CN115340424A - Coal gangue magnetized soil conditioner and preparation method thereof - Google Patents
Coal gangue magnetized soil conditioner and preparation method thereof Download PDFInfo
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- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
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Abstract
The invention provides a coal gangue magnetized soil conditioner and a preparation method thereof, belonging to the technical field of soil conditioners. The soil stabilizer not only has the function of ventilating and loosening soil, can improve the capacity of storing nutrients, but also can fix heavy metals, promote the development of plant root systems and the activity of beneficial microorganisms, treat the phenomena of soil hardening, desertification and salinization, improve the soil permeability, increase the water and fertilizer retention capacity of soil, reduce the water evaporation of the soil, increase the cation exchange capacity in the soil, promote trace elements to be better absorbed by the plant root systems, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of soil conditioners, in particular to a coal gangue magnetized soil conditioner and a preparation method thereof.
Background
The soil conditioner is also called soil conditioner, and is a material which can improve the physical property of soil and promote the nutrient absorption of crops, but does not provide plant nutrients. The soil amendment utility principle is to bind many small soil particles to form large, water stable aggregates. The method is widely applied to the aspects of preventing soil from being corroded, reducing water evaporation or excessive transpiration of the soil, saving irrigation water and promoting healthy growth of plants.
At present, the existing soil conditioners in the market are various in number, but the quantity of the soil conditioners prepared by utilizing solid wastes is small, and the Changhui technology successfully prepares the magnetic soil conditioner by utilizing magnetic separation iron ore tailings. According to the analysis of all-element chemical data of the coal gangue, the coal gangue has the conditions for preparing the magnetized soil conditioner, but at present, the coal gangue is used for preparing the soil conditioner, so that chemical substances such as heavy metals and the like which are not beneficial to the growth of crops are difficult to remove, and the Changhui technology adopts a magnetization treatment mode to easily change the coal gangue into inert substances with extremely low activity, and most of iron elements in the coal gangue are extracted, converted and recycled to prepare the coal gangue magnetized soil conditioner.
The coal gangue is a rock with dry-basis ash content of more than 50 percent and is a black-grey rock with low carbon content and harder than coal, which is produced in the processes of coal mine well construction, development and excavation, coal mining and coal washing. Coal gangue is a solid waste generated in the production and processing processes of coal, and the annual emission amount is about 10 percent of the annual coal yield. Coal gangue is piled up for a long time, and spontaneous combustion can occur when the internal temperature reaches a certain value, so the coal gangue is often divided into original coal gangue and spontaneous combustion coal gangue. Wherein the appearance of the original coal gangue is mostly black or gray black, and the coal slime and fine-particle coal gangue are mostly adhered on the surface. The content of carbon in the spontaneous combustion coal gangue is low, the porosity is relatively high, and the bulk density is 0.9-1.3g/cm 3 In between, the surface layer is mostly ceramic red or ceramic yellow, and the interior carbon is not fully combusted, so that a black core exists. The water absorption characteristic of the coal gangue has great influence on the comprehensive utilization of the coal gangue. The porosity of the coal gangue determines the water absorption characteristic of the coal gangueThe water absorption rate is about 2.0-6.0%, and the plasticity index is about 3.0-15. The water absorption of the spontaneous combustion coal gangue is about 3.0-11.6%, and the plasticity index is about 1.03-0.8. The main chemical composition of the coal gangue is Al 2 O 3 、SiO 2 And C, followed by CaO, fe 2 O 3 MgO, and the like. The mineral components mainly comprise kaolin, hydromica, bauxite, carbon and the like. The components of the coal gangue are affected by regions, and the differences of the components of the coal gangue are large in different regions of China.
The coal gangue is solid waste generated along with coal mining, and besides partial filling and comprehensive utilization, most of the coal gangue is stockpiled for a long time to form a gangue dump, so that land resources are occupied. The harm of the coal gangue to the natural environment is mainly reflected in the following aspects:
a. the coal gangue can form dust with small grain diameter in the stacking, transportation and other processes, and can be suspended in the atmosphere under the action of wind power, thus causing harm to human health. On the other hand, the coal gangue is easy to self-ignite due to the characteristics of the coal gangue, releases various harmful gases, and simultaneously generates a large amount of explosive smoke dust, so that the coal gangue can affect the surrounding atmospheric environment and the growth of animals and plants to different degrees during self-ignition.
b. In the process of stacking, harmful elements in the coal gangue can be dissolved under the action of rainfall and enter a water body or a soil environment, certain damage is caused to nutrients in the soil, and soil around a gangue hill can be acidified in severe cases, so that the health of a human body and the growth of vegetation are influenced.
Disclosure of Invention
The invention aims to provide a coal gangue magnetized soil conditioner and a preparation method thereof, which not only are beneficial to the effects of ventilating and loosening soil and can improve the capacity of storing nutrients, but also can fix heavy metals, promote the development of plant root systems and the activity of beneficial microorganisms, treat the phenomena of soil hardening, desertification and salinization, improve the soil permeability, increase the water and fertilizer retention capacity of soil, reduce the water evaporation of soil, increase the cation exchange capacity in soil, promote trace elements to be better absorbed by the plant root systems, and have wide application prospects.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a coal gangue magnetized soil modifier, which comprises the steps of crushing coal gangue, performing acid treatment, filtering, adding filter residue into a solution containing ferrous salt and cobalt salt, adding ammonia water to prepare magnetic coal gangue powder, further loading a nitrogen fertilizer, a phosphate fertilizer, a potash fertilizer and a carbon source, performing polydopamine modification on the surface, then soaking the polydopamine modified polydopamine powder in a solution containing engineering bacteria, culturing, separating magnets and drying to obtain the coal gangue magnetized soil modifier.
As a further improvement of the invention, the method comprises the following steps:
s1, crushing and sieving coal gangue to obtain coal gangue powder;
s2, adding the coal gangue powder obtained in the step S1 into an acid solution, heating for reaction, filtering, washing and drying to obtain acid-treated coal gangue powder, and recycling the filtrate to recover aluminum and iron;
s3, dispersing the gangue powder subjected to acid treatment in the step S2 in water, adding ferrous salt and cobalt salt, dropwise adding ammonia water while continuously stirring, adjusting pH, heating for reaction, filtering, washing, drying and calcining to obtain magnetic gangue powder;
s4, dissolving a nitrogen fertilizer, a phosphate fertilizer, a potassium fertilizer and a carbon source in water, adding the magnetized coal gangue powder in the step S3, and heating to remove the solvent to obtain the nutritional magnetic coal gangue powder;
s5, adding the nourished magnetic coal gangue powder obtained in the step S4 into water, adding dopamine hydrochloride and a catalyst, heating for reaction, separating a magnet, and washing to obtain modified coal gangue powder;
s6, inoculating the engineering bacteria strain to an MDA culture medium, and performing activated culture to obtain a strain seed solution;
and S7, soaking the modified coal gangue powder in the step S5 in the strain seed liquid in the step S6, culturing, carrying out magnet separation, and drying to obtain the coal gangue magnetized soil conditioner.
As a further improvement of the invention, the mesh number of the screen in the step S1 is 80-100 meshes.
As a further improvement of the invention, the acid solution in the step S2 is a hydrochloric acid or sulfuric acid solution with the weight percent of 7-12, the heating reaction temperature is 40-50 ℃, and the heating reaction time is 1-2h; adding alkali into filtrate, filtering and calcining to obtain ferric oxide, continuously adding weak acid into the filtrate in the previous step, filtering and calcining to obtain aluminum oxide; the alkali is NaOH or KOH; the weak acid is acetic acid.
As a further improvement of the invention, the mass ratio of the ferrous salt to the cobalt salt in the step S3 is 25-30; the pH value is adjusted to 7.7-8.2; the heating reaction is carried out at the temperature of 35-45 ℃ for 0.5-1h, and the calcination temperature is 450-700 ℃ for 2-4h.
As a further improvement of the present invention, in step S4, the nitrogen fertilizer is at least one selected from urea, ammonium nitrate, sodium nitrate and ammonium chloride; the phosphate fertilizer is selected from at least one of monopotassium phosphate, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate and sodium monohydrogen phosphate; the potash fertilizer is at least one of potassium chloride, potassium nitrate and potassium sulfate; the carbon source is at least one selected from glucose, maltose, lactose, sucrose, fructose and isomaltose; the mass ratio of the nitrogenous fertilizer to the phosphate fertilizer to the potash fertilizer to the carbon source is (3-5).
As a further improvement of the invention, the mass ratio of the nourished magnetic coal gangue powder, dopamine hydrochloride and catalyst in step S5 is (100); the catalyst is a Tris-HCl solution with pH = 5.5-6; the heating reaction is carried out at the temperature of 35-45 ℃ for 2-4h.
As a further improvement of the invention, in the step S6, the engineering bacteria comprise bacillus subtilis, bacillus licheniformis, nitrobacter and aspergillus oryzae in a mass ratio of 1-3; the bacteria content of the strain seed liquid is 10 7 -10 8 cfu/mL。
As a further improvement of the invention, the mass ratio of the modified coal gangue powder to the engineering bacteria agent in the step S7 is 1:2-3; the culture condition is 35-40 ℃ for 12-18h.
The invention further protects the coal gangue magnetized soil conditioner prepared by the preparation method.
The invention has the following beneficial effects:
(1) after the coal gangue is subjected to acid treatment to remove harmful substances such as heavy metals, iron impurities and the like, the obtained filtrate can be further recycled, and aluminum oxide, iron oxide and the like are obtained through recovery, so that the additional value of the coal gangue is improved;
(2) the invention further fixes iron and cobalt in situ on the acid-treated coal gangue powder, and calcines the coal gangue powder to obtain magnetic ferroferric oxide and cobalt oxide, thereby preparing the magnetic coal gangue powder, having self-cleaning effect on soil, improving the physical and chemical properties of the soil, treating the phenomena of soil hardening, desertification and salinization, improving the permeability of the soil, increasing the water and fertilizer retention capacity of the soil, reducing the water evaporation of the soil, increasing the cation exchange capacity in the soil, and promoting the trace elements to be better absorbed by plant roots.
(3) Because a large amount of aluminum oxide is removed in the acid treatment process, a large amount of holes are formed in the gangue powder subjected to acid treatment, nitrogen, phosphorus and potassium fertilizers and carbon sources are enriched, and after a layer of polydopamine layer is further deposited on the surface and modified, groups such as hydroxyl, amino, carboxyl and the like on the surface of the polydopamine are easy to fix subsequent engineering bacteria on one hand, and can be coordinated with heavy metal ions in soil on the other hand, so that the heavy metal is fixed, and the situation that the nutritive value of plants is influenced due to the fact that the plants absorb the heavy metal ions is avoided.
(4) The coal gangue magnetized soil conditioner prepared by the invention contains nutrient substances (such as carbon source, nitrogen fertilizer and the like) required by engineering bacteria, so the engineering bacteria are fermented and propagated in large quantity to generate a large quantity of nutrient substances beneficial to plant growth; and the plant root system growth and beneficial microorganism activities can be promoted because the plant root system growth promoter contains humic acid, organic matters, silicon, potassium, iron and various rare elements.
(5) Because the coal gangue magnetized soil conditioner has magnetism and higher content of C element, the coal gangue magnetized soil conditioner has the function of clearing, decomposing and adsorbing heavy metal ions in soil, such as Pb 2+ 、Cd 2+ 、Cu 2+ 、Cr 3+ The effect is obvious because of the equal heavy metal ions and the C element is in the soilThe fertilizer has activity, plays a role in ventilating and loosening soil for cohesive soil, and can improve the capacity of storing nutrients.
(6) When the coal gangue magnetized soil conditioner is applied to soil, a lot of micro magnetic fields are formed in the soil, and the micro magnetic fields can directly affect the soil and crops. The existence of a large amount of micro magnetic fields enhances the micro-aggregation effect of the soil, reduces the specific surface and the cohesive force, thereby playing the roles of breaking hardening and loosening the soil; the existence of a large number of micro magnetic fields adjusts the magnetic environment for the growth of crops, and improves the nutrient absorption and running capacity of the crops, thereby greatly improving the nutrient utilization rate.
(7) The coal gangue magnetized soil conditioner can promote nutrient absorption and improve soil fertility. The coal gangue has high content of organic matters, nitrogen, phosphorus and potassium, and can provide necessary nutrient elements for plant growth. The coal gangue also contains nutrient elements such as boron, molybdenum, sulfur and the like, so that the contents of trace elements and nutrient elements in the soil can be increased. Moreover, the coal gangue soil magnetization improver has higher humic acid capable of enhancing soil bioactivity, can reduce soil volume weight, increase soil porosity, improve the capacity of soil for keeping water and nutrients, enrich the diversity of soil microbial communities and improve the total amount of soil microbes.
(8) The coal gangue magnetized soil conditioner can adjust microbial community structure, improves soil microbial diversity microorganisms as necessary substances in soil, actively participates in adjusting soil structure, directly influences the biochemical activity of soil and the composition and conversion of soil nutrients, and is one of important indexes of soil fertility, wherein the internal circulation of soil nutrients, particularly nitrogen, is adjusted by the activity of the microorganisms to a great extent.
In conclusion, the coal gangue magnetized soil conditioner prepared by the invention not only is beneficial to the effect of ventilating and loosening soil, can improve the capacity of storing nutrients, but also can fix heavy metals, promote the growth of plant roots and the activity of beneficial microorganisms, treat the phenomena of soil hardening, desertification and salinization, improve the soil permeability, increase the water and fertilizer retention capacity of soil, reduce the water evaporation of soil, increase the cation exchange capacity in soil, promote trace elements to be better absorbed by the plant roots, and has wide application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The method for recycling aluminum and iron related in the embodiment and the comparative example comprises the steps of adding excessive NaOH into the filtrate, filtering, calcining to obtain iron oxide, continuously adding excessive acetic acid into the filtrate in the previous step, filtering, and calcining to obtain aluminum oxide.
Example 1
The embodiment provides a preparation method of a coal gangue magnetized soil conditioner, which comprises the following steps:
s1, crushing coal gangue, and sieving the crushed coal gangue through a 80-mesh sieve to obtain coal gangue powder;
s2, adding 100g of the coal gangue powder obtained in the step S1 into 200mL of 7wt% hydrochloric acid solution, heating to 40 ℃ for reaction for 1h, filtering, washing and drying to obtain acid-treated coal gangue powder, and recycling the filtrate to recover aluminum and iron;
s3, dispersing 50g of the coal gangue powder subjected to acid treatment in the step S2 in 200mL of water, adding 25g of ferrous chloride and 12g of cobalt chloride, dropwise adding 28wt% of ammonia water while continuously stirring, adjusting the pH to be =7.7, heating to 35 ℃, reacting for 0.5h, filtering, washing, drying, and calcining for 2h at 450 ℃ to obtain magnetic coal gangue powder;
s4, dissolving 3g of urea, 2g of monopotassium phosphate, 1g of potassium nitrate and 3g of maltose in 50mL of water, adding 20g of the magnetized coal gangue powder obtained in the step S3, heating to boil, and removing the solvent to obtain nutritional magnetic coal gangue powder;
s5, adding 100g of the nutritional magnetic gangue powder obtained in the step S4 into 200mL of water, adding 23g of dopamine hydrochloride and 2g of catalyst, wherein the catalyst is a Tris-HCl solution with pH =5.5, heating to 35 ℃ for reaction for 2h, and carrying out magnet separation and washing to obtain modified gangue powder;
s6, inoculating the engineering bacteria strain to an MDA culture medium, and performing activated culture at 35 ℃ for 18h to obtain a strain seed solution with the bacteria content of 10 7 cfu/mL; the engineering bacteria comprise bacillus subtilis, bacillus licheniformis, nitrobacter and aspergillus oryzae, and the mass ratio is 1;
s7, soaking 100g of the modified coal gangue powder obtained in the step S5 in 200g of the strain seed liquid obtained in the step S6, culturing at 35 ℃ for 12h, carrying out magnet separation, and drying to obtain the coal gangue magnetized soil conditioner.
Example 2
The embodiment provides a preparation method of a coal gangue magnetized soil conditioner, which comprises the following steps:
s1, crushing coal gangue, and sieving with a 100-mesh sieve to obtain coal gangue powder;
s2, adding 100g of the coal gangue powder obtained in the step S1 into 200mL of 12wt% sulfuric acid solution, heating to 50 ℃ for reaction for 2h, filtering, washing and drying to obtain acid-treated coal gangue powder, and recycling the filtrate to recover aluminum and iron;
s3, dispersing 50g of the gangue powder subjected to acid treatment in the step S2 in 200mL of water, adding 30g of ferrous chloride and 15g of cobalt chloride, dropwise adding 28wt% of ammonia water while continuously stirring, adjusting the pH =8.2, heating to 45 ℃, reacting for 1h, filtering, washing, drying, and calcining for 4h at 700 ℃ to obtain magnetic gangue powder;
s4, dissolving 5g of ammonium nitrate, 4g of sodium dihydrogen phosphate, 2g of potassium nitrate and 7g of glucose in 50mL of water, adding 20g of the magnetized coal gangue powder obtained in the step S3, heating to boil, and removing the solvent to obtain the nutritional magnetic coal gangue powder;
s5, adding 100g of the magnetic coal gangue powder subjected to nutrition in the step S4 into 200mL of water, adding 30g of dopamine hydrochloride and 3g of catalyst, wherein the catalyst is a Tris-HCl solution with the pH =6, heating to 45 ℃, reacting for 4h, and carrying out magnet separation and washing to obtain modified coal gangue powder;
s6, inoculating the engineering bacteria strain to an MDA culture medium, and performing activated culture at 40 ℃ for 24h to obtain a strain seed solution with the bacteria content of 10 8 cfuPer mL; the engineering bacteria comprise bacillus subtilis, bacillus licheniformis, nitrobacter and aspergillus oryzae, and the mass ratio is 3;
s7, soaking 100g of the modified coal gangue powder obtained in the step S5 in 300g of the strain seed liquid obtained in the step S6, culturing at 40 ℃ for 18h, carrying out magnet separation, and drying to obtain the coal gangue magnetized soil conditioner.
Example 3
The embodiment provides a preparation method of a coal gangue magnetized soil conditioner, which comprises the following steps:
s1, crushing coal gangue, and sieving the crushed coal gangue with a 100-mesh sieve to obtain coal gangue powder;
s2, adding 100g of the coal gangue powder obtained in the step S1 into 200mL of 10wt% hydrochloric acid solution, heating to 45 ℃, reacting for 1.5h, filtering, washing and drying to obtain acid-treated coal gangue powder, and recycling the filtrate to recover aluminum and iron;
s3, dispersing 50g of the coal gangue powder subjected to acid treatment in the step S2 in 200mL of water, adding 27g of ferrous chloride and 13.5g of cobalt chloride, dropwise adding 28wt% of ammonia water while continuously stirring, adjusting the pH to be =8, heating to 40 ℃, reacting for 1h, filtering, washing, drying, and calcining for 3h at 550 ℃ to obtain magnetic coal gangue powder;
s4, dissolving 4g of ammonium chloride, 3g of potassium phosphate, 1.5g of potassium sulfate and 5g of fructose in 50mL of water, adding 20g of the magnetized coal gangue powder obtained in the step S3, heating to boil, and removing the solvent to obtain the nutritional magnetized coal gangue powder;
s5, adding 100g of the nutritional magnetic gangue powder obtained in the step S4 into 200mL of water, adding 27g of dopamine hydrochloride and 2.5g of a catalyst, wherein the catalyst is a Tris-HCl solution with pH =5.7, heating to 40 ℃, reacting for 3h, and carrying out magnet separation and washing to obtain modified gangue powder;
s6, inoculating the engineering bacteria strain to an MDA culture medium, and performing activated culture at 37 ℃ for 22h to obtain a strain seed solution with the bacteria content of 10 8 cfu/mL; the engineering bacteria comprise bacillus subtilis, bacillus licheniformis, nitrobacter and aspergillus oryzae, and the mass ratio is (2);
s7, soaking 100g of the modified coal gangue powder in the step S5 in 250g of the strain seed liquid in the step S6, culturing for 15h at 37 ℃, separating by using a magnet, and drying to obtain the coal gangue magnetized soil modifier.
Comparative example 1
Step S4 was not performed, and other conditions were not changed, as compared with example 3.
The method comprises the following steps:
s1, crushing coal gangue, and sieving with a 100-mesh sieve to obtain coal gangue powder;
s2, adding 100g of the coal gangue powder obtained in the step S1 into 200mL of a hydrochloric acid solution with the concentration of 10wt%, heating to 45 ℃, reacting for 1.5h, filtering, washing and drying to obtain acid-treated coal gangue powder, and recycling the filtrate to recover aluminum and iron;
s3, dispersing 50g of the gangue powder subjected to acid treatment in the step S2 in 200mL of water, adding 27g of ferrous chloride and 13.5g of cobalt chloride, dropwise adding 28wt% of ammonia water while continuously stirring, adjusting the pH =8, heating to 40 ℃, reacting for 1h, filtering, washing, drying, and calcining for 3h at 550 ℃ to obtain magnetic gangue powder;
s4, adding 100g of the magnetic coal gangue powder in the step S3 into 200mL of water, adding 27g of dopamine hydrochloride and 2.5g of catalyst, wherein the catalyst is a Tris-HCl solution with the pH =5.7, heating to 40 ℃, reacting for 3h, and carrying out magnet separation and washing to obtain modified coal gangue powder;
s5, inoculating the engineering bacteria strain to an MDA culture medium, and performing activated culture at 37 ℃ for 22h to obtain a strain seed solution with the bacteria content of 10 8 cfu/mL; the engineering bacteria comprise bacillus subtilis, bacillus licheniformis, nitrobacter and aspergillus oryzae, and the mass ratio is (2);
s6, soaking 100g of the modified coal gangue powder in the step S4 in 250g of the strain seed liquid in the step S5, culturing for 15h at 37 ℃, separating by using a magnet, and drying to obtain the coal gangue magnetized soil modifier.
Comparative example 2
Step S5 was not performed, and other conditions were not changed, as compared with example 3.
The method comprises the following steps:
s1, crushing coal gangue, and sieving the crushed coal gangue with a 100-mesh sieve to obtain coal gangue powder;
s2, adding 100g of the coal gangue powder obtained in the step S1 into 200mL of 10wt% hydrochloric acid solution, heating to 45 ℃, reacting for 1.5h, filtering, washing and drying to obtain acid-treated coal gangue powder, and recycling the filtrate to recover aluminum and iron;
s3, dispersing 50g of the coal gangue powder subjected to acid treatment in the step S2 in 200mL of water, adding 27g of ferrous chloride and 13.5g of cobalt chloride, dropwise adding 28wt% of ammonia water while continuously stirring, adjusting the pH to be =8, heating to 40 ℃, reacting for 1h, filtering, washing, drying, and calcining for 3h at 550 ℃ to obtain magnetic coal gangue powder;
s4, dissolving 4g of ammonium chloride, 3g of potassium phosphate, 1.5g of potassium sulfate and 5g of fructose in 50mL of water, adding 20g of the magnetized coal gangue powder obtained in the step S3, heating to boil, and removing the solvent to obtain nutritional magnetized coal gangue powder;
s5, inoculating the engineering bacteria strain to an MDA culture medium, and performing activation culture at 37 ℃ for 22h to obtain a strain seed solution with the bacteria content of 10 8 cfu/mL; the engineering bacteria comprise bacillus subtilis, bacillus licheniformis, nitrobacter and aspergillus oryzae, and the mass ratio is (2);
s6, soaking 100g of the magnetic gangue powder subjected to nutrition in the step S5 in 250g of the strain seed liquid in the step S5, culturing at 37 ℃ for 15h, carrying out magnet separation, and drying to obtain the coal gangue magnetized soil conditioner.
Comparative example 3
Steps S6 and S7 were not performed, and other conditions were not changed, as compared with example 3.
The method comprises the following steps:
s1, crushing coal gangue, and sieving with a 100-mesh sieve to obtain coal gangue powder;
s2, adding 100g of the coal gangue powder obtained in the step S1 into 200mL of 10wt% hydrochloric acid solution, heating to 45 ℃, reacting for 1.5h, filtering, washing and drying to obtain acid-treated coal gangue powder, and recycling the filtrate to recover aluminum and iron;
s3, dispersing 50g of the gangue powder subjected to acid treatment in the step S2 in 200mL of water, adding 27g of ferrous chloride and 13.5g of cobalt chloride, dropwise adding 28wt% of ammonia water while continuously stirring, adjusting the pH =8, heating to 40 ℃, reacting for 1h, filtering, washing, drying, and calcining for 3h at 550 ℃ to obtain magnetic gangue powder;
s4, dissolving 4g of ammonium chloride, 3g of potassium phosphate, 1.5g of potassium sulfate and 5g of fructose in 50mL of water, adding 20g of the magnetized coal gangue powder obtained in the step S3, heating to boil, and removing the solvent to obtain nutritional magnetized coal gangue powder;
s5, adding 100g of the magnetic gangue powder subjected to nutrition in the step S4 into 200mL of water, adding 27g of dopamine hydrochloride and 2.5g of catalyst, wherein the catalyst is a Tris-HCl solution with pH =5.7, heating to 40 ℃, reacting for 3h, carrying out magnet separation, and washing to obtain the coal gangue magnetized soil modifier.
Test example 1
The gangue magnetized soil conditioner prepared in the embodiments 1-3 and the comparative examples 1-3 of the invention is uniformly mixed with the saline-alkali soil, and the application amount is 80kg/m 3 . After 30 days, the physicochemical properties of the improved soil were tested and the results are shown in table 1.
Soil volume weight and porosity: and (3) measuring the volume weight by adopting a ring cutter method, and respectively calculating the total porosity and the ventilation porosity of the soil by combining the measurement of the saturated water content of the soil and the measurement of the field moisture content.
Water-stable macro-aggregates: and (4) measuring by using a soil aggregate analyzer, and measuring the content of the water-stable aggregates with the particle size of more than 0.25 mm.
The pH value of the soil is as follows: pure water used was boiled in advance to remove carbon dioxide as measured by a pH meter, and the water-soil ratio was 2.5: 1.0 (volume-mass ratio) as recommended by the International soil society.
Soil organic matter: the measurement is carried out by adopting a potassium dichromate oxidation-external heating method.
And (3) determination of soil nutrients:
total nitrogen, alkaline hydrolysis nitrogen: determining total nitrogen by a Dumas azotometer firing method; determining alkaline hydrolysis nitrogen by an alkaline hydrolysis diffusion method;
available phosphorus, available potassium: the concrete method refers to the third edition of Bayshaden 'soil agro-chemical analysis'.
And (3) determination of soil microorganism content: the cells were cultured and counted by plate culture.
The soil urease and protease are determined by the method of soil enzyme determination in "soil enzyme and method research" of soil enzyme and method research "edited by Guanying shade (1986).
TABLE 1
From the above table, it can be seen that the coal gangue magnetized soil conditioner prepared in the embodiments 1-3 of the present invention has better physical and chemical properties, which are shown in that the soil fertility is enhanced, the soil microorganisms are increased, the soil enzyme activity is enhanced, and the physical structure of the soil is more suitable for plant growth. Soil microorganisms can promote the decomposition of organic matters and the conversion of nutrients in soil, and the richer the microorganisms are, the stronger the self-regulation capacity and activity of the soil are. The activity of soil enzymes directly influences the activity of soil microorganisms, and can reflect the activity of soil to a certain extent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a coal gangue magnetized soil conditioner is characterized by crushing coal gangue, performing acid treatment, filtering, adding filter residue into a solution containing ferrous salt and cobalt salt, adding ammonia water to prepare magnetic coal gangue powder, further loading a nitrogen fertilizer, a phosphate fertilizer, a potassium fertilizer and a carbon source, performing polydopamine modification on the surface, then soaking in a solution containing engineering bacteria, culturing, separating a magnet, and drying to obtain the coal gangue magnetized soil conditioner.
2. The method of claim 1, comprising the steps of:
s1, crushing and sieving coal gangue to obtain coal gangue powder;
s2, adding the coal gangue powder obtained in the step S1 into an acid solution, heating for reaction, filtering, washing and drying to obtain acid-treated coal gangue powder, and recycling the filtrate to recover aluminum and iron;
s3, dispersing the gangue powder subjected to acid treatment in the step S2 in water, adding ferrous salt and cobalt salt, dropwise adding ammonia water while continuously stirring, adjusting pH, heating for reaction, filtering, washing, drying and calcining to obtain magnetic gangue powder;
s4, dissolving a nitrogen fertilizer, a phosphate fertilizer, a potassium fertilizer and a carbon source in water, adding the magnetized coal gangue powder obtained in the step S3, and heating to remove the solvent to obtain the nutritional magnetic coal gangue powder;
s5, adding the nourished magnetic coal gangue powder obtained in the step S4 into water, adding dopamine hydrochloride and a catalyst, heating for reaction, separating a magnet, and washing to obtain modified coal gangue powder;
s6, inoculating the engineering bacteria strain to an MDA culture medium, and performing activated culture to obtain a strain seed solution;
and S7, soaking the modified coal gangue powder in the step S5 in the strain seed liquid in the step S6, culturing, carrying out magnet separation, and drying to obtain the coal gangue magnetized soil conditioner.
3. The method according to claim 2, wherein the mesh number of the screen in the step S1 is 80 to 100 mesh.
4. The preparation method according to claim 2, wherein the acid solution in step S2 is 7-12wt% hydrochloric acid or sulfuric acid solution, and the heating reaction is performed at 40-50 ℃ for 1-2h; adding alkali into the filtrate, filtering and calcining to obtain ferric oxide, continuously adding weak acid into the filtrate in the previous step, filtering and calcining to obtain aluminum oxide; the alkali is NaOH or KOH; the weak acid is acetic acid.
5. The preparation method according to claim 2, wherein the mass ratio of the ferrous salt to the cobalt salt in the step S3 is 25-30; the pH value is adjusted to 7.7-8.2; the heating reaction is carried out at the temperature of 35-45 ℃ for 0.5-1h, and the calcination temperature is 450-700 ℃ for 2-4h.
6. The method according to claim 2, wherein the nitrogen fertilizer in step S4 is at least one selected from urea, ammonium nitrate, sodium nitrate, and ammonium chloride; the phosphate fertilizer is selected from at least one of monopotassium phosphate, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate and sodium monohydrogen phosphate; the potash fertilizer is at least one of potassium chloride, potassium nitrate and potassium sulfate; the carbon source is at least one selected from glucose, maltose, lactose, sucrose, fructose and isomaltose; the mass ratio of the nitrogen fertilizer to the phosphate fertilizer to the potassium fertilizer to the carbon source is 3-5.
7. The preparation method according to claim 2, wherein the mass ratio of the nourished magnetic gangue powder, dopamine hydrochloride and catalyst in the step S5 is (100); the catalyst is a Tris-HCl solution with the pH = 5.5-6; the heating reaction is carried out at the temperature of 35-45 ℃ for 2-4h.
8. The preparation method according to claim 2, wherein the engineering bacteria in step S6 comprise bacillus subtilis, bacillus licheniformis, bacillus nitrobacter and aspergillus oryzae in a mass ratio of 1-3 to 2-4; the strain seed liquid has a bacteria content of 10 7 -10 8 cfu/mL。
9. The preparation method according to claim 2, wherein the mass ratio of the modified coal gangue powder to the engineering bacteria agent in the step S7 is 1:2-3; the culture condition is 35-40 ℃ for 12-18h.
10. A coal gangue magnetized soil conditioner prepared by the preparation method of any one of claims 1 to 9.
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