Disclosure of Invention
Aiming at the situation, the invention aims to overcome the defects of the prior art, and aims to provide the nano mineral powder, the preparation method and the application thereof in preparing fertilizer, which can effectively solve the problems of how to prepare the natural mineral nano material which can be comprehensively utilized and has low cost, and can be applied in preparing fertilizer, thereby realizing soil restoration improvement, no pollution and environmental protection.
The technical scheme of the invention is that the nano mineral powder is prepared from 40-50 parts by weight of kaolinite, 40-50 parts by weight of illite, 40-50 parts by weight of pyrophyllite and 50-70 parts by weight of bauxite serving as ore raw materials; wherein the total content of silicon dioxide in the ore raw material is 20-25%, and the total content of titanium dioxide is 1-1.4%;
the bauxite is one or the combination of any two or three of bauxite, bauxite and high bauxite.
The preparation method of the nano mineral powder comprises the following specific steps:
crushing treatment: feeding kaolinite, illite, pyrophyllite and bauxite into a crusher to crush into ore particles of 2-3 cm;
and (3) a flotation impurity removal stage: to the ore particles, 3 cubic water was added per ton of ore feedAdding water to prepare raw ore pulp, adding the raw ore pulp into grinding equipment (such as a ball mill), grinding the raw ore pulp until the ore particle size is less than 37 mu m, wherein the ore particle size accounts for 85% of the total mass of the raw ore pulp, obtaining primary ore pulp, adjusting the pH value of the primary ore pulp to be 7-12, conveying the primary ore pulp into a cyclone, separating the primary ore pulp under the pressure of 0.3MPa, enabling ore liquid with the particle size of less than 37 mu m to flow out of an upper overflow port of the cyclone to obtain an overflow A, enabling the rest of the overflow A to flow out of a bottom flow port and be an underflow A, returning the underflow A to the grinding equipment (the solid-liquid ratio in the grinding equipment is 1:3, wherein the solid unit is ton, and the liquid unit is cube), adding water into the overflow A to prepare secondary ore pulp with the solid content of 20-40%, adding a collector into the secondary ore pulp according to the amount of 800-2000g of the collector added per ton of ore raw material, and adjusting the pH value to be 7-12; the collector is any one or a combination of more of fatty acid, sodium fatty acid and sodium hexametaphosphate; the fatty acid is oleic acid (oleic acid with the content of 85 percent) or sodium oleate (sodium oleate with the content of 85 percent); introducing air into the secondary ore pulp according to the amount of 0.3 cubic air introduced into each ton of ore raw material, and simultaneously introducing the air into a flotation tank at 15-60 ℃ and the flow rate of 50-150m 3 Floating under the condition of/H to obtain a foam product overflow B and an underflow B, wherein the foam product overflow B is multi-scale mixture mixed pulp, and is discharged out of the system, and a flocculating agent is added into the underflow B, and the flocculating agent is anionic polyacrylamide (molecular formula (C3H 5 NO) n, and the molecular weight is 600-800 ten thousand anionic polyacrylamide); adding flocculant into the underflow B according to the weight of one ten per ton to three ten per ton of ore raw materials, simultaneously entering a settling tank, separating at the temperature of 15-60 ℃ and the flow rate of 30t/h to obtain overflow C and underflow C (the mass concentration of the underflow C is 30% -50%), recycling the overflow C in a clean water tank, and pressing the underflow C under the pressure of 0.8MPa (the equipment for pressing and separating is a membrane filter press) to obtain a primary ore cake A with the water content of 20% -30%;
and (3) a drying and grinding stage: drying the primary ore cake A at 800-1500 ℃ until the water content of the primary ore cake A is 6-10%, and then grinding the dried primary ore cake A by a dry method (the equipment for dry grinding is a Raymond mill) to obtain finished ore powder, wherein the average thickness of the finished ore powder is 51.4nm, namely nano ore powder (also called nano natural ore powder, hereinafter referred to as nano natural ore powder);
the invention also aims at providing the application of the nano mineral powder in preparing fertilizer.
The invention also aims to provide the application of the nano mineral powder in preparing the soil restoration type compound fertilizer.
A soil restoration type compound fertilizer for wheat and corn comprises the nano mineral powder.
The soil restoration type compound fertilizer for peanuts and garlic comprises the nano mineral powder.
The soil restoration type compound fertilizer for the solanaceous fruits comprises the nano mineral powder.
The method has the advantages that the source of the ore raw materials used in the method is wide, the cost is low, the selectable range is wide, the cost caused by primary processing is reduced, no harmful substances are generated after the method is used for processing, the method is environment-friendly and environment-friendly, the prepared nano mineral powder has high activity and is favorable for being absorbed by plant root systems in soil, the using effect of the fertilizer is improved, the specific natural ore is used as the raw material, the natural ore is prepared into the nano raw material through the high-energy ball milling technology, and meanwhile, the beneficial elements in the natural ore are purified through the floatation purification technology, so that the method has the function of supplementing the beneficial mineral elements of the soil and restoring the soil.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to examples.
Example 1
The nanometer mineral powder is prepared from 40 parts of kaolinite, 40 parts of illite, 40 parts of pyrophyllite and 50 parts of laterite serving as ore raw materials in parts by weight; wherein the total content of silicon dioxide in the ore raw material is 20 percent, and the total content of titanium dioxide is 1 percent.
Example 2
The nanometer mineral powder is prepared from 50 parts by weight of kaolinite, 50 parts by weight of illite, 50 parts by weight of pyrophyllite and 70 parts by weight of bauxite serving as ore raw materials; wherein the total content of silicon dioxide in the ore raw material is 22 percent, and the total content of titanium dioxide is 1.2 percent.
Example 3
The nanometer mineral powder is prepared from 45 parts of kaolinite, 45 parts of illite, 45 parts of pyrophyllite and 60 parts of bauxite serving as ore raw materials in parts by weight; wherein the total content of silicon dioxide in the ore raw material is 24 percent, and the total content of titanium dioxide is 1.3 percent.
Example 4
The nanometer mineral powder is prepared from 40 parts of kaolinite, 40 parts of illite, 50 parts of pyrophyllite, 35 parts of bauxite and 35 parts of bauxite serving as ore raw materials in parts by weight; wherein the total content of silicon dioxide in the ore raw material is 25 percent, and the total content of titanium dioxide is 1.1 percent.
Example 5
The nanometer mineral powder is prepared from 45 parts of kaolinite, 50 parts of illite, 45 parts of pyrophyllite, 10 parts of bauxite, 20 parts of bauxite and 20 parts of high bauxite serving as ore raw materials in parts by weight; wherein the total content of silicon dioxide in the ore raw material is 23 percent, and the total content of titanium dioxide is 1.4 percent.
Example 6
The preparation method of the nano mineral powder in the above embodiments 1 to 5 comprises the following specific steps:
crushing treatment: feeding kaolinite, illite, pyrophyllite and bauxite into a crusher to crush into ore particles of 2-3 cm;
and (3) a flotation impurity removal stage: adding water into ore particles according to the amount of adding 3 cubic meters of water into each ton of ore raw material to prepare raw ore pulp, adding the raw ore pulp into a ball mill, grinding the raw ore pulp until the ore particle size smaller than 37 mu m accounts for 85% of the total mass of the raw ore pulp to obtain primary ore pulp, adjusting the pH value of the primary ore pulp to 7, conveying the primary ore pulp into a cyclone, separating the primary ore pulp under the pressure of 0.3MPa, enabling ore liquid with the particle size smaller than 37 mu m to flow out of an overflow port at the upper part of the cyclone to obtain an overflow object A, enabling the rest of the overflow liquid to flow out of a bottom flow port to form an underflow object A, returning the underflow object A into the ball mill again, and fixing solids in the ball millThe liquid ratio is 1:3, wherein the solid unit is ton, the liquid unit is cube, the overflow A is added with water to prepare secondary ore pulp with the solid content of 20%, and oleic acid is added into the secondary ore pulp according to the amount of adding 800g of collector into each ton of ore raw material; adjusting the pH value to 7; introducing air into the secondary ore pulp according to the amount of 0.3 cubic air introduced into each ton of ore raw material, and simultaneously introducing the air into a flotation tank at 15 ℃ at a flow rate of 50m 3 Flotation under the condition of/h to obtain foam product overflow B and underflow B, wherein the foam product overflow B is discharged from the system; adding anionic polyacrylamide into the underflow B, wherein the anionic polyacrylamide is of which the molecular weight is 600-800 ten thousand; adding anionic polyacrylamide into the underflow B according to the weight of one ten thousandth of each ton of ore raw materials, simultaneously entering a settling tank, and separating under the conditions of the temperature of 15 ℃ and the flow speed of 30t/h to obtain an overflow C and an underflow C, wherein the mass concentration of the underflow C is 30%, the overflow C enters a clean water tank for recycling, the underflow C enters a membrane filter press, and the filter press is carried out under the condition of the pressure of 0.8MPa to obtain a primary ore cake A with the water content of 20%;
and (3) a drying and grinding stage: and (3) drying the primary ore cake A at 800 ℃ until the water content of the primary ore cake A is 6%, grinding the dried primary ore cake A by a Raymond mill to obtain finished ore powder, wherein the average thickness of the finished ore powder is 51.4nm, and the finished ore powder is nano ore powder.
Example 7
The preparation method of the nano mineral powder in the above embodiments 1 to 5 comprises the following specific steps:
crushing treatment: feeding kaolinite, illite, pyrophyllite and bauxite into a crusher to crush into ore particles of 2-3 cm;
and (3) a flotation impurity removal stage: adding water into ore particles according to the amount of adding 3 cubic meters of water into each ton of ore raw material to prepare raw ore pulp, adding the raw ore pulp into a ball mill, grinding the raw ore pulp until the ore particle size is less than 37 mu m and accounts for 85 percent of the total mass of the raw ore pulp to obtain primary ore pulp, adjusting the pH value of the primary ore pulp to be 12, then conveying the primary ore pulp into a cyclone, separating the primary ore pulp under the pressure of 0.3MPa, and flowing out ore liquid with the particle size of less than 37 mu m from an upper overflow port of the cyclone to obtain an overflow AThe rest flows out from the underflow opening and is an underflow A, the underflow A is returned to the ball mill again (the solid-liquid ratio in the ball mill is 1:3, the solid unit is ton, the liquid unit is cube), the overflow A is added with water to prepare a secondary ore pulp with the solid content of 40%, sodium oleate is added into the secondary ore pulp according to the amount of 2000g of collector added into each ton of ore raw material, and the pH value is adjusted to be 12; introducing air into the secondary ore pulp according to the amount of 0.3 cubic air introduced into each ton of ore raw material, and simultaneously introducing the air into a flotation tank at 60 ℃ and a flow rate of 150m 3 Floating under the condition of/h to obtain a foam product overflow B and an underflow B, wherein the foam product overflow B is discharged out of the system, and anionic polyacrylamide with the molecular weight of 600-800 ten thousand is added into the underflow B; adding anionic polyacrylamide into the underflow B according to the weight of three parts per million of ore raw materials, simultaneously entering a settling tank, separating at the temperature of 60 ℃ and the flow rate of 30t/h to obtain an overflow C and an underflow C (the mass concentration of the underflow C is 50%), recycling the overflow C in a clean water tank, pressing the underflow C under the pressure of 0.8MPa to obtain a primary ore cake A with the water content of 30%;
and (3) a drying and grinding stage: and (3) drying the primary ore cake A at 1500 ℃ until the water content of the primary ore cake A is 10%, and then carrying out dry grinding on the dried primary ore cake A by a Raymond mill to obtain finished ore powder, wherein the average thickness of the finished ore powder is 51.4nm, and the finished ore powder is nano ore powder.
Example 8
The preparation method of the nano mineral powder in the above embodiments 1 to 5 comprises the following specific steps:
crushing treatment: feeding kaolinite, illite, pyrophyllite and bauxite into a crusher to crush into ore particles of 2-3 cm;
and (3) a flotation impurity removal stage: adding water into ore particles according to the amount of adding 3 cubic meters of water into each ton of ore raw material, preparing raw ore pulp, putting into a ball mill, grinding until the ore particle size smaller than 37 mu m accounts for 85% of the total mass of the raw ore pulp to obtain primary ore pulp, adjusting the pH value of the primary ore pulp to be 10, and conveying into a ball millA cyclone, separating under the pressure of 0.3MPa, wherein ore liquid with the particle size smaller than 37 mu m flows out from an upper overflow port of the cyclone to obtain an overflow A, and the rest flows out from a bottom flow port to obtain an underflow A, wherein the underflow A returns to a ball mill again (the solid-to-liquid ratio in the ball mill is 1:3, the solid unit is ton, and the liquid unit is cube), the overflow A is added with water to prepare a secondary ore pulp with the solid content of 30%, and sodium fatty acid or 700g of sodium fatty acid and 700g of sodium hexametaphosphate are added into the secondary ore pulp according to the amount of 1400g of collector added into each ton of ore raw material, and the pH value is adjusted to 9; introducing air into the secondary ore pulp according to the amount of 0.3 cubic air introduced into each ton of ore raw material, and simultaneously introducing the air into a flotation tank at 30 ℃ at a flow rate of 100m 3 Floating under the condition of/h to obtain a foam product overflow B and an underflow B, wherein the foam product overflow B is discharged out of the system, and the underflow B is added with anionic polyacrylamide, and the anionic polyacrylamide has the molecular weight of 600-800 ten thousand; adding anionic polyacrylamide into the underflow B according to the amount of two ten thousandths of each ton of ore raw material, simultaneously entering a settling tank, and separating under the conditions of the temperature of 40 ℃ and the flow rate of 30t/h to obtain an overflow C and an underflow C (the mass concentration of the underflow C is 40%), wherein the overflow C enters a clean water tank for recycling, the underflow C enters a membrane filter press, and the pressure of is carried out under the condition of the pressure of 0.8MPa to obtain a primary ore cake A with the water content of 25%;
and (3) a drying and grinding stage: and (3) drying the primary ore cake A at 1000 ℃ until the water content of the primary ore cake A is 8%, and then carrying out dry grinding on the dried primary ore cake A by a Raymond mill to obtain finished ore powder, wherein the average thickness of the finished ore powder is 51.4nm, and the finished ore powder is nano ore powder.
The detection shows that the finished mineral powder has 30-39% of silicon dioxide, 1.8-2% of titanium dioxide, 0.8-1% of calcium and magnesium ions, 150-200ppm of rare earth elements (lanthanum and cerium) and 51.4nm of average thickness of nano mineral powder (1-100 nm is called as nano material); the foam product overflow B produced in the preparation method is multi-scale mixture impurity pulp, is a raw material for producing alumina, and mainly comprises diaspore, and can be recovered by an alumina plant after separation, so that the environment is not polluted.
The application of the nano mineral powder in the preparation of fertilizer is described in the embodiments 1-8;
the application of the nano mineral powder in the preparation of the soil restoration type compound fertilizer is described in the embodiments 1-8;
a soil restoration type compound fertilizer for wheat and corn comprises the following components in parts by weight: 20 parts of nano mineral powder, 34.5 parts of urea, 8.4 parts of potassium chloride and 37.1 parts of ammonium chloride are used as raw materials to prepare the composite fertilizer, the nano mineral powder, the urea, the potassium chloride and the ammonium chloride are uniformly mixed, and then the composite fertilizer is granulated, dried, cooled, sieved and coated by a conventional method to obtain the composite fertilizer (N-P) for wheat and corn soil restoration with 30 percent of nutrient content 2 O 5 -K 2 O 25-0-5cl)。
A soil restoration type compound fertilizer for peanuts and garlic comprises the following components in parts by weight: 30 parts of nano mineral powder, 23 parts of urea, 12 parts of monoammonium phosphate (total nutrient content 55%), 15 parts of potassium chloride, 10 parts of ammonium chloride, 0.06 part of ammonium heptamolybdate and boric acid (H) 3 BO 3 More than or equal to 99.5 percent) and 0.14 part of the fertilizer is used as raw materials, nano mineral powder, urea, monoammonium phosphate, potassium chloride, ammonium heptamolybdate and boric acid are uniformly mixed, then the mixture is put into a roller granulation device, and the mixture is granulated, dried, cooled, sieved and coated according to the conventional method, thus obtaining the soil restoration type compound fertilizer (N-P) for peanuts and garlic, wherein the nutrient content of the soil restoration type compound fertilizer is 30 percent 2 O 5 -K 2 O 16-5-9cl)。
A soil restoration type compound fertilizer for solanaceous fruits comprises the following components in parts by weight: 30 parts of nano mineral powder, 9 parts of urea, 21.5 parts of monoammonium phosphate, 19.5 parts of ammonium sulfate and potassium sulfate (K) 2 20 parts of O more than or equal to 60.0 percent) is used as raw materials, nano mineral powder, urea, monoammonium phosphate, ammonium sulfate and potassium sulfate are uniformly mixed, then the mixture enters roller granulation equipment, and granulation, drying, cooling, sieving and coating are carried out according to a conventional method, thus obtaining the soil remediation type compound fertilizer (N-P) for solanaceous fruits with 30 percent of nutrient content 2 O 5 -K 2 O 10-10-10S)。
In order to further illustrate the application value of the nano mineral powder prepared by the invention in the fertilizer, the application selects test fields on corn, peanut and capsicum respectively for experiments, and the results are as follows:
A. a test field with serious salinization of the soil in a yellow flood area is specially selected, wherein, one half of the test field only uses common fertilizer 28-5-5 (cl) (such as nitro controlled release fertilizer 28-5-5) as a control group during the corn planting period, and the other half uses the wheat and corn soil restoration type compound fertilizer (N-P) with 30 percent of nutrient content during the corn planting period 2 O 5 -K 2 O25-0-5 cl) as experimental group, corn disease occurrence and yield were sampled and investigated during planting, and corn yield statistics were combined as follows:
|
control group
|
Experimental group
|
Pre-planting soil EC 1:5 (ds/m)
|
1.32
|
1.32
|
Post-harvest soil EC 1:5 (ds/m)
|
1.30
|
0.98
|
Pre-planting soil PH
|
7.8
|
7.8
|
Post-harvest soil pH
|
7.7
|
7.4
|
Rust disease (%)
|
34.7
|
8.3
|
Length of bald tip (cm)
|
1.88
|
1.42
|
Corn hundred grain weight (g)
|
27.34
|
35.94
|
Corn yield (kg/mu)
|
559.6
|
723.2
|
Fertilizer per mu (kg/mu)
|
40
|
40
|
Fertilizer cost (Yuan/mu)
|
140
|
150
|
Corn sales income (Yuan/mu)
|
1343
|
1735.7 |
From the data, it can be seen that the wheat and corn soil restoration compound fertilizer (N-P) with 30% nutrient content is used for planting corn 2 O 5 -K 2 O25-0-5 cl), the EC value of the soil is obviously reduced, the pH value of the soil is improved, and the incidence rate of corn rust is greatly reducedMeanwhile, the length of the bald tip of the corn is obviously reduced, the hundred-grain weight is obviously improved, the yield of the corn is finally greatly improved, the improvement effect on salinized soil for planting the corn is obvious, the fertilizer input per mu is more than 10 yuan, the yield is increased by 163.6 kg, the yield per kg of the corn is 2.4 yuan, and the yield per mu is improved by 382.6 yuan.
B. Specially selects a peanut test field with middle continuous sitting disorder in a standing-horse shop area for five years, wherein one half of the peanut test field is planted with common fertilizer 18-10-12 (cl) (such as kenfeng compound fertilizer 18-10-12) as a control group during peanut planting, and the other half of the peanut test field is planted with the soil restoration compound fertilizer (N-P) for peanuts and garlic, wherein the nutrient content of the soil restoration compound fertilizer is 30 percent during peanut planting 2 O 5 -K 2 O16-5-9 cl) was used as an experimental group, and the occurrence rate of peanut diseases was sampled and investigated during the planting period, and the peanut yield was counted as follows:
|
control group
|
Experimental group
|
Pre-planting soil EC 1:5 (ds/m)
|
0.89
|
0.89
|
Post-harvest soil EC 1:5 (ds/m)
|
0.87
|
0.65
|
Pre-planting soil PH
|
5.3
|
5.3
|
Post-harvest soil pH
|
5.2
|
6.4
|
Incidence of root rot (%)
|
10.3
|
1.2
|
Incidence of southern blight (%)
|
15.4
|
2.3
|
Peanut yield (kg/mu)
|
481.28
|
528
|
Fertilizer per mu (kg/mu)
|
40
|
40
|
Fertilizer cost (Yuan/mu)
|
150
|
160
|
Peanut sales income (Yuan/mu)
|
2887.7
|
3168 |
From the above data, it can be seen that the soil restoration type compound fertilizer (N-P) for peanuts and garlic, which has a nutrient content of 30%, is used for planting peanuts 2 O 5 -K 2 O16-5-9 cl), the EC value and the pH value of the soil are obviously improved, the soil-borne diseases of the peanuts are greatly reduced, andthe yield of the peanuts is greatly improved, the continuous cropping obstacle soil for planting the peanuts has a remarkable improvement effect, the fertilizer is added for 10 yuan per mu, the yield is increased by 46.7 kg, the yield is increased by 6 yuan per kg, and the yield is increased by 270.2 yuan per mu.
C. Specially selects a block of pepper test field with moderate continuous sitting disorder for four years in a complex river region, wherein, half of the pepper test field is used only with common fertilizer 15-10-15S (such as potassium sulfate compound fertilizer 15-10-15-sea shoe-shaped gold ingot-middle farmer) as a control group during the pepper planting period, and the other half is used with the soil restoration compound fertilizer (N-P) for solanaceous fruits with 30 percent nutrient content during the pepper planting period 2 O 5 -K 2 O10-10-10S) as an experimental group, the incidence of pepper disease was sampled and investigated during planting, and the following was calculated in combination with the pepper yield:
|
control group
|
Experimental group
|
Pre-planting soil EC 1:5 (ds/m)
|
0.74
|
0.74
|
Post-harvest soil EC 1:5 (ds/m)
|
0.75
|
0.59
|
Pre-planting soil PH
|
5.5
|
5.5
|
Post-harvest soil pH
|
5.4
|
6.6
|
Incidence of bacterial wilt (%)
|
23.7
|
4.3
|
Incidence of sunscald (%)
|
7.8
|
3.7
|
Pepper yield (kg/mu)
|
344.6
|
409.7
|
Fertilizer per mu (kg/mu)
|
60
|
60
|
Fertilizer cost (Yuan/mu)
|
192
|
216
|
Pepper sales income (Yuan/mu)
|
6202.8
|
7374.6 |
From the data, the invention can be seen that the pepper uses the soil restoration type compound fertilizer (N-P 2 O 5 -K 2 O10-10-10S), the EC value and the ph of the soil are obviously improved, the bacterial wilt of the capsicum soil-borne disease is obviously reduced, the occurrence of sunburn is also greatly reduced, and finally the capsicum yield is obviously improvedThe amount of the fertilizer has obvious improvement effect on continuous cropping obstacle soil for planting the peppers, the fertilizer is added for more than 24 yuan per mu, the yield is increased by 65.1 kg, 18 yuan per kg of the peppers, the yield is increased by 1147.8 yuan per mu, and the benefit increasing effect is obvious.
The natural nano mineral preparation method adopted by the invention is a wet ball milling technology, has no dust pollution, has a flotation purification process, greatly improves the content of beneficial elements, has obvious use effect, can be sold to related companies as byproducts (foam product overflow B) through the test, achieves no external pollution discharge in the overall production process under the condition of increasing income, is environment-friendly, has low comprehensive production cost, further reduces the production cost of nano fertilizer, and provides preconditions for large-area popularization and application of the nano fertilizer.
The invention uses the combination of nano natural mineral powder and nitrogen, phosphorus and potassium fertilizer, replaces some raw materials produced by artificial chemistry with natural nutrition, and realizes the purposes of simulating nature, restoring nature and returning nature, and returning the cultivated land soil to better ecological nature, thereby better achieving the purpose of soil restoration. The soil fertilizer is one, and nano natural mineral powder is added into the fertilizer, so that on one hand, the support for sustainable development of agriculture is provided, on the other hand, the soil fertilizer is a new opportunity for fertilizer industry, and the current trend of fertilizer development in China is met. Through cost accounting, the cost of each 1 ton of nano mineral powder prepared by the method is about 300 yuan, the cost of each 1 ton of common nano mineral powder prepared by the prior art is about 900 yuan, and the ore raw materials used by the method do not need to be refined, are easy to purchase, and greatly reduce the cost of raw materials.