Acid-inhibiting and aluminum-controlling composite modifier as well as preparation method and application thereof

Abstract

The invention provides an acid-blocking and aluminum-controlling composite modifier and a preparation method and application thereof, the modifier is composed of microcrystalline activated minerals, a silicon-calcium material, a biomass alkaline material and a microbial agent, and the microbial agent comprises rhizobium, trichoderma harzianum and pseudomonas fluorescens. The specific raw material ratio can be adjusted according to different requirements, and the effect of materials with different ratios on improving the soil acidity and improving the crop yield and quality is researched by adopting field trials, so that an acid soil conditioner formula is formed; the preparation method comprises the steps of ultrafine grinding, microcrystal activation, hybridization, mixing and the like, the microcrystal activation adopts an activator solution for treatment, and an organic binder is added in the hybridization process to form an organic-inorganic hybrid structure. The composite modifier can effectively improve the physical action effect and the chemical reaction speed of the acid conditioner, and can be used for improving acid soil.

Description

Technical Field

[0001] The invention relates to the technical field of soil improvement, and in particular to an acid-blocking and aluminum-controlling composite improver and a preparation method and application thereof. Background Art

[0002] Soil acidification of cultivated land is a particularly prominent soil degradation problem caused by high-intensity resource input in my country. Compared with the pH distribution of the second soil survey in the 1980s, a large area of ​​cultivated land in the red soil region in southern my country has undergone acidification. In particular, the area of ​​highly acidic cultivated land soil (pH≤5.5) has increased, the pH has dropped by one level (from 5.5-6.5 to 4.5-5.5), and local acidification is serious. Soil acidification can cause a series of changes in soil physical, chemical and biological properties, leading to the evolution and degradation of agricultural productivity and ecosystems. Soil acidification causes soil nutrient impoverishment and enhanced activity of toxic elements in the soil, which has a toxic effect on plant growth and causes the decline of soil biodiversity and ecological function. The degradation of soil quality and the fragility of the ecological environment caused by soil acidification seriously threaten the efficient utilization of red soil resources and the development of production capacity. Further aggravation of soil acidification is bound to affect my country's food security and agricultural production and income. Studies have shown that for every 1 unit decrease in soil pH within the range of 4.2 to 6.4, the yield of rapeseed, peanuts, wheat, corn, and citrus decreases by an average of 51.9%. Soil acidification increases the activity of heavy metals. As soil acidification (pH decreases), the availability of soil Cd and Pb increases significantly, especially Cd, which is more active at low pH. This is one of the main reasons why "Cd rice" is common in acidic rice fields in the south. After soil acidification, not only does the activity of harmful heavy metals increase, causing excessive heavy metals in grains, but the activity of soil Al also increases significantly, causing Al poisoning in crops, resulting in a significant reduction in yield. Traditional amendments and existing improvement technologies can achieve a good effect in improving the acidity of farmland soil, but the improvement effect is short-lived and the soil becomes acidic again, resulting in a long-term fluctuation in the pH of farmland soil, which seriously affects the high and stable yield of crops. Summary of the invention

[0003] In view of this, the present invention proposes a composite improver for acid resistance and aluminum control and a preparation method and application thereof to solve the above problems.

[0004] The technical solution of the present invention is achieved as follows: a composite improver for acid resistance and aluminum control, comprising the following raw materials in parts by weight: 30-40 parts of microcrystalline activated minerals, 25-35 parts of silicon-calcium materials, 20-30 parts of biomass alkaline materials and 5-10 parts of microbial agents; the microbial agents are rhizobia, Trichoderma harzianum and Pseudomonas fluorescens in a mass ratio of (12-22):(8-10):(5-7), and the effective viable count of each of the microbial agents is 1×10 8 -10 10 cfu / mL.

[0005] Furthermore, the following raw materials are included in parts by weight: 35 parts of microcrystalline activated minerals, 30 parts of silicon-calcium materials, 25 parts of biomass alkaline materials and 8 parts of microbial agents.

[0006] Furthermore, the microcrystalline activated mineral includes 15-20 parts of phosphate rock powder and 15-20 parts of limestone.

[0007] Furthermore, the silicon-calcium material includes 10-15 parts of silicon-calcium fertilizer, 8-10 parts of slag, and 7-10 parts of oyster shell powder.

[0008] Furthermore, the slag is selected from steel slag, copper slag, lead-zinc slag, nickel slag, manganese slag or chromium slag.

[0009] Furthermore, the biomass alkaline material includes 12-18 parts of straw biomass charcoal and 8-12 parts of tung seed meal.

[0010] Furthermore, a method for preparing an acid-blocking and aluminum-controlling composite modifier comprises the following steps:

[0011] S1. Ultrafine grinding: Put the microcrystalline activated minerals and calcium silicon materials into the air flow mill for grinding, adjust the air flow speed to 150-300m / s, and the particle size to 1-10μm;

[0012] S2, microcrystalline activation: the above-mentioned pulverized microcrystalline activated mineral powder is slowly added to the activator solution, the mass volume ratio g / mL is controlled at 1:5-10, the reaction is carried out under stirring, the stirring speed is 100-300rpm, the reaction temperature is controlled at 40-80°C, the reaction time is 2-6 hours, after the reaction is completed, solid-liquid separation is performed to obtain activated microcrystalline activated mineral powder, washed with clean water to neutrality, and then dried at 80-120°C to constant weight for standby use;

[0013] S3, hybridization: preliminarily mix the biomass alkaline material with the silicon-calcium material of S1 and the microcrystalline activated mineral powder of S2, the mixing time is 15-30 minutes, the rotation speed is 50-100rpm, to obtain a preliminary mixed material, slowly add the organic binder solution to the preliminary mixed material and stir at the same time, the stirring speed is 100-300rpm, so that the organic binder is evenly wrapped on the surface of the inorganic raw material particles to form an organic-inorganic hybrid structure, continue stirring and mixing for 30-60min to ensure that the organic binder and the inorganic raw material are fully combined, granulate, and obtain a granular material with a particle size of 2-5mm;

[0014] S4, mixing: adding the microbial agent to the granular material of S3, adopting the method of low-speed stirring and mixing, the stirring speed is 30-60rpm, and the mixing time is 10-20 minutes, so as to avoid the microbial agent from being inactivated by excessive shear force, and to make the microbial agent evenly distributed on the surface and inside of the particles. The mixed material is the finished product of the multifunctional composite improver for acid resistance and aluminum control, which is packaged and stored.

[0015] Furthermore, the activator solution of S2 is a dilute sulfuric acid or hydrochloric acid solution with a concentration of 1-5 mol / L.

[0016] Furthermore, the organic binder solution of S3 is selected from guar gum, cellulose or sodium alginate solution with a mass fraction of 5-15%.

[0017] Furthermore, the composite improver is applied to acidic soil.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The present invention develops a multifunctional composite improver for long-term acid inhibition and targeted aluminum control based on the principle of long-term acid inhibition technology for the combination of organic fertilizer and chemical fertilizer, and the relationship model between silicate mineral weathering, proton consumption and aluminum activation. With the core of strengthening the physical protection of soil aggregates on cultivated soil, the soil organic matter content and biological function are improved, achieving the acid-blocking and aluminum-controlling fertilization effect of "aggregate-organic matter-biological function" interactive coupling. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The present invention is a process flow chart for the preparation of a composite improver for acid resistance and aluminum control. DETAILED DESCRIPTION

[0021] In order to better understand the technical content of the present invention, specific embodiments are provided below to further illustrate the present invention.

[0022] Unless otherwise specified, the experimental methods used in the embodiments of the present invention are all conventional methods.

[0023] Unless otherwise specified, the materials, reagents, etc. used in the embodiments of the present invention can be obtained from commercial sources.

[0024] Example 1

[0025] A composite modifier for acid resistance and aluminum control comprises the following raw materials in parts by weight: 30 parts of microcrystalline activated minerals, 25 parts of silicon-calcium materials, 20 parts of biomass alkaline materials and 5 parts of microbial agents; the microcrystalline activated minerals are 15 parts of phosphate rock powder and 15 parts of limestone; the silicon-calcium materials are 10 parts of silicon-calcium fertilizer, 8 parts of copper slag and 7 parts of oyster shell powder; the biomass alkaline materials are 12 parts of straw biochar and 8 parts of tung seed meal; the microbial agents are rhizobia, Trichoderma harzianum and Pseudomonas fluorescens in a mass ratio of 12:8:5, and the effective viable counts of the microbial agents are all 1×10 8 cfu / mL.

[0026] Example 2

[0027] A composite modifier for acid resistance and aluminum control comprises the following raw materials in parts by weight: 40 parts of microcrystalline activated minerals, 35 parts of silicon-calcium materials, 30 parts of biomass alkaline materials and 10 parts of microbial agents; the microcrystalline activated minerals are 20 parts of phosphate rock powder and 20 parts of limestone; the silicon-calcium materials are 15 parts of silicon-calcium fertilizer, 10 parts of steel slag and 10 parts of oyster shell powder; the biomass alkaline materials are 18 parts of straw biochar and 12 parts of tung seed meal; the microbial agents are rhizobia, Trichoderma harzianum and Pseudomonas fluorescens in a mass ratio of 22:10:7, and the effective live bacterial counts are all 1×10 10 cfu / mL.

[0028] Example 3

[0029] A composite modifier for acid resistance and aluminum control comprises the following raw materials in parts by weight: 35 parts of microcrystalline activated minerals, 30 parts of silicon-calcium materials, 25 parts of biomass alkaline materials and 8 parts of microbial agents; the microcrystalline activated minerals are 15 parts of phosphate rock powder and 20 parts of limestone; the silicon-calcium materials are 12 parts of silicon-calcium fertilizer, 10 parts of lead-zinc slag and 8 parts of oyster shell powder; the biomass alkaline materials are 15 parts of straw biochar and 10 parts of tung seed meal; the microbial agents are rhizobia, Trichoderma harzianum and Pseudomonas fluorescens in a mass ratio of 17:9:6, and the effective viable counts of the microbial agents are all 1×10 9 cfu / mL;

[0030] The above examples 1-3 adopt the following preparation method:

[0031] S1. Ultrafine grinding: Put the microcrystalline activated minerals and calcium silicon materials into the air flow mill for grinding, adjust the air flow speed to 150-300m / s, and the particle size to 1-10μm;

[0032] S2, microcrystalline activation: the above-mentioned pulverized microcrystalline activated mineral powder is slowly added to the activator solution, the mass volume ratio g / mL is controlled at 1:5-10, the activator solution is a dilute sulfuric acid or hydrochloric acid solution with a concentration of 1-5 mol / L, the reaction is carried out under stirring, the stirring speed is 100-300 rpm, the reaction temperature is controlled at 40-80°C, the reaction time is 2-6 hours, after the reaction is completed, solid-liquid separation is performed to obtain the activated microcrystalline activated mineral powder, the powder is washed with clean water to neutrality, and then dried at 80-120°C to constant weight for standby use;

[0033] S3, hybridization: preliminarily mix the biomass alkaline material with the silicon-calcium material of S1 and the microcrystalline activated mineral powder of S2, the mixing time is 15-30 minutes, the rotation speed is 50-100rpm, to obtain a preliminary mixed material, slowly add the organic binder solution to the preliminary mixed material while stirring, the stirring speed is 100-300rpm, the organic binder solution is selected from guar gum, cellulose or sodium alginate solution with a mass fraction of 5-15%, so that the organic binder is evenly wrapped on the surface of the inorganic raw material particles to form an organic-inorganic hybrid structure, continue stirring and mixing for 30-60min, granulate, and obtain a granular material with a particle size of 2-5mm;

[0034] S4, mixing: adding the microbial agent to the granular material in S3, adopting a low-speed stirring and mixing method, the stirring speed is 30-60rpm, and the mixing time is 10-20 minutes. The mixed material is the finished product of the multifunctional composite improver for acid resistance and aluminum control, which is packaged and stored.

[0035] Comparative Example 1

[0036] The difference between this comparative example and Example 3 is that the acid-blocking and aluminum-controlling composite modifier comprises the following raw materials in parts by weight: 15 parts of microcrystalline activated minerals, 40 parts of silicon-calcium materials, 12 parts of biomass alkaline materials and 18 parts of microbial agents.

[0037] Comparative Example 2

[0038] The difference between this comparative example and Example 3 is that the mineral of the acid-blocking and aluminum-controlling composite modifier is not activated.

[0039] Comparative Example 3

[0040] The difference between this comparative example and Example 3 is that the biomass alkaline material of the acid-blocking and aluminum-controlling composite modifier is not hybridized.

[0041] Comparative Example 4

[0042] The difference between this comparative example and Example 3 is that the acid-blocking and aluminum-controlling composite improver does not contain a microbial agent.

[0043] 1. Performance Testing

[0044] 1. pH test

[0045] The above composite modifier was added to the soil at 10 g / kg. The pH value of the soil was measured after 14 days. The initial soil pH value was 4.5.

[0046] 2. Aluminum ion fixation ability test

[0047] Add the improver to a solution containing 10.0 mg / L aluminum ions. After 7 days, measure the concentration of remaining aluminum ions in the solution and calculate the fixation rate of aluminum ions by the improver.

[0048]

[0049] Where C0 is the initial concentration of aluminum ions in the solution before the reaction,

[0050] C is the concentration of remaining aluminum ions in the solution after the reaction.

[0051] 3. Test results

[0052] Soil pH Aluminum ion concentration (mg / L) Aluminum ion fixation rate (%) Example 1 6.5 2.6 74.0 Example 2 6.3 2.5 75.0 Example 3 6.5 2.2 78.0 Comparative Example 1 6.0 3.1 69.0 Comparative Example 2 5.2 4.5 55.0 Comparative Example 3 5.4 5.2 48.0 Comparative Example 4 5.3 4.8 52.0

[0053] The above results show that the composite amendment has a good effect in improving soil pH, can effectively alleviate the problem of soil acidification, and at the same time has a role in fixing or converting aluminum ions.

[0054] 2. Field test related tests

[0055] 1. Experimental field selection: Select red soil with a pH value between 4.5-5.5 and medium and uniform soil fertility. The experimental field is divided into 7 treatment plots, each with an area of ​​no less than 30 square meters, and repeated 3-4 times. Before rice planting, deep plowing is carried out on the experimental field to a depth of 20-25 cm, breaking up soil clods to make the soil loose and flat. Then, base fertilizer is applied according to conventional rice planting requirements, and 30-40 kg of nitrogen, phosphorus and potassium compound fertilizer (15-15-15) is applied per mu. After fertilization, harrow the land to fully mix the fertilizer with the soil.

[0056] 2. Application of improver: 1-2 days before rice transplanting, evenly spread the improver on the surface of the test field, with a spraying amount of 10g / kg.

[0057] 3. Soil pH test: Soil samples were collected before rice planting, at tillering stage, booting stage and harvest stage for pH measurement.

[0058] 4. Rice yield determination: Early rice in mid-July to late July, late rice in mid-October to late October, each treatment plot adopts the actual yield measurement method. Randomly select 3 sample plots in the plot, each sample plot has an area of ​​1 square meter. Harvest all the rice plants in the sample plot, weigh them after threshing, and record the weight of rice in each sample plot. Then average the weight of rice in the 3 sample plots and convert it into yield per mu (kg / mu). At the same time, determine the moisture content of rice, convert the measured yield into the yield under the standard moisture content (13.5%), select an area of ​​more than 1 square meter at each point to investigate the number of effective ears, and take 3 holes of rice plants to investigate the number of ears and grains and fruit setting rate.

[0059] 5. Rice quality determination: Brown rice rate, polished rice rate, whole polished rice rate, and amylose content were determined according to the method in the national standard GB / T5502-2008 "Grain and Oil Inspection - Inspection of Rice Processing Precision". The determination was carried out according to the Kjeldahl method in the national standard GB5009.5-2016 "National Food Safety Standard - Determination of Protein in Food".

[0060] 6. Test results:

[0061] Table 1: Effects of soil pH

[0062]

[0063] Table 2: Impact of rice yield (kg / mu)

[0064]

[0065]

[0066] Table 3: Rice quality

[0067]

[0068] The treatment with the improver effectively increased the soil pH value, and as the rice growth process progressed, the pH value remained stable or continued to increase slightly. The improver treatment increased the soil pH value to 6.9 at the rice harvest period, indicating that the improver has a good effect on improving soil acidity and can maintain a suitable pH environment throughout the growth period of rice. After the application of the improver, all yield components were improved. The treatment agent of Example 3 increased the number of effective ears to 235,000 ears / mu and the yield to 560kg / mu; it shows that the improver can promote the growth and development of rice by improving soil conditions, thereby increasing yield. The treatment agent of Example 3 increased the brown rice rate to 89.6%, and the polished rice rate and whole polished rice rate were also increased. At the same time, the amylose content was reduced and the protein content was increased; it shows that the improver has a positive effect on improving rice quality while increasing rice yield.

[0069] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A composite improver for acid blocking and aluminum control, characterized in that: The raw materials include the following parts by weight: 30-40 parts of microcrystalline activated minerals, 25-35 parts of silicon-calcium materials, 20-30 parts of biomass alkaline materials and 5-10 parts of microbial agents; The microbial agent is rhizobium, Trichoderma harzianum and Pseudomonas fluorescens in a mass ratio of (12-22):(8-10):(5-7), and the effective viable count is 1×10 8 -10 10 cfu / mL.

2. The composite improver for acid-blocking and aluminum-controlling as claimed in claim 1, characterized in that: The invention comprises the following raw materials in parts by weight: 35 parts of microcrystalline activated minerals, 30 parts of silicon-calcium materials, 25 parts of biomass alkaline materials and 8 parts of microbial agents.

3. A composite improver for acid resistance and aluminum control as claimed in claim 1 or 2, characterized in that: The microcrystalline activated mineral comprises 15-20 parts of phosphate rock powder and 15-20 parts of limestone.

4. A composite improver for acid resistance and aluminum control as claimed in claim 1 or 2, characterized in that: The silicon-calcium material comprises 10-15 parts of silicon-calcium fertilizer, 8-10 parts of slag, and 7-10 parts of oyster shell powder.

5. The composite improver for acid resistance and aluminum control as claimed in claim 4, characterized in that: The slag is selected from steel slag, copper slag, lead-zinc slag, nickel slag, manganese slag or chromium slag.

6. The composite improver for acid-blocking and aluminum-controlling as claimed in claim 1 or 2, characterized in that: The biomass alkaline material includes 12-18 parts of straw biomass charcoal and 8-12 parts of tung seed meal.

7. The method for preparing an acid-blocking and aluminum-controlling composite modifier according to claim 1, characterized in that: The following steps are involved: S1. Ultrafine grinding: Put the microcrystalline activated minerals and calcium silicon materials into the air flow mill for grinding, adjust the air flow speed to 150-300m / s, and the particle size to 1-10μm; S2, microcrystalline activation: the above-mentioned pulverized microcrystalline activated mineral powder is slowly added to the activator solution, the mass volume ratio g / mL is controlled at 1:5-10, the reaction is carried out under stirring, the stirring speed is 100-300rpm, the reaction temperature is controlled at 40-80°C, the reaction time is 2-6 hours, after the reaction is completed, solid-liquid separation is performed to obtain activated microcrystalline activated mineral powder, washed with clean water to neutrality, and then dried at 80-120°C to constant weight for standby use; S3, hybridization: preliminarily mix the biomass alkaline material with the silicon-calcium material of S1 and the microcrystalline activated mineral powder of S2, the mixing time is 15-30 minutes, the rotation speed is 50-100rpm, to obtain a preliminary mixed material, slowly add the organic binder solution to the preliminary mixed material and stir at the same time, the stirring speed is 100-300rpm, so that the organic binder is evenly wrapped on the surface of the inorganic raw material particles to form an organic-inorganic hybrid structure, continue stirring and mixing for 30-60min, granulate, and obtain a granular material with a particle size of 2-5mm; S4, mixing: adding the microbial agent to the granular material in S3, adopting a low-speed stirring and mixing method, the stirring speed is 30-60rpm, and the mixing time is 10-20 minutes. The mixed material is the finished product of the multifunctional composite improver for acid resistance and aluminum control, which is packaged and stored.

8. The method for preparing an acid-blocking and aluminum-controlling composite modifier according to claim 7, characterized in that: The activator solution of S2 is a dilute sulfuric acid or hydrochloric acid solution with a concentration of 1-5 mol / L.

9. The method for preparing an acid-blocking and aluminum-controlling composite modifier according to claim 7, characterized in that: The organic binder solution of S3 is selected from guar gum, cellulose or sodium alginate solution with a mass fraction of 5-15%.

10. Use of the acid-blocking and aluminum-controlling composite modifier according to claim 1 in improving acidic soil, characterized in that: The composite amendment is applied to acidic soil.

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