CN109896871B - Green silicon fertilizer and preparation method thereof - Google Patents
Green silicon fertilizer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a green silicon fertilizer,belongs to the technical field of fertilizer preparation. The method comprises the following steps: mixing talcum powder and calcium carbonate and roasting; and after the roasting, cooling the roasted product to 600-800 ℃ along with the furnace, and then air-cooling to room temperature to obtain the green silicon fertilizer. The invention takes calcium carbonate as modifier to modify talcum powder, and the two raw materials are subjected to chemical reaction under the condition of roasting to generate Ca2Mg(Si2O7) And a small amount of Ca3Mg(SiO4)2(ii) a Meanwhile, the roasted product is cooled to 600-800 ℃ and then cooled in air, so that the further reaction of the roasted product is avoided, and the melting of silicon is also avoided; the high content of effective silicon in the green silicon fertilizer is ensured; in addition, due to Al in the raw material2O3The content is low, so that the finally obtained green silicon fertilizer has low heavy metal content and meets the requirement of environmental protection.
Description
Technical Field
The invention relates to the technical field of fertilizer preparation, in particular to a green silicon fertilizer and a preparation method thereof.
Background
With the continuous development of modern agriculture and industrial process, the amount of farmland fertilizers is more and more, particularly, the amount of elements such as nitrogen, phosphorus, potassium and the like is greatly increased, and the amount of farmyard manure is less and less; thus the proportion of nitrogen, phosphorus, potassium and silicon in the soil is seriously unbalanced. Meanwhile, the silicon element can improve the supply capacity of the soil to available nitrogen, phosphorus and potassium, and adjust the iron-manganese ratio and the supply of calcium, zinc and manganese. Therefore, the method has important significance in comprehensively developing and utilizing abundant talc resources in China to produce relatively scarce green silicon fertilizer in China.
Chinese patent publication No. CN106365899A discloses that raw materials are added into a ball mill in a certain proportion for ball milling, then the raw materials are put into a high-temperature sintering furnace at 800 ℃ for calcination for a certain time, and then the raw materials are pulverized to obtain the silicon fertilizer. But it uses Al as a raw material2O3The content and the heavy metal content are high,the finally prepared silicon fertilizer has high heavy metal content, and after the silicon fertilizer is used, the heavy metal in soil is easy to exceed the standard, the underground water quality is seriously influenced, and the environment protection is not facilitated; and also does not accord with the environmental protection concept. In addition, the operation of directly reducing the heavy metal content of the raw materials in the fertilizer is complicated, and secondary pollution is generated and is not beneficial to the environment. Therefore, the development of a fertilizer with simple method, high effective silicon content and low heavy metal content is urgent.
Disclosure of Invention
In view of the above, the present invention aims to provide a green silicon fertilizer and a preparation method thereof. The green silicon fertilizer provided by the invention has the advantages of low heavy metal content, high effective silicon content and high adsorption average pore diameter; the fertilizer has high fertility and meets the requirement of environmental protection; meanwhile, the preparation method is simple and convenient and is easy to operate.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a green silicon fertilizer, which comprises the following steps:
mixing talcum powder and calcium carbonate and roasting; and cooling the roasted product to 600-800 ℃ along with the furnace, and then air-cooling to room temperature to obtain the green silicon fertilizer.
Preferably, the talc powder and calcium carbonate are in a molar ratio of 1: 1.4 to 2.4.
Preferably, the particle size of the talcum powder is 20-200 meshes; the particle size of the calcium carbonate is 20-200 meshes.
Preferably, the purity of the calcium carbonate is analytical grade.
Preferably, the purity of the talcum powder is 85-99.9%.
Preferably, the roasting temperature is 1050-1200 ℃ and the roasting time is 30-210 min.
Preferably, the heating power for heating to the roasting temperature is 4-5 kW.
The invention also provides the green silicon fertilizer prepared by the preparation method of the technical scheme, and the green silicon fertilizer is prepared from Ca2Mg(Si2O7) And a small amount of Ca3Mg(SiO4)2Composition is carried out; the effective silicon content is 17.11-19.93%;the average adsorption pore diameter is 17.906-19.704 nm; the single-point specific surface area is 1.298-1.356 m2(ii)/g; the green silicon fertilizer belongs to citric soluble silicon fertilizer, the solubility in 2% citric acid and ultrapure water can reach 0.0365g/100mL and 0.0146g/100mL respectively, and no aluminum is detected.
The invention provides a preparation method of a green silicon fertilizer, which comprises the following steps: mixing talcum powder and calcium carbonate and roasting; and after the roasting, cooling the roasted product to 600-800 ℃ along with the furnace, and then air-cooling to room temperature to obtain the green silicon fertilizer. The invention takes calcium carbonate as modifier to modify talcum powder, and the two raw materials are subjected to chemical reaction under the condition of roasting to generate Ca2Mg(Si2O7) And a small amount of Ca3Mg(SiO4)2(ii) a Meanwhile, the roasted product is cooled to 600-800 ℃ and then cooled in air, so that the further reaction of the roasted product is avoided, and the melting of silicon is also avoided; the high content of effective silicon in the green silicon fertilizer is ensured; in addition, due to Al in the raw material2O3The content is low, so that the finally prepared green silicon fertilizer has low heavy metal content and is environment-friendly. In addition, the preparation method is simple and convenient, has low cost and does not cause environmental pollution. As can be seen from the examples: the green silicon fertilizer is mainly composed of Ca2Mg(Si2O7) And a small amount of Ca3Mg(SiO4)2Composition is carried out; the effective silicon content is 17.11-19.93%; the average adsorption pore diameter is 17.906-19.704 nm; the single-point specific surface area is 1.298-1.356 m2(ii)/g; the green silicon fertilizer belongs to citric acid soluble silicon fertilizer, the solubility of the green silicon fertilizer dissolved in 2% citric acid and ultrapure water can reach 0.0365g/100mL and 0.0146g/100mL respectively, and no aluminum is detected.
Drawings
FIG. 1 is a graph showing the relationship between the different molar ratios of calcium carbonate and talc and the effective silicon content.
FIG. 2 is a graph showing the relationship between different calcination temperatures and the effective silicon content of talc powder.
FIG. 3 is a graph showing the relationship between different roasting temperatures and the effective silicon content in green silicon fertilizer.
FIG. 4 is a graph showing the relationship between different roasting times and the effective silicon content in green silicon fertilizer.
FIG. 5 is a graph showing the effective calcium and magnesium contents of the green silicon fertilizer obtained in example 2 dissolved in 2% citric acid and ultrapure water, respectively.
FIG. 6 is a scanning electron micrograph of talc powder and the green silicon fertilizer obtained in example 2.
FIG. 7 is a TG-DSC curve chart of talc powder and the green silicon fertilizer obtained in example 2.
FIG. 8 is an XRD spectrum of talc powder, the green silicon fertilizer obtained in example 2 and the green silicon fertilizer obtained under different conditions.
FIG. 9 shows FT-IR spectra of talc powder, green silicon fertilizer obtained in example 2 and green silicon fertilizer obtained under different conditions.
FIG. 10 is a graph showing isothermal adsorption/desorption curves of talc powder and green silica fertilizer obtained in example 2.
Detailed Description
The invention provides a preparation method of a green silicon fertilizer, which comprises the following steps:
mixing talcum powder and calcium carbonate and roasting; and cooling the roasted product to 600-800 ℃ along with the furnace, and then air-cooling to room temperature to obtain the green silicon fertilizer.
The present invention mixes talcum powder and calcium carbonate and calcines them. In the invention, the particle size of the talcum powder is preferably 20-200 meshes, more preferably 50-190 meshes, and even more preferably 100-180 meshes. In the invention, the purity of the talcum powder is preferably 85-99.9%, more preferably 90-99.8, and even more preferably 94-99.7%. In the invention, the purity of the talcum powder is preferably calculated by the mass fraction ratio of magnesium oxide in the talcum powder, and in the embodiment of the invention, the theoretical chemical composition of MgO in the talcum powder is 31.90%; the mass fraction of MgO in the talcum powder adopted in the embodiment of the invention is 31.04%; therefore, the purity (P) of the talc powder in the examples of the present invention was 31.04%/31.90% — 97.30%.
The source of talc powder in the present invention is not particularly limited, and it may be obtained by a production method known to those skilled in the art or may be a commercially available product, as long as the above purity requirement is satisfied. In the embodiment of the present invention, the talc powder is preferablyThe preparation method comprises the following steps: crushing talc ore and ball milling into talc powder with a ball mill. In the present invention, the talc preferably includes the following components in mass fraction: al (Al)2O30.3～0.9％、CaO 0.11～0.25％、Fe2O3 0.44～0.95％、MgO 29.04～34.01％、Na2O 0.03～0.23％、P2O50.01～0.12％、 SiO255-70.1%; the loss on ignition is 4.43-8.24%.
In the present invention, the particle size of the calcium carbonate is preferably 20 to 200 mesh, more preferably 50 to 190 mesh, and even more preferably 100 to 180 mesh. In the present invention, the purity of the calcium carbonate is preferably analytically pure. The source of the calcium carbonate is not particularly limited in the present invention, and it may be prepared by a preparation method known to those skilled in the art or may be a commercially available product.
In the present invention, the molar ratio of the talc powder to the calcium carbonate is preferably 1: 1.4 to 2.4, and more preferably 1: 1.6-2.2, more preferably 1: 1.8 to 2.0. The mixing method of the talcum powder and the calcium carbonate is not particularly limited in the invention, and the mixing method known to those skilled in the art can be adopted. In an embodiment of the present invention, the mixing manner preferably includes: weighing the talcum powder and the calcium carbonate according to a molar ratio, wherein the weight ratio of the total weight of the talcum powder and the calcium carbonate to the water is 1: 1-5, adding water, and grinding for 5-15 min; and after grinding, drying the ground product at 100-110 ℃ to constant weight so as to uniformly mix the talcum powder and the calcium carbonate. In the invention, the mixing mode enables the calcium carbonate and the talcum powder to be fully mixed, which is beneficial to combining the calcium carbonate and the talcum powder together; thereby being beneficial to subsequent full roasting and further achieving the effect of improving the effective silicon content in the green silicon fertilizer.
In the invention, the roasting temperature is preferably 1050-1200 ℃, and is further preferably 1100-1150 ℃; the roasting time is preferably 30-210 min, more preferably 60-180 min, and even more preferably 90-120 min. In the invention, the heating power for raising the temperature to the roasting temperature is preferably 4-5 kW.
In the present invention, the calcination enables calcium carbonateChemically reacting with talcum powder to generate Ca2Mg(Si2O7) And a small amount of Ca3Mg(SiO4)2(ii) a The effective silicon content in the green silicon fertilizer is obviously improved.
After the roasting, the roasted product is cooled to 600-800 ℃ along with the furnace, and then air-cooled to room temperature, so as to obtain the green silicon fertilizer.
In the invention, the roasted product is cooled to 600-800 ℃ along with the furnace, so that the further reaction of the roasted product and the possible further melting phenomenon of silicon caused by the lower and lower temperature and the lower and lower cooling speed are avoided, and the effective silicon content in the green silicon fertilizer is improved; in addition, the safety of experimental operation is improved, the test tube cannot be taken out at an overhigh temperature, the experimental operation is convenient, and the requirements of energy conservation and consumption reduction are met.
The invention also provides the green silicon fertilizer prepared by the preparation method of the technical scheme. In the invention, the green silicon fertilizer is mainly composed of Ca2Mg(Si2O7) And a small amount of Ca3Mg(SiO4)2Composition is carried out; the effective silicon content is 17.11-19.93%; the average adsorption pore diameter is 17.906-19.704 nm; the single-point specific surface area is 1.298-1.356 m2(ii)/g; the green silicon fertilizer belongs to citric soluble silicon fertilizer, the solubility in 2% citric acid and ultrapure water can reach 0.0365g/100mL and 0.0146g/100mL respectively, and no aluminum is detected.
The green silicon fertilizer provided by the invention has high effective silicon content, does not dissolve heavy metals in 2% citric acid and ultrapure water, does not damage the soil structure, pollutes underground water, and meets the requirement of environmental protection.
The green silicon fertilizer and the preparation method thereof provided by the invention are described in detail below with reference to examples, but the invention is not to be construed as being limited by the scope of the invention.
Example 1:
weighing talcum powder and calcium carbonate according to a certain molar ratio, and then mixing the talcum powder and the calcium carbonate according to the ratio of the total weight of the talcum powder and the calcium carbonate to the weight of water of 1: 3 adding water to grind for 5min, and then drying at 105 ℃ to constant weight to obtain a mixture; roasting the mixture at a certain temperature, and after roasting and sintering, cooling a roasted product to 600-800 ℃ along with a furnace; and naturally cooling to room temperature to obtain the green silicon fertilizer.
Wherein the calcium carbonate is analytically pure calcium carbonate purchased from west longa science ltd; the talcum powder is prepared by the following steps: smashing talc ore collected from Guangxi Guilin and ball-milling the smashed talc ore into fine talc powder by using a ball mill, so that the fine talc powder can pass through a 200-mesh separation sieve to obtain talc powder;
the treated talc powder was examined by an X-ray fluorescence spectrometer, and the chemical components of the obtained talc powder are shown in table 1.
TABLE 1 Main chemical composition of talc used in this example
The theoretical chemical composition of MgO in the talcum powder is 31.90 percent; the mass fraction of MgO in the talcum powder prepared in the embodiment is 31.04%; therefore, the purity (P) of the talc obtained in this example was calculated from the ratio of 31.04% by mass of magnesium oxide to 31.9% by mass of MgO in the talc, which was 97.30% for 31.04%/31.90%.
Measuring the effective silicon content by adopting a silicon-molybdenum blue spectrophotometry
The principle is as follows: in an acidic solution, monosilicic acid and ammonium molybdate can generate yellow molybdenum-silicon heteropoly acid, then oxalic acid is used for masking phosphorus, ammonium ferrous sulfate is used for reducing the phosphorus into a silicon-molybdenum blue complex, the color depth of the complex is in a direct proportion to the concentration of effective silicon, and the complex accords with the Ranber-beer law within a certain range.
(1) Drawing of standard curve
Mixing 1000 mu g/mL of SiO2The standard solution was diluted to obtain 5.0mL of 1000. mu.g/mL SiO2Putting the standard solution into a 100mL volumetric flask, fixing the volume and shaking up; the 50. mu.g/mL standard solution at this time was stored in a 100mL polyethylene bottle and kept ready for use.
Respectively suck 0.0, 1.0, 2.0, 3.0, 4.0 and 6.050 μ g/mL SiO2The standard solution was placed in a 50mL volumetric flask, and then 6.0mL of H with a concentration of 0.3mol/L was added2SO4And 5.0mL of a 5% ammonium molybdate solution and shaken well. Standing at 30 ℃ (+ -3 ℃) for 8-10 min, adding 5.0mL of 5% oxalic acid solution, immediately adding 5.0mL of 6% ammonium ferrous sulfate solution, fixing the volume, standing for 15min, and measuring the absorbance of the solution at 680nm wavelength by using a 1cm cuvette on a spectrophotometer. The measured absorbance was plotted on the ordinate and the silica solubility on the abscissa. From the results, it was found that the silica concentration was in a good linear relationship in the range of 0 to 6ug/mL, the square of the correlation coefficient R was 0.9997, and the unary linear regression equation was that y was 0.1355x + 0.0666.
(2) Method for measuring available silicon content
Weighing 0.1000g of a green silicon fertilizer sample to be tested in a dry and clean 250mL conical flask, accurately adding 100mL of a leaching agent (2% citric acid aqueous solution), oscillating for 30min at 190r (+ -5 r)/min on a constant temperature reciprocating oscillator at 29 ℃ (-1 ℃), immediately dry filtering and discarding the initial 5.0mL of filtrate; sucking 5.0mL of the original filtrate filtered by the filter paper, diluting the original filtrate in a 100mL volumetric flask, shaking the original filtrate to a constant volume, standing the diluted filtrate for 10min, sucking VmL from the 100mL volumetric flask at the moment in a 50mL volumetric flask, and respectively sucking a certain amount of 50 mu g/mL SiO in the following steps of drawing a standard curve2Step after the standard solution is in a 50mL volumetric flask.
H% (in terms of SiO) of effective silicon content in the tested green silicon fertilizer sample2Meter) is calculated from equation 2:
in the formula: h% is the effective silicon content; m is the mass of the green silicon fertilizer sample, g; c. C1The concentration (mu g/mL) of silicon dioxide corresponding to the absorbance measured by the test solution on the standard working curve; c. C0The concentration (mu g/mL) of silicon dioxide corresponding to the absorbance measured by the blank test solution on the standard working curve; v is the volume of filtrate dilution aspirated (mL); the filtrate dilutions VmL were 5.0mL each taken when determining effective silicon content.
Influence of (I) mole ratio of talcum powder to calcium carbonate on effective silicon content
In example 1, talc and calcium carbonate were added in a molar ratio of 1: 1.4-2.4 (1: 1.4, 1: 1.6, 1: 1.8, 1: 2.0, 1: 2.2, 1: 2.4 respectively), accurately weighing corresponding mass, and respectively roasting at 1000 ℃ and 1100 ℃ for 60 min. By adopting the method for measuring the effective silicon, the relationship between different molar ratios and the effective silicon content in the green silicon fertilizer is analyzed, and the result is shown in figure 1. As can be seen from fig. 1: the mol ratio of the talcum powder to the calcium carbonate is 1: 1.4, 1: 1.6, 1: 1.8, 1: 2.0, 1: 2.2, 1: 2.4, the effective silicon content in the green silicon fertilizer roasted at 1100 ℃ is 14.37%, 15.40%, 16.14%, 16.83%, 15.35% and 14.61% respectively; the effective silicon content in the green silicon fertilizer roasted at 1000 ℃ is 5.81%, 6.00%, 6.25%, 6.54%, 5.36% and 4.13% respectively; obviously, the effective silicon content in the green silicon fertilizer increases and then decreases along with the increase of the addition amount of calcium carbonate, and when the amount of calcium carbonate is added to a state that the molar ratio is n (talcum powder): n (calcium carbonate) ═ 1: 2, when the raw materials are respectively roasted at 1100 ℃ and 1000 ℃ for 60min, the effective silicon content can respectively reach 16.83 percent and 6.54 percent. Therefore, the green silicon fertilizer has an optimal molar ratio in the molar ratio of the materials, namely n (talcum powder): n (calcium carbonate) ═ 1: 2.
(II) influence of roasting temperature on effective silicon content in green silicon fertilizer
The relationship between the effective silicon content and different roasting temperatures in each talc powder sample after the single talc powder is roasted at 30 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and 1200 ℃ for 60min is studied, and the result is shown in fig. 2. As can be seen from fig. 2: the effective silicon content of the talcum powder is 3.84 percent at most after being roasted at 1000 ℃, the effective silicon content is only 1.97 percent at normal temperature, and the effective silicon content of the talcum powder is not very high on the whole.
Mixing talcum powder and calcium carbonate according to a molar ratio of 1: 2, mixing; roasting at 30 deg.C (room temperature), 950 deg.C, 1000 deg.C, 1050 deg.C, 1100 deg.C, 1150 deg.C and 1200 deg.C for 60 min; the relationship between the effective silicon content in each green silicon fertilizer and different roasting temperatures is studied, and the result is shown in fig. 3. As can be seen from fig. 3: along with the gradual increase of the roasting temperature, the effective silicon content in the green silicon fertilizer sample is gradually increased; at 1150 ℃, the effective silicon content of the green silicon fertilizer is 17.81 percent, which is improved by 0.98 percent compared with the effective silicon content of 16.83 percent at 1100 ℃; at 1200 ℃, the effective silicon content of the green silicon fertilizer is 18.40 percent, which is improved by 0.59 percent compared with that at 1150 ℃; the more slowly the effective silicon content increases. 1150 c is used as a suitable firing temperature since it is limited in that the energy consumption will be greater as the temperature increases.
(III) Effect of calcination time on effective silicon content
Controlling the molar quantity of the talcum powder and the calcium carbonate to be 1: 2; controlling the roasting temperature to 1150 ℃; respectively controlling the roasting time to be 10min, 30min, 60min, 90min, 120min, 150min, 180min and 210 min; the relationship between the roasting time and the effective silicon content in the green silicon fertilizer is researched, and the result is shown in figure 4.
As can be seen from fig. 4: at 1150 ℃, when the roasting time is increased from 10min to 120min, the effective silicon content in the green silicon fertilizer is increased relatively quickly, and the effective silicon content reaches 19.09% in 120 min; and the effective silicon content is 19.29 percent at 150min, which is only improved by 0.2 percent compared with the effective silicon content at 120 min. With a further increase in time, the effective silicon content decreases to a different extent, probably because of the melting phenomena which occur over time. When the molar ratio of the talcum powder to the calcium carbonate is 1: 2. The roasting temperature is 1150 deg.C, and the suitable time for roasting is 120 min.
Example 2:
according to a molar ratio of 1: 2, weighing talcum powder and calcium carbonate, and then mixing the talcum powder and the calcium carbonate according to the ratio of the total weight of the talcum powder and the calcium carbonate to the weight of water of 1: 3 adding water to grind for 10min, and then drying at 105 ℃ to constant weight to obtain a mixture; roasting the mixture at 1150 ℃ for 120min, and after roasting, cooling the roasted product to 600-800 ℃ along with the furnace; and naturally cooling to room temperature to obtain the green silicon fertilizer.
Roasting the raw material talcum powder for 120min at 1150 ℃, and cooling a roasted product to 700 ℃ along with a furnace after roasting and sintering; then naturally cooling to room temperature to obtain talcum powder for comparative study; and when various subsequent tests are carried out, the talcum powder is subjected to roasting treatment.
Firstly, the effective contents of calcium, magnesium and aluminum in the green silicon fertilizer obtained in the embodiment are measured
A0.1000 g sample of the green silicon fertilizer was weighed into a dry 250mL Erlenmeyer flask and exactly 100mL of leachant (2% citric acid and ultrapure water, respectively) was added. Shaking with a constant temperature reciprocal shaker at 29 deg.C (+ -1 deg.C) and 190r (+ -5 r)/min for 30min, immediately dry filtering and discarding the initial 5.0mL of filtrate; 5.0mL of the original filtrate filtered through the filter paper was pipetted and diluted into a 100mL volumetric flask. The effective calcium and magnesium concentrations of the diluent are detected by ICP-AES, and the effective calcium and magnesium content L percent is calculated by the following formula 3.
In the formula: l% is effective calcium and magnesium content; c is effective calcium and magnesium concentration (mg/L) detected by ICP-AES.
Each sample treatment was repeated three times to obtain the effective calcium and magnesium contents of the green silicon fertilizer respectively dissolved in 2% citric acid and ultrapure water, and the results are shown in fig. 5; and the aluminum content of the solution is not detected by error bar analysis. As can be seen from fig. 5: the effective calcium and magnesium contents of the green silicon fertilizer obtained in the embodiment dissolved in 2% citric acid are 15.35% and 5.69% respectively; the effective calcium and magnesium contents dissolved in ultrapure water are respectively 0.30% and 0.15%. The effective calcium and magnesium contents of talcum powder dissolved in 2% citric acid are respectively 0.51% and 0.11%; the effective calcium and magnesium contents dissolved in ultrapure water are respectively 0.07% and 0.03%. Obviously, the effective calcium and magnesium contents of the green silicon fertilizer material 2% citric acid and the ultrapure water obtained by the implementation are higher than those of the green silicon fertilizer material prepared by dissolving talcum powder in 2% citric acid and ultrapure water. Therefore, the green silicon fertilizer obtained in the embodiment has high effective silicon content, has good effective calcium and magnesium contents, is an element beneficial to human bodies and an element required by the current soil loss, and is beneficial to plant growth.
(II) the pH value and the solubility of the green silicon fertilizer obtained in the embodiment
A0.5000 g sample of the green silicon fertilizer was weighed into a dry 250mL Erlenmeyer flask, 250mL of the solution (2% citric acid and ultrapure water, respectively) was added, and the mixture was shaken at 180r (+ -5 r)/min for 30min on a constant temperature reciprocating shaker at 30 ℃ (+ -1 ℃), and each sample treatment was repeated three times. The whole covered with the porcelain crucible and the mass of quantitative filter paper (ash content 0.015%) were weighed, immediately dry-filtered and the first 5mL of filtrate was discarded, and the pH (+ -0.01) of the original filtrate after filtration through the medium-speed quantitative filter paper was measured using a thunder magnet PHS-3E type pH meter.
After all the filter paper and the residues are filtered, the filter paper and the residues are accurately placed into a porcelain crucible by using tweezers, and the porcelain crucible is placed in a muffle furnace to be roasted for 30min at 1000 ℃ (a small gap is reserved on a porcelain crucible cover). And (3) cooling to 700 ℃, taking out, cooling to normal temperature, weighing, and calculating the solubility of the sample according to the formula 4.
S＝[0.5-(m3-m2×0.00015-m1)]/250X 100 formula 4;
in the formula: s is the solubility of the sample (g/100 mL); m is1The integral mass (g) of the cover contained in the porcelain crucible; m is2The quantitative filter paper mass (g) used; m is3The filter paper and the residue are placed in a porcelain crucible and are cooled to normal temperature after being roasted, and the whole weighed mass (g) is covered.
The solubility and pH of talc and the green silicon fertilizer obtained in this example in different solutions, and the Relative Standard Deviation (RSD) are shown in Table 2.
TABLE 2 solubility and pH of talc powder and green silicon fertilizer obtained in example 2 in 2% citric acid and ultrapure water, respectively
As can be seen from table 2: the green silicon fertilizer and the talcum powder obtained in the embodiment are respectively dissolved in 2% citric acid or ultrapure water and are in a slightly soluble state, and the solubility of the green silicon fertilizer is better than that of the talcum powder; the solubility of the green silicon fertilizer in 2 percent citric acid and ultrapure water can reach 0.0365g/100mL and 0.0146g/100mL respectively. Meanwhile, the solution of the green silicon fertilizer obtained in this example dissolved in ultrapure water has a pH of 10.36 slightly basic, and the alkalinity is higher than that of the solution of talc dissolved in ultrapure water (pH of 7.26); the pH value of the solution of the green silicon fertilizer dissolved in 2% citric acid obtained in the embodiment is 2.34, the solution is acidic, and the acid strength is slightly lower than that of the solution of talcum powder dissolved in 2% citric acid.
(III) scanning electron microscope analysis of the Green silicon Fertilizer obtained in this example
Scanning electron microscopes with different magnifications are adopted to analyze the morphological characteristics of the talcum powder and the green silicon fertilizer obtained in the embodiment, and the result is shown in FIG. 6; in fig. 6, fig. 6(a), fig. 6(a1) and fig. 6(a2) are scanning electron micrographs of talc powder magnified 1000 times, 5000 times and 10000 times, respectively; fig. 6(b), 6(b1) and 6(b2) are scanning electron micrographs of the green silicon fertilizer obtained in this example at 1000, 5000 and 10000 times magnification, respectively. As can be seen from fig. 6: the talcum powder is flat and irregular and has certain wax-like luster and larger particles. The green silicon fertilizer obtained in the embodiment has small particles, and the structure is damaged, so that a large amount of particles are presented; the green silicon fertilizer obtained by the implementation can be clearly observed under microscopic observation under the magnification of 10000 times: talc and calcium carbonate are mostly present in the form of aggregates which are cemented together.
(IV) thermogravimetric-differential scanning calorimetry analysis of the green silicon fertilizer obtained in the example
Respectively mixing talcum powder and the green silicon fertilizer obtained in the embodiment with a proper amount of water, uniformly grinding, and heating and drying at the speed of 5 ℃/min in the air atmosphere, wherein the heating and drying temperature range is 30-1300 ℃, and performing TG-DSC analysis, wherein the result is shown in figure 7, and figure 7(A) is a TG-DSC chart of the talcum powder; FIG. 7(B) is a TG-DSC of the green silicon fertilizer obtained in example 2. As can be seen from fig. 7: the weight of the talcum powder is increased between 30 and 898 ℃, and the weight is increased by about 1.30% at a temperature of about 777 ℃; the obvious weight loss phenomenon appears at 898-1300 ℃, the weight loss is about 3.48% at 1092 ℃, and the after weight loss shows a gentle trend. Obviously, the talc powder has an endothermic phenomenon at 30-1300 ℃ because of the loss of hydroxyl and water in the talc powder under a heating environment. The green silicon fertilizer prepared by the embodiment has the same weight increase phenomenon at 30-639 ℃, the weight increase is about 0.79% at 557 ℃, the weight loss phenomenon occurs at 639-1300 ℃, the weight loss is about 17.26% at 1000 ℃, and the green silicon fertilizer is mainly caused by the fact that calcium carbonate is largely decomposed into calcium oxide and carbon dioxide. Obviously, the green silicon fertilizer prepared by the embodiment has an endothermic phenomenon at 30-1300 ℃, but a small exothermic peak appears at 728-759 ℃, and the exothermic peak does not appear at the whole temperature of 30-1300 ℃, and the reaction temperature is possibly reduced at this time and is covered by the decomposition endothermic peak of calcium carbonate. By comparing the TGDSC images of the talcum powder and the green silicon fertilizer obtained in the embodiment, the addition of calcium carbonate is beneficial to reducing the reaction temperature and reducing the energy loss.
(V) X-ray diffraction analysis of the green silicon fertilizer obtained in the implementation
XRD analysis is carried out on the talcum powder and the green silicon fertilizer obtained in the embodiment by using a full-automatic X-ray diffractometer, and the result is shown in figure 8; in fig. 8, fig. 8(a) is an XRD pattern of talc powder, fig. 8(B) is an XRD pattern of 950 ℃ green silicon fertilizer (the preparation method is the same as in example 2 except that it is calcined for 950 ℃ -1h), fig. 8(C) is an XRD pattern of 1000 ℃ green silicon fertilizer (the preparation method is the same as in example 2 except that it is calcined for 1000 ℃ -1h), fig. 8(D) is an XRD pattern of 1050 ℃ green silicon fertilizer (the preparation method is the same as in example 2 except that it is calcined for 1050 ℃ -1h), fig. 8(E) is an XRD pattern of 1100 ℃ green silicon fertilizer (the preparation method is the same as in example 2 except that it is calcined for 1100 ℃ -1h), fig. 8 (F) is an XRD pattern of 1150 ℃ green silicon fertilizer (the preparation method is the same as in example 2 except that it is calcined for 1150 ℃ -1h), fig. 8(G) is an XRD pattern of 1200 ℃ green silicon fertilizer (the preparation method is the same as in example 2, the difference is only in XRD pattern of roasting 1200-1H), and figure 8(H) is the green silicon fertilizer obtained in the example 2. The measuring angle range of the full-automatic X-ray diffractometer is 5-90 degrees, and the step length is 0.0263 degrees.
As can be seen from fig. 8: the talcum powder and the green silicon fertilizer obtained in the embodiment 2 are mainly composed of Ca2Mg(Si2O7) And a small amount of Ca3Mg(SiO4)2And (4) forming. From the XRD patterns of the calcined products produced under other different conditions, it can be observed that: when the roasting time is 1100-1 h, the main roasting product of the talcum powder and the calcium carbonate is Ca2Mg(Si2O7) And Ca3Mg(SiO4)2The calcination product is gradually changed to high-purity Ca with the increase of calcination time or calcination temperature2Mg(Si2O7) Close together with increasingly smaller amounts of Ca3Mg(SiO4)2(ii) occurs; at the roasting temperature of 950-1 h, a small amount of CaMgFe (OH) (PO) appears in the roasted product4)2(H2O)4And Ca (OH)2Its CaMgFe (OH) (PO)4)2(H2O)4The occurrence of (A) is influenced by the main component of the talcum powder; as the roasting temperature is increased to 1000-1 h, Ca begins to appear in the main roasting product3Mg(SiO4)2(ii) a At 1050-1 h, the roasted product is mainly CaMg (CO)3)2、 Ca2(SiO4) MgO and Ca3Mg(SiO4)2This is the product of the decomposition of talc by heat and the chemical reaction with calcium carbonate at high temperature.
(VI) Infrared spectroscopic analysis of the Green silicon Fertilizer obtained in this example
Infrared FT-IR analysis was performed on the talc powder and the green silicon fertilizer obtained in this example using a fourier transform infrared spectrometer, the results are shown in fig. 9; FIG. 9 is a FT-IR diagram of talc powder in FIG. 9(A), a FT-IR diagram of 950 ℃ green silicon fertilizer (the same preparation method as in example 2 except for calcination for 950 ℃ -1h), a FT-IR diagram of 1000 ℃ green silicon fertilizer (the same preparation method as in example 2 except for calcination for 1000 ℃ -1h), a FT-IR diagram of 1050 ℃ green silicon fertilizer (the same preparation method as in example 2 except for calcination for 1050 ℃ -1h), a FT-IR diagram of 1100 ℃ green silicon fertilizer (the same preparation method as in example 2 except for calcination for 1100 ℃ -1h), and a FT-IR diagram of 1150 ℃ green silicon fertilizer (the same preparation method as in example 2 except for calcination for 1150 ℃ -1h) in FIG. 9(F), FIG. 9G shows 1200 deg.C green silicon fertilizer (preparation method and application thereof)Example 2 is the same, except for FT-IR chart of roasting 1200 ℃ -1H), and FIG. 9(H) is the green silicon fertilizer obtained in this example. The scanning range of the Fourier transform infrared spectrometer is 400-4000 cm-1。
As can be seen from fig. 9: the peak of talc in FIG. 9(A) appeared at 3677.53cm-1、 1017.49cm-1And 671.36cm-1Thereby determining the presence of talc; at 3444.82cm-1The peak position occurs due to the liquid H21645.90cm caused by O stretching vibration-1May be due to the liquid state H2O variation angle vibration induced sum 460.01cm-1The weak absorption peak is caused by PO4 3-PO of4Asymmetric angulation. FIGS. 9(B) to 9(H) are 500 to 700cm-1The absorption peak appeared due to carbon bromine stretching, which was 478cm in both FIG. 9(G) and FIG. 9(H)-1All of them had weak peaks, probably due to P-Cl expansion or problems in the flaking process, at 935cm in FIG. 9(B), FIG. 9(C), FIG. 9(E), FIG. 9(F), FIG. 9(G) and FIG. 9(H)-1The peak position in the vicinity was caused by symmetric stretching of O-P-O, 888.05cm in FIG. 9(D)-1The absorption peaks appeared probably due to Si-C, FIG. 9(B), FIG. 9(D), FIG. 9(G) and FIG. 9(H) at 980cm-1The weak absorption peak appearing nearby is mainly caused by C-O stretching; FIG. 9(B), FIG. 9(C), FIG. 9(D), FIG. 9(G) and FIG. 9(H) are at 1100cm-1The peak position appearing nearby is caused by antisymmetric expansion and contraction of Si-O-Si, and 1350-1500 cm is shown in FIG. 9(B), FIG. 9(C), FIG. 9(D), FIG. 9(E) and FIG. 9(H)-1The broad and weak absorption peak at (A) represents the alcohol COH in-plane bending vibration at 1640cm in FIGS. 9(B) to 9(H)-1The relatively broad absorption peak represents liquid H2O variable angle vibration, at 3400cm in FIGS. 9(B) to 9(H)-1The absorption peak is mainly due to liquid H2O stretching vibration, and the length of the distance from 3500 cm to 3950cm in FIGS. 9(B) to 9(D)-1A sharp absorption peak appears in between, which represents gaseous H2And O, stretching and vibrating.
Seventhly, the specific surface area and the pore diameter of the green silicon fertilizer obtained in the embodiment are analyzed
Analyzing the specific surface area and the aperture of the talcum powder and the green silicon fertilizer obtained in the embodiment 2 by using a full-automatic specific surface area analyzer; the measured isothermal adsorption/desorption curves of the talcum powder and the green silicon fertilizer of the example 2 are shown in figure 10: fig. 10(a) is an isothermal adsorption/desorption curve of talc powder, and fig. 10(B) is an isothermal adsorption/desorption curve of the green silicon fertilizer obtained in example 2.
As can be seen from fig. 10: the isothermal adsorption line of the talcum powder and the green silicon fertilizer obtained in the embodiment has a slightly different form, but the isothermal adsorption line is in an inverse S shape on the whole, and the front section of the adsorption curve rises slowly and slightly protrudes upwards. The adsorption capacity is increased sharply when the relative pressure is close to 1.0, and the phenomenon of adsorption saturation is not presented; this indicates that capillary condensation occurs during the nitrogen adsorption process, indicating that both the talc powder and the green silicon fertilizer obtained in example 2 contain a certain amount of mesopores and macropores. The adsorption curve and desorption curve of the talcum powder and the green silicon fertilizer in the example 2 are not overlapped at the higher pressure part to form a hysteresis loop, according to the division of the type of the hysteresis loop by the International Union of Pure and Applied Chemistry (IUPAC), the hysteresis loop of both is shown as H3 type, and the isotherm and the hysteresis loop show that the main pore is mesopore, which reflects that the basic pore type can be 'slit type' pore.
The results of the single-point specific surface area, the multi-point specific surface area, the total pore volume adsorbed, the average pore diameter adsorbed, and the micropore analysis (slit-type pore HK method; pore width <2nm) of the talc powder and the green silicon fertilizer of example 2 are shown in Table 3.
TABLE 3 Talc powder and Green silicon Fertilizer Single-Point specific surface area, Multi-Point specific surface area, Total pore volume adsorbed, average pore diameter adsorbed, and micropore analysis (slit-type pore HK method; pore width <2nm)
As can be seen from table 3: the single-point specific surface area of the talcum powder can reach 6.568m2The concentration of the silicon fertilizer is higher than that of the green silicon fertilizer obtained in example 2; meanwhile, the test results of the multipoint specific surface area, the total adsorption pore volume and the micropore analysis of the talcum powder are all compared with the test results of the embodiment2 the obtained green silicon fertilizer is much higher. The average adsorption pore size of the green silicon fertilizer obtained in example 2 can reach 18.809nm, which is higher than the average adsorption pore size of 14.180nm of talcum powder. This phenomenon is due to the fact that calcium carbonate interacts with talc at high temperatures causing the structure of the talc to be destroyed and agglomerated pores to appear.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of a green silicon fertilizer comprises the following steps:
mixing talcum powder and calcium carbonate and roasting; cooling the roasted product to 600-800 ℃ along with the furnace, and then air-cooling to room temperature to obtain a green silicon fertilizer;
the mole ratio of the talcum powder to the calcium carbonate is 1: 1.4-2.4;
the roasting temperature is 1050-1200 ℃, and the roasting time is 30-210 min.
2. The preparation method according to claim 1, wherein the particle size of the talc powder is 20 to 200 mesh; the particle size of the calcium carbonate is 20-200 meshes.
3. The method of claim 1, wherein the calcium carbonate is analytically pure.
4. The preparation method according to claim 1, wherein the purity of the talc powder is 85 to 99.9%.
5. The method according to claim 1, wherein the heating power for raising the temperature to the baking temperature is 4 to 5 kW.
6. The green silicon fertilizer obtained by the preparation method of any one of claims 1 to 5, wherein the green silicon fertilizer is characterized by being prepared by using a silicon-containing organic solventFertilizer composition Ca2Mg(Si2O7) And a small amount of Ca3Mg(SiO4)2Composition is carried out; the effective silicon content is 17.11-19.93%; the average adsorption pore diameter is 17.906-19.704 nm; the single-point specific surface area is 1.298-1.356 m2(ii)/g; the green silicon fertilizer belongs to citric soluble silicon fertilizer, the solubility in 2% citric acid and ultrapure water can reach 0.0365g/100mL and 0.0146g/100mL respectively, and no aluminum is detected.
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