CN112210383A - Microbial/industrial solid waste modifier for acid soil modification and preparation method thereof - Google Patents
Microbial/industrial solid waste modifier for acid soil modification and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a microorganism/industrial solid waste modifying agent for modifying acid soil and a preparation method thereof, wherein the microorganism/industrial solid waste modifying agent for modifying acid soil comprises the following components in parts by weight: 20-30 parts of industrial solid waste, 5-8 parts of a thiobacillus ferrosus liquid, 40-60 parts of a biomass-based bacterial carrier, 3-5 parts of urea and 3-5 parts of polyallylamine. The invention can quickly and harmlessly oxidize potential acid soil, adjust the pH value of the oxidized soil, ensure that the acid is completely eradicated, and also has the functions of fixing soil heavy metals and increasing soil fertility.
Description
Technical Field
The invention belongs to the field of soil improvement, and particularly relates to a microorganism/industrial solid waste modifying agent for modifying acid soil and a preparation method thereof.
Background
Acid sulfate soil is a very poor soil type distributed in coastal zones of tropical and subtropical humid climatic regions, and actually plays a role as a potential pollution source in harbor ecosystems. Coastal zones are areas of high economic development and the densest population, and face strong pressure to develop tourism, mining, fisheries, agriculture, ports and industry. In coastal areas with small and golden soil, the problems of soil degradation such as loss and pollution of acid sulfate soil are increasingly prominent, and the development of land productivity is severely restricted. Dredged soil blown-filled ashore in reclamation work for tropical and subtropical estuary contains a large amount of reducing sulfide, namely pyrite (FeS)2) Mainly, the dry process of open-air stacking can contact air, and a large amount of acidic substances are generated by oxidation, so that the hydraulic filling operation is influenced, and meanwhile, the environment is polluted and the human body and the building are damaged. In order to avoid the problem of acid damage caused by direct hydraulic reclamation, chemical neutralization treatment is carried out on the dredged soil to prevent the dredged soil from generating acid percolate to pollute soil and water environment after being oxidized. ASS develops from the matrix of the soil rich in reducing sulphides and, after oxidation, produces sulphuric acid which strongly acidifies the soil. Under strong acid environment, the pH is greatly increased according to the solubility of variable elements such as aluminum, iron, manganese and other trace elements, thereby generating toxic action on plants, and the toxic substances can also influence the survival of aquatic organisms when being discharged into rivers and estuaries along with lateral water flowing.
Acid Sulfate Soils (ASS) are mainly soils that develop from sulfide mineralized soil precursors or soils affected by the weathering and acidification of sulfide minerals. Acid sulfate soils are classified into potential acid sulfate soils (potential acid sulfate soils) and actual acid sulfate soils (actual acid sulfate soils) according to the development conditions of the soil. The WRB system enables the pH to be 3.5-5, the upper layer to be a sulfur layer (the content of water-soluble sulfate is more than 0.05 percent, the thickness of the coating is more than 15cm), and sulfide matrix is located in the depth of 100cm below the ground surface (the dry soil contains more than 0.75 percent of sulfur, andsoil layer thickness greater than 15cm) is classified as ASS. In field identification, the soil with a sulfur layer on the surface layer is light yellow and has yellow jarosite or yellow brown schlerian mineral tuberculosis, and the pH value of the soil is lower than 4.0; the soil layer containing sulfide mature soil matrix is golden yellow and glossy in a wet state, has pH of 6.0-7.0, is often accompanied by odor of rotten eggs, is unstable in color, is often blackened after aeration, and can reduce the pH value to 2.5 after oxidation and oxidation of hydrogen. The matrix of ASS is commonly referred to as pyrite deposit, and most scholars consider pyrite (FeS) although other reducing sulfides, iron monosulfide (FeS) and organic sulfides, are also present in this matrix2) Is the most predominant reducing sulfide because pyrite is the most thermodynamically stable sulfur-containing mineral phase under natural reducing conditions.
At present, the most main recovery and reconstruction technologies for acidic sulfate soil in China are approximately as follows: irrigation and drainage engineering technology, lime application neutralization technology, crop cultivation technology and the like, and the improvement agent for treating the acid soil is single. The technologies play an important role in improvement and treatment, but have some disadvantages, most of which are limited to adding neutralizing materials and soil conditioners to directly neutralize potential acidity, and domestic researches on acid sulfate soil improvement mainly adopt improving materials, wherein the common soil improving materials comprise lime, montmorillonite, organic fertilizers and the like. These techniques still stay at the level of "treating head with headache and treating foot with pain", and cannot solve the problems fundamentally, and often cause repeated outbreaks of acid injury, so the effect is not obvious in practice.
Disclosure of Invention
The invention aims to solve the problems and provides a microorganism/industrial solid waste modifying agent for modifying acid soil and a preparation method thereof, which can rapidly and harmlessly oxidize potential acid soil, adjust the pH value of the oxidized soil, ensure that the acid is completely eradicated, and also have the functions of fixing soil heavy metals and increasing soil fertility.
The purpose of the invention is realized as follows:
the invention relates to a microorganism/industrial solid waste modifying agent for modifying acid soil, which comprises the following components in parts by weight:
wherein the content of the first and second substances,
the species of Acidithiobacillus strain ATCC 19859;
the industrial solid waste is calcium-aluminum slag treated by cetyl trimethyl ammonium bromide, nitric acid and ammonia water;
the biological system-based bacterial carrier is prepared by washing a mixture of corn straws and shaddock peels with water, drying, crushing, sieving, baking, treating with hydrochloric acid, removing ash, filtering, washing with water, and drying.
The thiobacillus ferrosus liquid in the microorganism/industrial solid waste modifier for acid soil modification is prepared by mixing the following components in parts by weight: 2-3 parts of iron-sulfur bacillus, 20-30 parts of coral sand, 1-2 parts of ammonium sulfate, 1-2 parts of potassium hydrogen phosphate, 0.5-1 part of magnesium sulfate heptahydrate, 0.5-1 part of potassium chloride, 0.5-1 part of calcium nitrate and 40-60 parts of water.
The coral sand in the microorganism/industrial solid waste improver for modifying the acid soil is treated by the following steps:
mixing coral sand with nitric acid or hydrochloric acid, soaking, filtering, mixing the filter residue with ammonia water solution or sodium hydroxide solution, soaking, filtering, washing the filter residue with water, and drying.
The coral sand in the microorganism/industrial solid waste improver for modifying the acid soil is treated by the following steps:
placing coral sand and 1mol/L nitric acid or hydrochloric acid in a beaker, stirring, mixing and soaking for 2-3 h at the rotation speed of 400r/min, filtering to obtain filter residue, placing the obtained filter residue in a sodium hydroxide solution with the mass fraction of 1mol/L, stirring, mixing and soaking for 1-2 h at the rotation speed of 600r/min, washing the filtered filter residue with deionized water for 3-5 times, then placing the obtained filter residue in an oven, and drying at the temperature of 105-110 ℃ to constant weight to obtain the pretreated coral sand.
70-80 parts of industrial solid waste with a chemical formula of CaO & Al in the microbial/industrial solid waste modifier for acid soil modification2O3·CaCl2·FeO·10H2Sequentially using a nitric acid solution to adjust the pH value of the pretreated calcium-aluminum slag to 1.5-2, stirring for 3 hours, then cooling the solution to room temperature, using ammonia water to adjust the pH value of the solution to 8.3-9 during stirring, adding a hexadecyl trimethyl ammonium bromide solution with the hexadecyl trimethyl ammonium bromide content of 2-5 parts after metal ions in the solution are fully precipitated, performing suction filtration, drying, and then putting into a muffle furnace to calcine for 3 hours at 300-650 ℃.
The preparation method of the industrial solid waste in the microorganism/industrial solid waste modifying agent for modifying the acid soil comprises the following steps:
putting calcium-aluminum slag into a reaction kettle containing deionized water, and carrying out water bath at 65 ℃; with 1mol/L HNO3After the pH value of the solution is adjusted to be 1.5-2, magnetically stirring the solution for 3 hours at the rotating speed of 400r/min so as to hydrolyze and acidolyze metal oxides in the calcium-aluminum slag; after 3h, when the temperature of the solution is reduced to room temperature, adjusting the pH value of the solution to 3.2 by using 6mol/L ammonia water, stirring for 1h, continuously adjusting the pH value of the solution to 9 by using the ammonia water, and stirring for 1h to fully precipitate metal ions in the aqueous solution; separating the mixture in the solution by adopting a suction filtration or high-speed centrifugation method; drying the separated solid, adding water and a hexadecyl trimethyl ammonium bromide solution of 2g/L, magnetically stirring for 30min under the condition that the rotating speed is 400r/min, centrifuging, putting the solid in a drying oven of 105 ℃ for drying for 24h, grinding and screening to 100 meshes after drying; and calcining the dried and ground sample at the temperature of 300-650 ℃ for 3 h.
The preparation of the biological system-based bacterial carrier in the microorganism/industrial solid waste modifying agent for modifying the acid soil comprises the following steps:
(1) washing a mixture of corn straws and shaddock peels with water, drying the mixture in an oven at 50-70 ℃, crushing the mixture by using a crusher, and sieving the crushed mixture with a 100-mesh sieve for later use;
(2) and (2) placing the corn straws and the shaddock peels treated in the step (1) in a muffle furnace, firing for 12-24 hours at 400-600 ℃, adjusting the pH value of the prepared carbonized product to 3.2-4 by using hydrochloric acid, removing ash after 10-14 hours, filtering, washing to be neutral by using distilled water, and drying in an oven at 70-80 ℃.
The preparation of the thiobacillus ferrosus liquid in the microorganism/industrial solid waste modifier for acid soil modification comprises the following steps: mixing and soaking coral sand and hydrochloric acid, filtering to obtain filter residue, placing the filter residue in a sodium hydroxide solution, mixing and soaking, filtering, washing and drying to obtain the pretreated coral sand.
The preparation of the thiobacillus ferrosus liquid in the microorganism/industrial solid waste modifier for acid soil modification comprises the following steps: mixing 20-30 parts of pretreated coral sand, 2-3 parts of iron-sulfur bacillus, 1-2 parts of ammonium sulfate, 1-2 parts of potassium hydrogen phosphate, 0.5-1 part of magnesium sulfate heptahydrate, 0.5-1 part of potassium chloride for fermentation, 0.5-1 part of calcium nitrate and 40-60 parts of water, and culturing for 5-10 days at the temperature of 15-25 ℃.
The invention also provides a preparation method of the microbial/industrial solid waste modifier for modifying acid soil, which comprises the following steps:
s1: preparing a biological system-based bacterial vector;
s2: modification treatment of industrial solid waste;
s3: pretreating coral sand;
s4: preparing a thiobacillus ferrosus bacterial liquid;
s5: weighing the following components in parts by weight:
the components are placed in a mixer at the rotating speed of 1000r/min, and the mixing and stirring time is 30 min.
The invention obtains the calcium-aluminum slag through modification, has quick oxidation,the material with the capability of quickly neutralizing and adsorbing heavy metal ions has the neutralizing effect of hydroxide in the first modified calcium-aluminum slag during the use process, and anions such as SO can be adsorbed between layers of the layered double hydroxide generated by modification4 2-，S2O3 2-Etc. the laminated plate can adsorb heavy metals such as Cu, Cr, Cd, etc., Fe in them2+Interaction with oxidizing bacteria can accelerate the rate of oxidation.
According to the invention, by preparing and culturing the iron-sulfur bacillus liquid, in the using process, coral sand is pretreated firstly, the coral sand has a highly regular pore structure, the pore size is uniformly distributed, and the coral sand has a huge high specific surface area, so that the growth and the culture of the iron-sulfur bacillus are facilitated, and the service life of the iron-sulfur bacillus liquid is further prolonged. The iron-sulfur bacillus can react with urea to generate carbonate ions, the carbonate ions are easily decomposed to generate water and carbon dioxide, the consumption of hydrogen ions can play a role in adjusting the pH value of soil, water can be directly supplied to plants for utilization, and the carbon dioxide is released from the soil, so that the pore structure of the soil is enriched, air and moisture can permeate into the soil, and the water retention performance of the soil is improved. And secondly, the generated carbon dioxide can act with polyallylamine in the raw material, so that the polyallylamine is crosslinked, a good fixing effect is realized on soil, and the water loss and soil erosion are effectively reduced.
The biomass-based bacterial vector is prepared by using the pretreated corn straws and the shaddock peels, and in the using process, because the biomass-based bacterial vector has higher pH value and generates a large number of functional groups under the pyrolysis reaction, the functional groups can exist in the form of anions under the condition of higher pH value and react with H+Association reaction is carried out, so that the biomass-based bacterial carrier has a lime effect, the oxidation reaction of the soil can be accelerated by hydroxyl radicals carried by the biomass-based bacterial carrier, the morphological distribution of heavy metals in the polluted soil can be changed by the biomass-based bacterial carrier, the soil pollution condition is improved, and the effect on chromium is most obvious.
Detailed Description
The present invention will be further described with reference to the following examples.
The invention discloses a microorganism/industrial solid waste modifying agent for modifying acid soil, which comprises the following components in parts by weight:
wherein the content of the first and second substances,
the iron-sulfur bacillus liquid is prepared by mixing iron-sulfur bacillus with coral sand, ammonium sulfate, potassium hydrogen phosphate, magnesium sulfate heptahydrate, potassium chloride and calcium nitrate;
the coral sand is prepared by mixing and pretreating coral sand, nitric acid and an ammonia water solution;
the species of Acidithiobacillus strain ATCC 19859;
the industrial solid waste is prepared by modifying pretreated calcium-aluminum slag, hexadecyl trimethyl ammonium bromide, nitric acid and ammonia water;
the chemical formula of the pretreated calcium-aluminum slag is CaO-Al2O3·CaCl2·FeO·10H2O；
The biological system-based bacterial vector comprises the following pretreatment steps: the pre-treated corn straw and shaddock peel are placed in a muffle furnace and baked for 2 hours at 400 ℃, the prepared carbonized product is treated for 12 hours by 200mL of 1mol/L hydrochloric acid, ash content is removed, the carbonized product is filtered, washed by distilled water to be neutral and dried in an oven at 70-80 ℃.
The pretreatment steps for pretreating the corn straws and the shaddock peels comprise: washing corn stalks and grapefruit peels with water, drying the corn stalks and the grapefruit peels in an oven at 60 ℃, crushing the corn stalks and the grapefruit peels by using a small crusher, and sieving the corn stalks and the grapefruit peels with a 100-mesh sieve.
A preparation method of a microorganism/industrial solid waste modifier for modifying acid soil comprises the following steps:
s1: preparation of Bio-based bacterial vectors
Washing corn straws and shaddock peels with water, drying, crushing, sieving with a 100-mesh sieve, calcining a product for 24 hours by using a muffle furnace, treating the prepared carbonized product with hydrochloric acid, standing, filtering, washing with distilled water to be neutral, and drying to obtain a modified biomass-based bacterial carrier;
s2: modification treatment of industrial solid waste
Putting calcium-aluminum slag into a beaker filled with deionized water, putting into a temperature water bath, and using 1mol/LHNO3Adjusting the pH value of the solution to 3.2, after 3 hours, when the temperature of the solution is reduced to room temperature, continuously adjusting the pH value of the solution to 9 by using ammonia water, fully precipitating metal ions in the aqueous solution, performing suction filtration, drying, and calcining in a muffle furnace for 3 hours;
s3: coral sand pretreatment
Mixing and soaking coral sand and hydrochloric acid, filtering to obtain filter residue, placing the filter residue in a sodium hydroxide solution, mixing and soaking, filtering, washing and drying to obtain pretreated coral sand;
s4: preparation of iron-sulfur bacillus bacterial liquid
Mixing and fermenting the pretreated coral sand, the iron-sulfur bacillus, 3.0g/L ammonium sulfate, 0.5g/L potassium hydrogen phosphate, 0.5g/L magnesium sulfate heptahydrate and 0.1g/L potassium chloride, and obtaining mixed bacterial liquid by 0.01/L calcium nitrate;
s5: stirring and mixing the modified biomass-based bacteria carrier, the mixed bacterial liquid containing the iron-sulfur bacillus, the industrial solid waste, the urea and the polyallylamine.
Wherein the content of the first and second substances,
the step S1 includes the following steps: washing corn straws and shaddock peels with water, placing the washed corn straws and shaddock peels in an oven at 60 ℃ for 12 hours, drying the washed corn straws and shaddock peels, crushing the washed corn straws and the shaddock peels by using a crusher, sieving the ground corn straws and the shaddock peels with a 100-mesh sieve, calcining the obtained product at 400 ℃ in a muffle furnace for 24 hours, placing the prepared carbonized product in a beaker, mixing the carbonized product with 200mL of 1mol/L hydrochloric acid, performing ultrasonic treatment for 3 hours, standing the mixture, filtering the mixture to obtain filter residues, washing the filter residues to be neutral by using distilled water, and placing the filter residues.
The step S2 includes the following steps: putting the calcium-aluminum slag into a beaker filled with deionized water, and putting the beaker into a water bath kettle at the temperature of 65 ℃; with 1mol/L HNO3The solution adjusts the pH of the solution to stabilize the pH of the solution at 1.5-2. Magnetically stirring for 3 hours at the rotating speed of 400r/min to fully perform hydrolysis and acidolysis reactions on metal oxides in the calcium-aluminum slag; after 3h, when the temperature of the solution is reduced to room temperature, adjusting the pH value of the solution by using ammonia water with certain concentration to enable the pH value of the solution to be stable at 3.2, stirring for 1h, then continuously adjusting the pH value of the solution by using the ammonia water to enable the pH value to be stable at about 9, and stirring for 1h to enable metal ions in the aqueous solution to be fully precipitated; separating the mixture in the solution by adopting a suction filtration or high-speed centrifugation method; drying the separated solid, adding water and hexadecyl trimethyl ammonium bromide with certain mass, magnetically stirring for 30min under the condition that the rotating speed is 400r/min, centrifuging, putting the solid in a drying oven at 105 ℃ for drying for 24h, grinding and screening to 100 meshes after drying; the dried and ground sample was calcined at a temperature of 300 ℃ and 650 ℃ for 3 h.
Step S3 specifically includes: placing coral sand and 1mol/L hydrochloric acid in a beaker, stirring, mixing and soaking for 2-3 h at the rotation speed of 400r/min, filtering to obtain No. 1 filter residue, then placing No. 1 filter residue in a sodium hydroxide solution with the mass fraction of 1mol/L, stirring, mixing and soaking for 1-2 h at the rotation speed of 600r/min, filtering to obtain No. 2 filter residue, washing the No. 2 filter residue with deionized water for 3-5 times, then placing the No. 2 filter residue in an oven, and drying to constant weight at the temperature of 105-110 ℃ to obtain the pretreated coral sand.
Step S4 specifically includes: mixing and fermenting pretreated coral sand, iron-sulfur bacillus, 3.0g/L ammonium sulfate, 0.5.0g/L potassium hydrogen phosphate, 0.5g/L magnesium sulfate heptahydrate and 0.1g/L potassium chloride, placing 0.01g/L calcium nitrate in a reverse culture dish, and culturing for 5-10 days at the temperature of 15-25 ℃ to obtain a mixed bacterial liquid;
in step S5, the rotation speed of the mixer is 1000r/min, and the mixing and stirring time is 30 min.
The components and parts by weight of the components of examples 1-4 are shown in Table 1:
TABLE 1 examples 1 to 4
| Components | Example 1 | Example 2 | Example 3 | Example 4 |
| Industrial solid waste | 30 | 10 | 30 | 40 |
| Acidithiobacillus liquid | 5 | 5 | 10 | 5 |
| Biomass-based bacterial vectors | 40 | 40 | 40 | 40 |
| Urea | 5 | 5 | 5 | 5 |
| Polyallylamine | 5 | 5 | 5 | 5 |
Preparation of modified biomass-based bacterial vectors:
washing corn straws and shaddock peels with water, placing the washed corn straws and the shaddock peels in an oven at 60 ℃ for 12 hours, drying the washed corn straws and the shaddock peels, crushing the washed corn straws and the shaddock peels by using a crusher, sieving the ground corn straws and the shaddock peels with a 100-mesh sieve, calcining the obtained product at 400 ℃ in a muffle furnace for 24 hours, placing the prepared carbonized product in a beaker, mixing the carbonized product with 1mol/L hydrochloric acid, adjusting the pH value to 3.2-4, carrying out ultrasonic treatment for 3 hours, standing the obtained product, filtering the obtained product to obtain filter residues, washing the filter residues with distilled water to be neutral, and.
Preparing modified industrial solid waste:
taking 75 parts of CaO & Al2O3·CaCl2·FeO·10H2Putting the pretreated calcium-aluminum slag of O into a beaker filled with deionized water, and putting into a water bath kettle at the temperature of 65 ℃; with 1mol/L HNO3The solution adjusts the pH of the solution to stabilize the pH of the solution at 1.5-2. Magnetically stirring for 3 hours at the rotating speed of 400r/min to fully perform hydrolysis and acidolysis reactions on metal oxides in the calcium-aluminum slag; after 3h, when the temperature of the solution is reduced to room temperature, adjusting the pH value of the solution by using 6mol/L ammonia water to enable the pH value of the solution to be stable at 3.2, stirring for 1h, then continuously adjusting the pH value of the solution by using the ammonia water to enable the pH value of the solution to be stable at 9, and stirring for 1h to enable metal ions in the aqueous solution to be fully precipitated; separating the mixture in the solution by adopting a suction filtration or high-speed centrifugation method; drying the separated solid, adding water and a hexadecyl trimethyl ammonium bromide solution with the hexadecyl trimethyl ammonium bromide content of 3 parts and the hexadecyl trimethyl ammonium bromide content of 2g/L, magnetically stirring for 30min under the condition that the rotating speed is 400r/min, drying the solid in a drying oven at the temperature of 105 ℃ for 24h after centrifugation, grinding and screening to 100 meshes after drying; the dried and ground sample was calcined at a temperature of 300 ℃ and 650 ℃ for 3 h.
Preparing pretreated coral sand:
placing 5g of coral sand and 1mol/L hydrochloric acid in a beaker, stirring, mixing and soaking for 2-3 h at the rotation speed of 400r/min, filtering to obtain No. 1 filter residue, then placing No. 1 filter residue in a sodium hydroxide solution with the mass fraction of 1mol/L, stirring, mixing and soaking for 1-2 h at the rotation speed of 600r/min, filtering to obtain No. 2 filter residue, washing the No. 2 filter residue to 3-5 times with deionized water, then placing the No. 2 filter residue in an oven, and drying to constant weight at the temperature of 105-110 ℃ to obtain the pretreated coral sand.
Preparing a thiobacillus ferrosus bacterial liquid:
mixing 25 parts of coral sand, 3 parts of Acidithiobacillus ferrooxidans, 3.0g/L ammonium sulfate solution with 2 parts of ammonium sulfate, 0.5.0g/L potassium hydrogen phosphate with 2 parts of potassium hydrogen phosphate, 0.5g/L magnesium sulfate heptahydrate solution with 1 part of magnesium sulfate heptahydrate, and 0.1g/L potassium chloride solution with 1 part of potassium chloride, fermenting, placing 0.01g/L calcium nitrate with 1 part of calcium nitrate in a reverse culture dish, and heating at the temperature
Culturing for 5-10 days at 15-25 ℃ to obtain a thiobacillus ferrooxidans bacterial liquid;
preparing a microorganism/industrial solid waste modifier for modifying acid soil:
and (3) placing the modified biomass-based bacteria carrier, the iron-sulfur bacillus liquid, the modified industrial solid waste, the urea and the polyallylamine into a mixer, and mixing and stirring for 30min under the condition of the rotation speed of 1000 r/min.
And (3) performance testing:
the mixture is mixed with acid soil according to the use amount of 10g/kg, and an indoor simulation experiment is carried out. The used acid soil is acid soil of a mangrove forest region with the depth range from the surface to 20cm, the pH value after oxidation is 3.22, and the net acidity is 8.2 cmol/kg; the water content of the soil is controlled to be 60-80% in the experimental process.
Soil samples are respectively taken after 1 month and 3 months of using the microorganism/industrial solid waste modifying agent for modifying the acid soil and a neutralizing agent, wherein the acid soil modifying agent is not applied to a control group, the neutralizing agent is mainly a mixture of lime and montmorillonite in a ratio of 2:1, and the ratio of the neutralizing agent to the soil is 10 g/kg.
The detection indexes are respectively as follows:
water-soluble acidity: i.e. the amount of water-soluble acid contained in the soil.
pH-KCl: namely the pH value of the solution of the acid soil after the extraction of KCl solution with the solid-to-liquid ratio of 1: 40.
pH-OX: namely the pH value of the solution of the acid soil after being oxidized by hydrogen peroxide with excessive pH value of 7.0.
The results are shown in table 2:
TABLE 2 test results of examples 1-4 with control and using agent only
From the above results, it is understood that the optimum ratio of the microorganism for acid soil modification/industrial solid waste improver of the present invention is example 1. Because the acidic sulfate soil has potential acidity, the solution extracted by potassium chloride still shows neutrality, and the acidic soil is exposed after being oxidized by hydrogen peroxide, the microbial/industrial solid waste modifier for modifying the acidic soil can effectively and quickly oxidize the acidic soil, improve the pH value of the soil, reduce the content of water-soluble acid of the acidic soil, and play a role in improving the property of the acidic soil. In addition, the industrial waste contains calcium and magnesium oxide which can fix heavy metal ions in soil, and the biomass-based carrier can improve soil fertility and help plants to grow.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (10)
1. The microbial/industrial solid waste modifying agent for modifying the acid soil is characterized by comprising the following components in parts by weight:
wherein the content of the first and second substances,
the Acidithiobacillus strain model ATCC 19859;
the industrial solid waste is calcium-aluminum slag treated by cetyl trimethyl ammonium bromide, nitric acid and ammonia water;
the biological system-based bacterial carrier is prepared by washing, drying and crushing a mixture of corn straws and shaddock peels, sieving, burning to obtain a carbonized product, treating the carbonized product with hydrochloric acid to remove ash, filtering, washing with water, and drying.
2. The microbial/industrial solid waste improver for acid soil modification according to claim 1, wherein the Acidithiobacillus ferrosus liquid is prepared by mixing the following components in parts by weight: 2-3 parts of iron-sulfur bacillus, 20-30 parts of coral sand, 1-2 parts of ammonium sulfate, 1-2 parts of potassium hydrogen phosphate, 0.5-1 part of magnesium sulfate heptahydrate, 0.5-1 part of potassium chloride, 0.5-1 part of calcium nitrate and 40-60 parts of water.
3. The microbial/industrial solid waste improver for acidic soil modification according to claim 2, wherein the coral sand is subjected to the following treatment steps:
mixing coral sand with nitric acid or hydrochloric acid, soaking, filtering, mixing the filter residue with ammonia water solution or sodium hydroxide solution, soaking, filtering, washing the filter residue with water, and drying.
4. The microbial/industrial solid waste improver for acidic soil modification according to claim 3, wherein the coral sand is subjected to the following treatment steps:
placing coral sand and 1mol/L nitric acid or hydrochloric acid in a beaker, stirring, mixing and soaking for 2-3 h at the rotation speed of 400r/min, filtering to obtain filter residue, placing the obtained filter residue in a sodium hydroxide solution with the mass fraction of 1mol/L, stirring, mixing and soaking for 1-2 h at the rotation speed of 600r/min, washing the filtered filter residue with deionized water for 3-5 times, then placing the obtained filter residue in an oven, and drying at the temperature of 105-110 ℃ to constant weight to obtain the pretreated coral sand.
5. The microbial/industrial solid waste improver for acid soil modification according to claim 1, wherein 70 to 80 parts by weight of the industrial solid waste has a chemical formula of CaO-Al2O3·CaCl2·FeO·10H2Sequentially using a nitric acid solution to adjust the pH value of the pretreated calcium-aluminum slag to 1.5-2, stirring for 3 hours, then cooling the solution to room temperature, using ammonia water to adjust the pH value of the solution to 8.3-9 during stirring, adding a hexadecyl trimethyl ammonium bromide solution with the hexadecyl trimethyl ammonium bromide content of 2-5 parts after metal ions in the solution are fully precipitated, performing suction filtration, drying, and then putting into a muffle furnace to calcine for 3 hours at 300-650 ℃.
6. The microbial/industrial solid waste improver for acid soil modification according to claim 5, wherein the preparation of the industrial solid waste comprises the steps of:
putting calcium-aluminum slag into a reaction kettle containing deionized water, and carrying out water bath at 65 ℃; with 1mol/L HNO3After the pH value of the solution is adjusted to be 1.5-2, magnetically stirring the solution for 3 hours at the rotating speed of 400r/min so as to hydrolyze and acidolyze metal oxides in the calcium-aluminum slag; after 3h, when the temperature of the solution is reduced to room temperature, adjusting the pH value of the solution to 3.2 by using 6mol/L ammonia water, stirring for 1h, continuously adjusting the pH value of the solution to 9 by using the ammonia water, and stirring for 1h to fully precipitate metal ions in the aqueous solution; separating the mixture in the solution by adopting a suction filtration or high-speed centrifugation method; drying the separated solid, adding water and 2g/L cetyl trimethyl ammonium bromide solution, magnetically stirring for 30min at 400r/min, centrifuging, drying the solid in a drying oven at 105 deg.C for 24h, drying, grinding, and sieving100 meshes; and calcining the dried and ground sample at the temperature of 300-650 ℃ for 3 h.
7. The microbial/industrial solid waste improver for acidic soil modification according to claim 1, wherein the preparation of the bio-based bacterial carrier comprises:
(1) washing a mixture of corn straws and shaddock peels with water, drying the mixture in an oven at 50-70 ℃, crushing the mixture by using a crusher, and sieving the crushed mixture with a 100-mesh sieve for later use;
(2) and (2) placing the corn straws and the shaddock peels treated in the step (1) in a muffle furnace, firing for 12-24 hours at 400-600 ℃, adjusting the pH value of the prepared carbonized product to 3.2-4 by using hydrochloric acid, removing ash after 10-14 hours, filtering, washing to be neutral by using distilled water, and drying in an oven at 70-80 ℃.
8. The microbial/industrial solid waste improver for acid soil modification according to claim 1, wherein the preparation of the Acidithiobacillus ferrosus solution comprises the following steps: mixing and soaking coral sand and hydrochloric acid, filtering to obtain filter residue, placing the filter residue in a sodium hydroxide solution, mixing and soaking, filtering, washing and drying to obtain the pretreated coral sand.
9. The microbial/industrial solid waste improver for acid soil modification according to claim 1, wherein the preparation of the Acidithiobacillus ferrosus solution comprises the following steps: mixing 20-30 parts of pretreated coral sand, 2-3 parts of iron-sulfur bacillus, 1-2 parts of ammonium sulfate, 1-2 parts of potassium hydrogen phosphate, 0.5-1 part of magnesium sulfate heptahydrate, 0.5-1 part of potassium chloride for fermentation, 0.5-1 part of calcium nitrate and 40-60 parts of water, and culturing for 5-10 days at the temperature of 15-25 ℃.
10. The method for preparing a microbial/industrial solid waste improver for acid soil modification according to claim 1, comprising the steps of:
s1: preparing a biological system-based bacterial vector;
s2: modification treatment of industrial solid waste;
s3: pretreating coral sand;
s4: preparing a thiobacillus ferrosus bacterial liquid;
s5: weighing the following components in parts by weight:
the components are placed in a mixer at the rotating speed of 1000r/min, and the mixing and stirring time is 30 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117718315A (en) * | 2024-01-05 | 2024-03-19 | 浙江大学 | Method for regulating pH of copper-polluted acid soil by using soybean urease |
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Application publication date: 20210112 |