction temperature is 80°C, the reaction time is 10min, stack and store for 24h, and carry out aging chemical reaction to obtain water-soluble quick-acting silicon fertilizer;

(2) Preparation of weakly acidic silicon fertilizer

The water-soluble quick-acting silicon fertilizer that step (1) prepares is pulverized to 100 orders and takes by weighing 45kg, adds urea 15kg, ammonium chloride 15kg, ammonium sulfate 10kg, common calcium superphosphate 13kg, zinc sulfate 2kg, obtains water-soluble quick-acting, citrate dissolve long-term Efficient weakly acidic silicon fertilizer;

(3) Granulation

After the weakly acidic silicon fertilizer prepared in step (2) is granulated with a granulator, the obtained silicon fertilizer granules are coated with the water-soluble quick-acting silicon fertilizer prepared in step (1), and 1 ton of silicon fertilizer granules use 5 kg of water-soluble The quick-acting silicon fertilizer is coated to obtain multi-element silicon fertilizer granules.

The product contains 25% silicon (130% of the standard), ammonium nitrogen content 12.71%, available phosphorus content 2%, calcium content 6.75%, sulfur content 20.5%, zinc content 0.4%, iron content 0.45%, pH value 5.95, It is a "triammonium" product that is very popular in calcareous soils in the north (the utilization rate of nitrogen is increased by an average of 10-30%).

Physicochemical index test of water-soluble silicon quenched in the fly ash prepared by the method of the present invention

Add fly ash to water, mix evenly, then add concentrated sulfuric acid, stir and react under sealed conditions, the reaction temperature is 80°C-250°C, the reaction time is 5min, stack and store for 24h-720h, and perform aging reaction to obtain water-soluble Quick-acting silicon fertilizer; its reaction conditions and physical and chemical properties of the product are as shown in Table 1, different data indicators of water-soluble quick-acting silicon fertilizer obtained at different temperatures, different proportions, and different aging times (T).

Table 1

Field Test Report on Fertilizer Efficiency Identification of Silicon Fertilizer

1. Purpose of the test

The silicon fertilizer produced by Liaoning Dongmeng Fertilizer Technology Co., Ltd. is fly ash treated with sulfuric acid, which contains water-soluble silicon accounting for more than 18% of the available silicon, which can enhance the disease resistance and lodging resistance of rice, increase yield and improve quality. To verify its fertilizer efficiency, we conducted experiments on rice crops.

2. Materials and methods

1. Materials for testing: (1) Silicon fertilizer: containing effective silicon ≥ 20%, and water-soluble silicon accounting for more than 18%. Compound fertilizer (20-8-12);

2. Test crop: rice

3. Test location: Linghai, Panjin

4. Soil for test: paddy soil

5. Test treatment:

(1) CK conventional fertilization (compound fertilizer 50kg/mu)

(2) CK+ the embodiment of the present invention 1 multi-element silicon fertilizer granule 10kg/ mu (CK+)

(3) CK+ the embodiment of the present invention 1 multi-element silicon fertilizer granule 25kg/ mu (CK+)

(4) CK+ the embodiment of the present invention 1 multi-element silicon fertilizer granule 50kg/ mu (CK+)

6. Field design: no repetition is set for the experiment, and the plot area is 33m ² ;

7. Time and method of fertilization:

Treatment (1) Evenly sprinkle all the compound fertilizer on the surface before raking the ground, and rake it into the soil layer: Treatment (2), treatment (3) Mix all the multi-element silicon fertilizer granules and compound fertilizer evenly, Sprinkle on the ground before; 25kg of multi-element silicon fertilizer granules in treatment (4) is applied in the same way as treatment (3), 25kg is topdressed at the tillering stage, and other management is carried out according to local customs.

3. Results and analysis

The experiments were conducted in Ping'an Village, Jianye Township, Linghai City, Jinzhou (2014), Manjingzi Village, Xibaqian Township (2015), and Jiangnan Village, Qingshui Town, Dawa County, Panjin City.

1. Effects on rice growth traits

Table 2 of the survey results of growth traits shows that the application of multi-element silicon fertilizer granules in Example 1 of the present invention to rice can promote the growth of rice compared with conventional fertilization (CK).

Table 2 Survey table of rice growth traits

2. Impact on rice yield and benefit

From Table 3 of the yield survey results, the trend of each year is consistent, and the application of silicon fertilizer increases the yield compared with conventional fertilization, with an average increase of 20-55kg of rice per mu, and the yield increase rate is 3.2%-8.1%; the input-output ratio is 4:1-6 : 1, wherein 50kg of multi-element silicon fertilizer granules obtained with mu application has the best effect.

Table 3 Rice Yield Survey Form

4. Conclusion

1, the multi-element silicon fertilizer granule of the present invention has yield increasing effect to paddy rice;

2. The application of multi-element silicon fertilizer granules can also enhance the lodging resistance of rice;

3. Apply multi-element silicon fertilizer granules to increase the economic benefits of rice;

4. Multi-element silicon fertilizer granules can be widely used in rice production.

Mechanism of increasing rice yield by applying multi-element silicon fertilizer granules:

The growth of rice requires a lot of silicon, but the acidic soil in the south is not completely lacking in silicon; most of them are not lacking in silicon and calcium. The reason why alkaline effective silicon and calcium fertilizers increase the yield of rice in acidic soil is that alkaline silicon activates ineffective silicon in acidic soil and acidic siliciophilic bacteria, and alkaline silicon is needed to maintain its reproduction, which is convenient for rice to absorb silicon. Increase to make the conduction tissue of rice developed, which is conducive to the transmission of oxygen to the root system, thereby enhancing the oxygen capacity of the root system and improving the ability of the root system to absorb various nutrients. The stem is thicker, the leaves are firmer, the root system is developed, and there is no premature aging Phenomenon. These traits improve lodging resistance, are beneficial to photosynthesis, and prolong the time of photosynthesis, so the yield is increased.

Our three-year practice in Panjin and its surrounding areas, the largest saline-alkaline soil rice production area in Northeast China, has proved that: three days (72h) of applying modified water-soluble and available silicon elements, rice stems are firm and new roots (white roots) It is 5-15mm longer than the control group CK, and some plots will produce white new roots within 24 hours; when multi-element silicon fertilizer granules are applied, the rice can absorb silicon as soon as possible, and the yield is 10-35% higher than that of the control group CK. "Silicon" increases production by 5-20%, and is called by rice farmers: the first time to see the magic fertilizer.

The rational ratio of the water-soluble quick-acting silicon fertilizer and nitrogen prepared by the invention is the long-acting nitrogen fertilizer. Chemical fertilizers urea, ammonium bicarbonate, and ammonium sulfate have nitrogen utilization rates of 30-35%, 20-22%, and 40-45%, respectively. Adding water-soluble quick-acting silicon fertilizer, resulting in granular, multi-element silicon fertilizer has obvious effect on increasing production, and the data is basically the same as that of Southwest University of Science and Technology and Mianyang Agricultural Bureau. The utilization ratios are respectively increased by 8-12%, 15-30%, and 10-15%.

The above are only specific embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A method for preparing multi-element silicon fertilizer by quenching water-soluble silicon from fly ash, is characterized in that: The specific steps are: (1) Quenching water-soluble silicon from fly ash According to the parts by weight, add 100 parts of fly ash to 10 parts to 25 parts of water, mix well, then add 11 parts to 40 parts of concentrated sulfuric acid, stir and react under sealed conditions, the reaction temperature is 80 ° C ~ 250 ° C, the reaction The time is 5min-20min, stacked and stored for more than 24h, and the aging reaction is carried out to obtain the water-soluble quick-acting silicon fertilizer; (2) Preparation of weak acid, neutral or weak alkaline silicon fertilizer Pulverize the water-soluble quick-acting silicon fertilizer prepared in step (1) to 100-200 mesh, add ammonium salt, adjust the pH value, and obtain water-soluble quick-acting, citrate-soluble and long-acting weakly acidic, neutral or weakly alkaline silicon fertilizer; (3) Granulation After the weak acid, neutral or weakly alkaline silicon fertilizer prepared in step (2) is granulated with a granulator, the obtained silicon fertilizer granules are coated with the water-soluble quick-acting silicon fertilizer prepared in step (1), and the silicon fertilizer The mass ratio of the fertilizer granules to the water-soluble quick-acting silicon fertilizer is 1:0.003-1:0.005 to obtain multi-element silicon fertilizer granules. 2. the method for preparing multi-element silicon fertilizer by quenching water-soluble silicon from fly ash according to claim 1, is characterized in that: when step (2) adjusts pH value to alkaline, described ammonium salt is bicarbonate Ammonium. 3. the method for preparing multi-element silicon fertilizer by quenching water-soluble silicon from fly ash according to claim 1, is characterized in that: when step (2) adjusts the pH value to acidity or neutrality, described ammonium salt is Ammonium sulfate and ammonium bicarbonate. 4. the method for preparing multi-element silicon fertilizer by quenching water-soluble silicon from fly ash according to claim 1, is characterized in that: when weakly acidic, neutral or weakly alkaline silicon fertilizer is granulated, according to the nutritional requirements of soil amount, adding at least one of nitrogen fertilizer, phosphorus fertilizer, and medium and trace element fertilizer. 5. The method for preparing multi-element silicon fertilizer by extracting water-soluble silicon from fly ash according to claim 1, characterized in that: the aging time of step (1) is 1 day to 30 days. 6. The method for preparing multi-element silicon fertilizer by quenching water-soluble silicon from fly ash according to claim 1, characterized in that: the stirring reaction temperature in step (1) is 120°C to 180°C, and the reaction time is 5min , the aging time is 1 day to 15 days. 7. the method for preparing multi-element silicon fertilizer by quenching water-soluble silicon from fly ash according to claim 1, is characterized in that: in step (1), the mass ratio of described water and concentrated sulfuric acid is 1:1.1～ 1:1.6. 8. The method for preparing multi-element silicon fertilizer by quenching water-soluble silicon from fly ash according to claim 1, characterized in that: the mass percentage of silicon in the fly ash is 55% to 65%, calcium The mass percent content of the fly ash is 3% to 8%, and the fineness of the fly ash is 100 to 200 mesh. 9. The method for preparing multi-element silicon fertilizer by extracting water-soluble silicon from fly ash according to claim 1, characterized in that: the mass concentration of the concentrated sulfuric acid is 90% to 96%. 10. The method for preparing multi-element silicon fertilizer by extracting water-soluble silicon from fly ash according to claim 1, characterized in that: the pH value of the fly ash is 7.4-10.