CN111908965A - Silicon-calcium-potassium-sulfur fertilizer with fly ash as matrix and preparation method thereof - Google Patents
Silicon-calcium-potassium-sulfur fertilizer with fly ash as matrix and preparation method thereof Download PDFInfo
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- CN111908965A CN111908965A CN202010575978.6A CN202010575978A CN111908965A CN 111908965 A CN111908965 A CN 111908965A CN 202010575978 A CN202010575978 A CN 202010575978A CN 111908965 A CN111908965 A CN 111908965A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
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Abstract
The invention relates to the technical field of fertilizer preparation, in particular to a silicon-calcium-potassium-sulfur fertilizer taking fly ash as a matrix, which is characterized by comprising 20-80 parts of fly ash, 5-50 parts of sulfur powder, 30-45 parts of calcium hydroxide and 8-12 parts of potassium hydroxide in parts by mass. Also relates to a preparation method of the fertilizer, which is characterized by comprising the following steps: sequentially adding sulfur powder, calcium hydroxide and potassium hydroxide into hot water, carrying out hydrothermal activation, and stirring until the sulfur powder is completely dissolved to form a mixture A; then adding the fly ash into the mixture A and stirring to form a mixture B; and finally, drying the mixture B until the water content is 3% -9%, cooling and granulating. The fertilizer is alkalescent, has complete nutrient components such as silicon, calcium, potassium, sulfur and the like, can be used for adjusting the physicochemical property of acid soil and promoting the level of medium and trace elements, achieves the aim and effect of balanced fertilization, and has higher application value and market popularization potential. The preparation method has the advantages of simple process, easily-accessible raw materials, and low cost.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of fertilizer preparation, and particularly relates to a silicon-calcium-potassium-sulfur fertilizer taking fly ash as a matrix and a preparation method thereof.
[ background of the invention ]
Fly ash is a highly dispersed aggregate of fine particles, and is fly ash collected from a combustion furnace, a pulverized coal furnace or other burner flues after coal is combusted at about 1300 ℃. The fly ash is mainly made of SiO2、Al2O3、 Fe2O3、CaO、MgO、K2O、Na2O、SO3And organic matter which is not burnt out, and also contains As, Cu, Zn, Cd, Cr, Ge, Hg and other trace elements. Most fly ash has a particle size distribution similar to that of silt, ranging from 1 μm to hundreds of microns, but typically less than 75 μm.
China is a world large coal resource country, and is also the largest coal producing country and consuming country in the world, and the yield and consumption of the Chinese coal in 2017 respectively account for 47.7% and 50.0% of the world. However, coal consumption also causes local environmental pollution and ecological damage. At present, the coal for electric power in China accounts for more than 50% of the total coal consumption, and a large amount of suspended particulate matters, smoke dust and harmful gases are discharged into the atmosphere in the coal burning process of a power plant, so that the environment and the human health are seriously harmed; after burning coal, a large amount of coal-fired wastes such as fly ash, furnace slag, flue gas desulfurization gypsum and the like are generated. China has become the largest world-wide coal-fired waste product, and the proportion of the fly ash in all coal-fired wastes is the largest (67-90%). At present, fly ash becomes the biggest single solid pollution source in China, and annual output is increased year by year.
The long-term natural accumulation of the fly ash not only occupies a large area of cultivated land, but also can threaten the surrounding water or soil environment by leaching and epibiotic migration of harmful trace elements in the fly ash; fly ash is also one of the main sources of atmospheric pollutants aerosol. Therefore, the negative influence of the fly ash on the ecological environment must be considered, and the problem of environment pollution of the fly ash is urgently solved.
At present, fly ash is comprehensively utilized to different degrees at home and abroad. The comprehensive utilization degree of the fly ash in China is increasingly improved, according to research reports on market research and investment strategy of solid waste treatment equipment in China 2015-2020, the comprehensive utilization rate of the fly ash in China in 2011 is about 69.96%, the fluctuation in 2014 is increased to 70.07%, and about 30% of the fly ash is poured into an ash pond or stacked in arable land, mountain ditches and sloping fields every year.
At present, the comprehensive utilization of the fly ash in China is mainly used in the fields of building material products, construction engineering, road engineering, filling materials, ceramic industry, soil improvement, fertilizer production and the like.
The particle structure of fly ash determines that fly ash water is more readily available to plants than soil moisture. The fly ash contains a large amount of Ca, Fe, Mg, Cu, Zn and other trace elements, can improve clay soil, raw soil, acid soil and saline-alkali soil, adjust the temperature and pH value of the soil, supplement nutrient components of the soil and provide a good soil environment for the growth of crops. The fly ash contains P, N, K-containing compound, so that the fly ash can be generally used for processing and manufacturing chemical fertilizers and promoting the growth of crops. The fly ash contains a certain amount of Fe2O3, so that the fly ash can be used for producing fly ash magnetic fertilizer, increasing soil magnetism, improving soil structure and gaps, and improving the ventilation, water passing and water retention capacity of soil. In addition, the fly ash, the excrement and the household garbage can be used for processing the harmless microbial compound fertilizer, so that the problem of soil alkalization is effectively solved. Compared with the traditional fertilizer, the fly ash fertilizer has good fertilizer efficiency and long fertilizer efficiency action time, and solves the problems of low fertilizer efficiency, environmental pollution and the like of the organic fertilizer.
Chinese patent with publication number CN 1172879C and application number 01139524.9 discloses a method for producing silicon-calcium-sulfur fertilizer by using phosphogypsum and fly ash, which solves the problems that the phosphogypsum can only be used for alkaline soil due to high acidity when being directly applied as fertilizer and the fly ash is low in fertilizer efficiency when being applied independently to a certain extent, and has a relatively simple process. However, the fertilizer prepared by the solid-phase reaction has poor uniformity and uneven mutual reaction, so that the utilization rate of the effective components of the prepared fertilizer is low, the performance is poor and other adverse results are caused.
Chinese patent publication No. CN 107188766a discloses a method for preparing a silicon composite fertilizer from fly ash, which is more complex in process and more in raw material variety.
Chinese patent with publication number CN 103724097A, relating to a nano-particle compound fertilizer and a preparation method thereof, the components of the compound fertilizer comprise 50-80 parts of fly ash, 10-20 parts of chemical fertilizer, 5-8 parts of sodium carbonate and 1-2 parts of adhesive by weight; the preparation method comprises the steps of weighing the fly ash and the sodium carbonate, grinding, stirring, adding into a reaction kettle, aging and crystallizing; filtering and washing the aged and crystallized fly ash and sodium carbonate to obtain fly ash crystals; drying the fly ash crystals to obtain fly ash powder; then adding adhesive and/or water, granulating, spraying with a spray gun, and drying. The fly ash is mainly used as a fertilizer slow-release carrier, and the application of the fly ash containing fertilizer elements is insufficient.
In journal, state of production and prospect of potassium mineral fertilizer (wang jia ming, shanghai chemical industry, 2011, 5 th), it is mentioned that a new process for preparing potassium-containing multi-element microporous mineral fertilizer from potassium-rich silicate rock at low cost by adopting a newly developed low-temperature hydrothermal chemical reaction technology is provided. Although the reaction conditions are reduced to a certain extent, the method still needs to be carried out at a higher temperature (190-200 ℃) and a pressure (1.1-1.3 MPa). Inconvenience is brought to the preparation process.
Based on the defects of the process, the patent application discloses a fly ash-based silicon-calcium-potassium-sulfur fertilizer and a preparation method thereof.
[ summary of the invention ]
One of the purposes of the invention is to provide a silicon-calcium-potassium-sulfur fertilizer with fly ash as a matrix, so as to solve the defects of low nutrient utilization rate, single nutrient and the like in the existing fertilizer.
The invention also aims to provide a preparation method of the silicon-calcium-potassium-sulfur fertilizer by taking the fly ash as a matrix, which takes the fly ash as a main raw material and is matched with sulfur powder, slaked lime (calcium hydroxide), potassium hydroxide and other auxiliary materials to prepare the weak alkaline mineral fertilizer rich in silicon, calcium, potassium, sulfur and other plant absorption nutrient elements through simple and effective synthesis. The preparation method has simple process, easily-accessible raw materials, and low cost.
In order to achieve the purpose, the invention provides the following technical scheme: a silicon-calcium-potassium-sulfur fertilizer with fly ash as a matrix comprises the following material components in parts by mass: 20-80 parts of fly ash, 5-50 parts of sulfur powder, 30-45 parts of calcium hydroxide and 8-12 parts of potassium hydroxide.
Preferably, the fly ash comprises fly ash produced in pulverized coal furnaces, stoker furnaces, and circulating fluidized bed boilers.
Preferably, the purity of the sulfur powder is more than 99%.
Preferably, the calcium hydroxide is > 90% pure.
Preferably, the sodium hydroxide is > 95% pure.
The invention also provides a preparation method of the silicon-calcium-potassium-sulfur fertilizer by taking the fly ash as a matrix, which comprises the following preparation steps:
s1: weighing 20-80 parts of fly ash, 5-50 parts of sulfur powder, 30-45 parts of calcium hydroxide and 8-12 parts of potassium hydroxide according to parts by mass;
s2: sequentially adding the weighed sulfur powder, calcium hydroxide and potassium hydroxide into hot water, carrying out hydrothermal activation, and stirring until the sulfur powder is completely dissolved to form a mixture A;
s3: adding the weighed fly ash into the mixture A and stirring to form a mixture B;
s4: and drying the mixture B until the water content is 3-9%, and granulating to obtain the silicon-calcium-potassium-sulfur fertilizer containing the fly ash.
Preferably, in step S2, the solid-to-liquid ratio of the mass of the sulfur powder to the volume of the hot water is 1: (3-5).
Preferably, in step S2, the temperature of hydrothermal activation is 30-80 ℃, and the stirring speed is 30-120 r/min.
Preferably, in step S3, the stirring speed is 30-120 r/min.
Preferably, the grain size of the silicon-calcium-potassium-sulfur fertilizer is 0.5-3.5 mm.
The beneficial effects of the invention at least comprise:
the invention aims to improve the resource utilization degree of the fly ash, and takes the fly ash as a main raw material, materials containing elements such as calcium, potassium, sulfur and the like are added, and the elements in the fly ash are further activated through hydrothermal activation, so that the alkalescent compound fertilizer which is urgently needed by acid soil and is rich in nutrient elements such as silicon, calcium, potassium, sulfur and the like is produced. The fertilizer has great significance for improving the level of trace elements in soil and crops and inhibiting soil acidification and salinization. Specifically, the method comprises the following steps:
1) the production raw materials of the invention are mostly composed of natural mineral substances, have the advantages of convenient material acquisition, low cost and the like, comprehensively utilize the component characteristics of the fly ash which is solid waste, and embody the scientific ideas of resource circulation and agricultural high-efficiency utilization;
2) through hydrothermal reaction, the activation temperature of the fly ash in the system can be reduced to 30-80 ℃ from about 1000 ℃ in the prior art, the reaction temperature is greatly reduced, the preparation process is easier to realize, and energy is saved;
3) the compound fertilizer prepared by the invention is alkalescent, has complete nutrient components such as silicon, calcium, potassium, sulfur and the like, can be used for improving or adjusting the physicochemical property of acid soil and comprehensively improving the level of medium and trace elements, thereby achieving the aim and effect of balanced fertilization and having higher application value and market popularization potential.
[ description of the drawings ]
FIG. 1 is a schematic view of the process flow for preparing Si-Ca-K-S fertilizer.
[ detailed description ] embodiments
The present invention will be described in further detail below with reference to specific embodiments and drawings, but the present invention is not limited to the specific embodiments below.
The following examples are not provided to limit the scope of the present invention, nor are the steps described to limit the order of execution, and the directions described are limited to the drawings. Modifications of the invention which are obvious to those skilled in the art in view of the prior art are also within the scope of the invention as claimed.
Example 1
The process flow for producing the silicon-calcium-potassium-sulfur fertilizer by adopting the process is shown in figure 1, and the adopted raw material compatibility (by mass parts) is as follows: 20 parts of fly ash, 5 parts of sulfur powder, 30 parts of slaked lime and 8 parts of potassium hydroxide. The process flow comprises the following steps: firstly, according to the mass of sulfur powder: dissolving sulfur powder into water according to a solid-liquid ratio of 1:3, adding slaked lime (calcium hydroxide) and potassium hydroxide, stirring, heating the water to 67 ℃, stirring at a speed of 60r/min to completely dissolve the sulfur powder into the water, adding fly ash, continuously stirring until the materials are completely uniform, taking out the materials, drying until the water content is 5%, cooling, granulating to obtain the calcium-silicon-potassium-sulfur fertilizer with the particle size of 0.5mm, and packaging. The hydrothermal process, especially in alkaline environment, can promote decomposition and activation and accelerate the preparation process of the fertilizer. The fertilizer prepared by the materials and the method has low required temperature and pressure, easily-achieved process conditions and simpler fertilizer preparation. The following components are obtained through the third-party component inspection: the prepared fertilizer contains 72% of effective nutrients, wherein the effective calcium oxide is more than 27%, the effective silicon dioxide is more than 22%, the effective potassium oxide is more than 5.2%, the effective sulfur trioxide is more than 6%, and the fertilizer contains various medium and trace elements. The pH value of the product is 10.2, the production cost can be controlled below 550 yuan/ton, and the product is a mineral compound fertilizer containing a plurality of silicon, calcium, potassium and sulfur.
The used fly ash is generated in a pulverized coal furnace, a chain furnace or a circulating fluidized bed boiler, is uniform and fine, and has high calcium content, the purity of the used sulfur powder is more than 99 percent, the purity of calcium hydroxide is more than 90 percent, and the purity of sodium hydroxide is more than 95 percent.
Example 2
The material compatibility (by mass percent) of the silicon-calcium-potassium-sulfur fertilizer produced by adopting the process is as follows: 47% of fly ash, 10% of sulfur powder, 33% of slaked lime and 10% of potassium hydroxide. The process flow comprises the following steps: firstly, according to the mass of sulfur powder: dissolving sulfur powder into hot water according to a solid-liquid ratio of 1:5, then adding slaked lime (calcium hydroxide) and potassium hydroxide, heating the water to 30 ℃, stirring at a speed of 120r/min to completely dissolve the sulfur powder, then adding fly ash, continuously stirring at a speed of 120r/min until the materials are uniform, taking out the materials, and drying until the water content is 9%; then the mixture is granulated and processed into particles with the particle size of about 1.5mm, namely the silicon-calcium-potassium-sulfur fertilizer, and the particles are packaged to prepare the mineral compound fertilizer. Wherein the following is obtained by the third-party component inspection: the produced fertilizer contains more than 65% of available nutrients, more than 30% of available calcium oxide, more than 15% of available silicon dioxide, more than 5.5% of available potassium oxide, more than 12.5% of available sulfur trioxide, and various trace elements. The pH value of the product is 11.3, the production cost can be controlled below 520 yuan/ton, and the product is a mineral compound fertilizer containing a plurality of silicon, calcium, potassium and sulfur, and can be used for conditioning or improving acid or saline-alkali soil.
Example 3
The raw material compatibility (by mass portion) adopted for producing the silicon-calcium-potassium-sulfur fertilizer by the process is as follows: 80 parts of fly ash, 50 parts of sulfur powder, 45 parts of slaked lime and 12 parts of potassium hydroxide. The process flow comprises the following steps: firstly, according to the mass of sulfur powder: dissolving sulfur powder into hot water according to a solid-liquid ratio of 1:4, then adding slaked lime and potassium hydroxide, heating the water to 80 ℃, stirring at a speed of 30r/min to completely dissolve the sulfur powder, then adding fly ash, continuously stirring at a speed of 30r/min until the materials are uniform, taking out the materials, and drying until the water content is 3%; then the mixture is granulated and processed into spherulites with the grain diameter of about 3.5mm, namely the silicon-calcium-potassium-sulfur fertilizer, and the spherulites can be prepared into the mineral compound fertilizer after being packaged. Wherein the following is obtained by the third-party component inspection: the produced fertilizer contains more than 68% of available nutrients, more than 31% of available calcium oxide, more than 23% of available silicon dioxide, more than 7% of available potassium oxide, more than 7% of available sulfur trioxide, and various trace elements. The pH value of the product is 10.7, the production cost can be controlled at 480 yuan/ton, and the product is a mineral compound fertilizer containing silicon, calcium, potassium and sulfur. Can condition acidified soil in southern regions and supplement mineral nutrient components which are lacked in the soil. The above examples show that the total available nutrients in the fertilizer prepared by the method are more than 60%, wherein the available calcium oxide is more than 25%, the available silicon dioxide is more than 12%, the available potassium oxide is more than 5%, the available sulfur trioxide is more than 5%, and the fertilizer contains various medium and trace elements and is weakly alkaline. The production raw materials of the invention are mostly composed of natural mineral substances, and the invention has the advantages of convenient material acquisition, low cost and the like, and the product can be used for improving or adjusting the physicochemical property of acid soil and comprehensively improving the level of medium trace elements. Has higher application value and market popularization potential.
Claims (10)
1. The silicon-calcium-potassium-sulfur fertilizer taking fly ash as a matrix is characterized by comprising the following material components in parts by mass: 20-80 parts of fly ash, 5-50 parts of sulfur powder, 30-45 parts of calcium hydroxide and 8-12 parts of potassium hydroxide.
2. The fly ash based si-ca-k-s-fertilizer of claim 1, wherein the fly ash comprises fly ash produced in pulverized coal furnaces, stoker furnaces, and circulating fluidized bed boilers.
3. The fly ash-based silicon-calcium-potassium-sulfur fertilizer as claimed in claim 1, wherein the purity of the sulfur powder is more than 99%.
4. The fly ash-based silico-calcium-potassium-sulfur fertilizer as claimed in claim 1, wherein the purity of the calcium hydroxide is > 90%.
5. The fly ash-based silico-calcium-potassium-sulfur fertilizer as claimed in claim 1, wherein the purity of the sodium hydroxide is > 95%.
6. The method for preparing the silicon-calcium-potassium-sulfur fertilizer by taking fly ash as the matrix according to any one of claims 1 to 5, which is characterized by comprising the following preparation steps:
s1: weighing 20-80 parts of fly ash, 5-50 parts of sulfur powder, 30-45 parts of calcium hydroxide and 8-12 parts of potassium hydroxide according to parts by mass;
s2: sequentially adding the weighed sulfur powder, calcium hydroxide and potassium hydroxide into hot water, carrying out hydrothermal activation, and stirring until the sulfur powder is completely dissolved to form a mixture A;
s3: adding the weighed fly ash into the mixture A and stirring to form a mixture B;
s4: and drying the mixture B until the water content is 3-9%, and granulating to obtain the silicon-calcium-potassium-sulfur fertilizer containing the fly ash.
7. The method for preparing the silicon-calcium-potassium-sulfur fertilizer by using the fly ash as the matrix according to claim 6, wherein the method comprises the following steps: in step S2, the solid-to-liquid ratio of the mass of sulfur powder to the volume of hot water is 1: (3-5).
8. The method for preparing the silicon-calcium-potassium-sulfur fertilizer by using the fly ash as the matrix according to claim 6, wherein the method comprises the following steps: in step S2, the temperature of hydrothermal activation is 30-80 ℃, and the stirring speed is 30-120 r/min.
9. The method for preparing the silicon-calcium-potassium-sulfur fertilizer by using the fly ash as the matrix according to claim 6, wherein the method comprises the following steps: in step S3, the stirring speed is 30-120 r/min.
10. The method for preparing the silicon-calcium-potassium-sulfur fertilizer by using the fly ash as the matrix according to claim 6, wherein the method comprises the following steps: the grain size of the silicon-calcium-potassium-sulfur fertilizer is 0.5-3.5 mm.
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| CN112430158A (en) * | 2020-12-16 | 2021-03-02 | 锡林郭勒职业学院 | Preparation and application method of compound fertilizer matrix |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108239536A (en) * | 2016-12-26 | 2018-07-03 | 中国科学院过程工程研究所 | A kind of soil conditioner and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108239536A (en) * | 2016-12-26 | 2018-07-03 | 中国科学院过程工程研究所 | A kind of soil conditioner and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112430158A (en) * | 2020-12-16 | 2021-03-02 | 锡林郭勒职业学院 | Preparation and application method of compound fertilizer matrix |
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Application publication date: 20201110 |