CN113736473B - Granular acid soil conditioner and preparation method thereof - Google Patents

Granular acid soil conditioner and preparation method thereof Download PDF

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CN113736473B
CN113736473B CN202111215702.8A CN202111215702A CN113736473B CN 113736473 B CN113736473 B CN 113736473B CN 202111215702 A CN202111215702 A CN 202111215702A CN 113736473 B CN113736473 B CN 113736473B
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soil
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CN113736473A (en
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吴玉龙
王永红
何丰
张洪江
王青松
刘光海
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Lomon Land Agricultural Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

The invention belongs to the field of soil conditioners, and discloses a granular acid soil conditioner which comprises the following components in parts by weight: 10-20 parts of alkaline blast furnace slag; 15-25 parts of powdered rock phosphate; 15-25 parts of superfine powder; 10-15 parts of regenerated collagen fiber powder; 30-45 parts of a crumb accelerator; the grain size of the superfine powder is less than 1000 meshes; the regenerated collagen fiber powder is prepared from tanning solid waste; the pellet accelerator is a graft copolymer of acrylamide and cellulose, and the graft copolymer is loaded with alkaline blast furnace slag; the acid soil conditioner disclosed by the invention can be used for efficiently treating acid soil and avoiding other damages to the soil. The invention also provides a preparation method of the soil conditioner, the preparation method is simple, the high-strength granular acid soil conditioner can be prepared, the application is convenient, and the preparation method can be realized on the existing fertilizer production device.

Description

Granular acid soil conditioner and preparation method thereof
Technical Field
The invention relates to the field of soil conditioners, in particular to a granular acid soil conditioner and a preparation method thereof.
Background
Soil acidification, which is the process of continuously decreasing the pH value of soil and increasing the exchangeable acid of soil, is a natural process accompanying the generation and development of soil, and mainly generates hydrogen ions (H) by the dissociation of carbonic acid and organic acid + ) And (5) driving. In southern areas mainly in tropical and subtropical regions, the area of strong acid soil (pH is less than 5.5) is increasing continuously, the problem of soil acidification becomes one of main factors for restricting the growth of crops, aluminum harm and heavy metal harm caused by soil acidification seriously affect the yield and quality of crops, and even bring about the problem of food safety.
The problem of treatment of acidified soil is always more important in agricultural research, and at present, the treatment modes of acidified soil mainly include two types: (1) applying an alkaline substance (such as quicklime); and (2) applying an organic fertilizer. For mode (1): the alkaline substance is applied to improve the acidity of the soil quickly, but the long-term application causes soil hardening and causes deterioration of the water, fertilizer, gas and heat environment of the soil, and the quicklime is mostly powdery, needs manual application when being applied, and is time-consuming and labor-consuming; for mode (2): the organic fertilizer can improve the granular structure of the soil, increase the colloid content of the soil, reduce the leaching loss of base particles and further improve the soil acidification phenomenon, but the effect of the organic fertilizer on the improvement of the soil acidification is slow, and the application of the organic fertilizer usually needs manual application and also consumes time and labor.
Because the two modes have more or less problems and because the two modes consume time and labor during application, common growers often do not select to apply the two modes, and then the soil is left to be continuously acidified, so that the soil acidification problem is further aggravated.
Disclosure of Invention
The first purpose of the invention is to provide a granular acid soil conditioner which can effectively treat acid soil and avoid other damages to the soil.
The second purpose of the invention is to provide the preparation method of the granular acid soil conditioner, which is simple, can prepare the high-strength granular acid soil conditioner, is convenient to apply and can be realized on the existing fertilizer production device.
In order to achieve the purpose, the invention adopts the technical scheme that:
firstly, the invention provides a granular acid soil conditioner which comprises the following components in parts by weight: 10-20 parts of alkaline blast furnace slag; 15-25 parts of powdered rock phosphate; 15-25 parts of superfine powder; 10-15 parts of regenerated collagen fiber powder; 30-45 parts of a crumb accelerator; the grain size of the superfine powder is less than 1000 meshes; the regenerated collagen fiber powder is prepared from tanning solid waste; the pellet accelerator is a graft copolymer of acrylamide and cellulose, and the graft copolymer is loaded with alkaline blast furnace slag.
Further, the granular acid soil conditioner comprises the following components in parts by weight: 15-20 parts of alkaline blast furnace slag; 20-25 parts of powdered rock phosphate; 15-20 parts of superfine powder; 10-15 parts of regenerated collagen fiber powder; 30-40 parts of aggregate accelerator.
The formula comprises the following components: the preparation method of the crumb accelerating agent comprises the following steps:
(1) Straw treatment: crushing straws, stirring and soaking the crushed straws in 0.5mol/L sodium hydroxide solution according to the ratio of the weight of the straws to the volume of the sodium hydroxide solution being 1;
(2) Graft copolymerization: adding the straw fibers and acrylamide treated in the step (1) into a reaction container in proportion, dropwise adding sodium hydroxide into the reactor, adding deionized water, and uniformly stirring; then adding N, N-methylene bisacrylamide and introducing nitrogen, and stirring until the mixture is uniformly mixed to obtain a mixed solution; adding alkaline blast furnace slag into the mixed solution, uniformly stirring, adding potassium persulfate, heating to 60-70 ℃, and reacting for 2-4 hours with stirring; drying and crushing to obtain the product. Wherein the mass ratio of acrylamide to N, N-methylene-bisacrylamide is 1 -3 (ii) a The mass ratio of acrylamide to potassium persulfate was 1 -2 。
In the reaction, the mass ratio of the straw fiber to the acrylamide to the alkaline blast furnace slag is 1; the particle size of the alkaline blast furnace slag is 30-50 meshes.
In the reaction, the straw is selected from one or two of rice straw or wheat straw.
The preparation method of the regenerated collagen fiber powder in the granular acid soil conditioner comprises the following steps:
A. mechanically crushing the leather solid waste to enable the particle size of the leather solid waste to be smaller than 20 meshes;
B. and B, performing alkali treatment on the crushed material obtained in the step A, and drying to obtain regenerated collagen fiber powder.
Specifically, the leather solid wastes in the step A comprise meat residues, hair, scrap leather scraps and the like generated in the leather making process; the alkali treatment in the step B comprises the following specific operations: and B, stirring and soaking the crushed material in the step A for 1-2 hours by adopting 0.5mol/L sodium hydroxide solution, wherein the using amount of the sodium hydroxide solution is 100 times of the weight of the crushed material by volume.
In the present application, the ultrafine powder is an ultrafine powder prepared from a biomass carbon.
In the application, the powdered rock phosphate is medium-low grade powdered rock phosphate, and the particle size of the powdered rock phosphate is less than 30 meshes.
The preparation method of the granular acid soil conditioner comprises the following steps:
s1, weighing the phosphorite powder and the superfine powder in proportion, and dry-mixing; s2, mixing the mixture obtained in the step S1 and the regenerated collagen fiber powder, adding the mixture into a rotary drum granulator, heating, adding water, controlling the granulation time, and preparing to obtain base particles with the average particle size of 1-2 cm; s3, weighing the alkaline blast furnace slag and the granulation accelerant according to the proportion, mixing the alkaline blast furnace slag and the granulation accelerant with the basic particles prepared in the step S2, adding the mixture into the rotary drum granulator again, heating, adding water, controlling the granulation time for granulation, and drying and screening the granules after the granulation is finished to obtain 2-4 cm granules.
Specifically, the granulation temperature is controlled to be 60-70 ℃ in step S2, and 90-120 ℃ in step S3.
The design principle of the acid soil conditioner is as follows:
(1) 10-20 parts of alkaline blast furnace slag is designed in the formula, and the acid soil can be improved by providing direct alkaline substances;
(2) During preparation, the superfine powder and the phosphate rock powder are mixed, the superfine powder with the ultra-large specific surface area is tightly adsorbed with the phosphate rock powder, after the superfine powder reaches the soil, the phosphorus element in the superfine powder and the phosphate rock powder generates competitive adsorption action and is preferentially adsorbed and fixed by the soil, so that the added phosphorus element can be prevented from being fixed by the soil, and the current situation of lack of available phosphorus in acid soil is effectively solved;
(3) After the ground phosphate rock and the superfine powder are mixed, the ground phosphate rock and the superfine powder are mixed with the regenerated collagen fiber powder to form particles of 1-2 cm, on one hand, the ground phosphate rock and the regenerated collagen fiber powder are heated and granulated to ensure that the ground phosphate rock and the regenerated collagen fiber powder are mixed into particlesThe collagen fiber powder is effectively combined, and the regenerated collagen fiber contains various active functional groups such as hydroxyl, carboxyl, amino and the like, and can be combined with phosphorus in the phosphate rock powder to generate the effect of an ion bridge, so that the phosphorus in the low-grade and medium-grade phosphate rock powder is activated and can be slowly released to be absorbed and utilized by crops; on the other hand, the active functional group contained in the regenerated collagen fiber powder can bind to free H in the soil after entering the soil + And Al 3+ Thereby improving the acid environment of the soil;
(4) The graft copolymer loaded with the alkaline blast furnace slag is added, so that the effect of slowly releasing alkaline substances can be achieved, long-acting alkaline substance supply in soil is provided, and alkaline damage caused by excessive alkaline substances applied at one time is avoided; because acrylamide is unstable to alkali, the stability of the loaded alkaline blast furnace slag can be influenced, and the stability of the loaded alkaline blast furnace slag is realized by adopting a mode of graft copolymerization of the acrylamide and cellulose; more importantly, free cations (mainly Al) in soil can be treated by adding a graft copolymer of acrylamide and cellulose 3+ And Cr 3+ ) The combination process mainly depends on the fixation of the three-dimensional network structure of the graft copolymer and the electrostatic adsorption of the graft copolymer to free cations, and the addition of the graft copolymer can introduce aggregates into soil, thereby improving the granular structure of the soil and improving the porosity of the soil.
(5) According to the method, a three-dimensional network structure with super-strong adsorption capacity is formed through graft copolymerization of acrylamide and straw fibers; and the alkaline blast furnace slag is added in the copolymerization process, so that the alkaline blast furnace slag can be uniformly fixed in a three-dimensional network structure; the method is mainly based on the purposes of improving the alkali resistance of polyacrylamide and combining free cations; the aim can be achieved by selecting the straw fiber after alkali treatment, so that a more expensive finished product of carboxymethyl cellulose does not need to be selected.
(6) This application is through forming the core earlier, again on the core surface parcel alkaline blast furnace slag and the mode of aggregate promoter, the proportion of rational distribution stickness material and grittiness material for the granulation is easily controllable, can prepare and obtain the round granule soil conditioner that the granule is regular, intensity is high.
The beneficial effects of the invention are:
the granular acid soil conditioner can effectively improve the acid soil environment, starts from the most fundamental two problems (phosphorus is easy to be fixed and aluminum and heavy metal are harmful) of the acid soil environment, and solves the harm of the acid soil to the growth of crops; the soil conditioner is prepared from solid wastes, so that the preparation process is simple and the cost is low; in addition, the regulator of this application is the granule, can be convenient for mechanized fertilization, promotes its popularization and application.
Drawings
FIG. 1 is a diagram of an experimental apparatus used in Experimental example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention is further described with reference to specific embodiments below. Those whose conditions are not specified in the examples were carried out according to the conventional conditions or conditions recommended by the manufacturer. The reagents used, or those not indicated together with the manufacturer, are conventional products which are commercially available. All features disclosed in this specification may be combined in any combination, except features or/and steps which are mutually exclusive.
The following examples will give a more complete understanding of the invention to those skilled in the art, but are not intended to limit the invention in any way.
Example 1
The embodiment provides a granular acid soil conditioner, which is prepared by the following specific steps:
preparation of pellet accelerator:
(1) Straw treatment: crushing straws, stirring and soaking the crushed straws in 0.5mol/L sodium hydroxide solution according to the ratio of the weight of the straws to the volume of the sodium hydroxide solution being 1;
(2) Graft copolymerization: adding the straw fibers and acrylamide treated in the step (1) into a reaction container in proportion, adding deionized water with the same mass as that of the acrylamide, and uniformly stirring; then adding N, N-methylene bisacrylamide and introducing nitrogen, and stirring until the mixture is uniformly mixed to obtain a mixed solution; adding alkaline blast furnace slag into the mixed solution, uniformly stirring, adding potassium persulfate, heating to 65 ℃, and stirring for reacting for 3 hours; drying and crushing to obtain the product. Wherein the mass ratio of the straw fiber to the acrylamide to the alkaline blast furnace slag satisfies 1; the mass ratio of acrylamide to N, N-methylene-bisacrylamide is 1 -3 (ii) a The mass ratio of acrylamide to potassium persulfate was 1 -2 。
Preparing regenerated collagen fiber powder:
A. mechanically crushing the leather solid waste to enable the particle size of the leather solid waste to be smaller than 20 meshes;
B. and B, stirring and soaking the crushed material obtained in the step A for 1.5 hours by adopting 0.5mol/L sodium hydroxide, wherein the using amount of a sodium hydroxide solution is 100 times of the weight of the crushed material in terms of volume, filtering after stirring and soaking, and drying to obtain regenerated collagen fiber powder.
Preparing a granular acid soil conditioner:
s1, weighing the phosphate rock powder and the superfine powder prepared from the biomass carbon according to a proportion, and dry-mixing;
s2, mixing the mixture obtained in the step S1 and the regenerated collagen fiber powder, adding the mixture into a rotary drum granulator, heating to 60 ℃, adding water, controlling the granulation time, and preparing to obtain base particles with the average particle size of 1-2 cm;
s3, weighing the alkaline blast furnace slag and the granulation accelerant according to the proportion, mixing the alkaline blast furnace slag and the granulation accelerant with the basic particles prepared in the step S2, adding the mixture into the rotary drum granulator again, adding water, heating to 100 ℃, controlling the granulation time, and drying and screening after the granulation is finished to obtain particles of 2-4 cm.
Wherein: 20 parts of alkaline blast furnace slag; 20 parts of ground phosphate rock; 15 parts of superfine powder; 10 parts of regenerated collagen fiber powder; 35 parts of aggregate accelerator.
Example 2
This example provides a granular acid soil conditioner differing from example 1 in that: when the granular acid soil conditioner is prepared, the mixture ratio of each component is as follows: 15 parts of alkaline blast furnace slag; 20 parts of ground phosphate rock; 20 parts of superfine powder; 15 parts of regenerated collagen fiber powder; 30 parts of pellet accelerator.
Example 3
This example provides a granular acid soil conditioner differing from example 1 in that: when preparing the pellet accelerator: the mass ratio of the straw fiber to the acrylamide to the alkaline blast furnace slag satisfies 1.
Comparative example 1
The comparative example provides a granular acid soil conditioner, which comprises 50 parts of alkaline blast furnace slag and 50 parts of powdered rock phosphate, and the granular acid soil conditioner is prepared by uniformly mixing the alkaline blast furnace slag and the powdered rock phosphate.
Comparative example 2
The comparative example provides a granular acid soil conditioner comprising 30 parts of alkaline blast furnace slag; 30 parts of ground phosphate rock; 25 parts of superfine powder and 15 parts of regenerated collagen fiber powder. The method for producing regenerated collagen fibers was the same as in example 1.
The preparation method of the granular acid soil conditioner is different from that of the example 1 in that: and step S2, simultaneously adding the dry powder mixture obtained in the step S1, alkaline blast furnace slag and regenerated collagen fiber powder, and supplementing 2 parts of water glass, dissolving in water, spraying into a granulator and granulating.
Comparative example 3
The difference between the preparation method and the example 1 is that all the raw materials are weighed according to a certain proportion and then directly mixed and added into a granulator, the temperature is raised to 100 ℃, the granulation time and the water addition amount are controlled, and granules with the length of 2-4 cm are obtained after drying and screening.
Examples of the experiments
Experimental example 1 soil column experiment
Soil for experiment: the basic physicochemical properties of experimental soil, red loam in ren county, sichuan province, are shown in Table 1:
TABLE 1 basic Properties of the soil for the experiments
Figure BDA0003310539730000091
The experimental device is shown in the attached figure 1:
the experimental process comprises the following steps:
filling an experimental soil column: taking the sieved soil sample according to the field volume weight, and taking 1.4g/cm 3 And calculating the weight of soil in the soil column, wherein the weight of the soil in the soil column is 1100g at the lower layer and 1100g at the upper layer respectively. During filling, gauze is placed at the bottom and the joint of each layer of the soil columns, the filling of soil samples in the soil columns needs to be uniform, and the joints among the soil columns need to be smooth. The upper soil column is filled with 800g of soil sample, and the rest 300g of soil sample is uniformly mixed with 30g of granular acid soil conditioner and filled into the surface layer of the soil column. And slowly irrigating distilled water to the surface of the soil column until the water reaches the bottommost part, and continuously keeping the soil surface to stay in a water layer of 2 cm.
Sampling and measuring: and taking soil samples 10cm away from the surface layer of the soil when the soil columns are filled for 10d and 60d respectively, air-drying, and measuring the pH value, the quick-acting phosphorus and the content of exchangeable aluminum respectively.
The measuring method comprises the following steps: pH value: measuring the PH of NY-T1377-2007 soil; quick-acting phosphorus: sodium bicarbonate leaching-molybdenum antimony colorimetry resistance; exchangeable aluminum: potassium chloride exchange-neutralization titration
The measurement results are shown in table 2:
TABLE 2 physicochemical properties of the soil after application of an acidic soil conditioner
Figure BDA0003310539730000101
The above results show that: compared with comparative examples 1-3, the soil conditioner can reduce the content of exchangeable aluminum in soil, promote the increase of the content of available phosphorus in the soil and effectively improve the acid environment of the soil.
Experimental example 2 field test
The experimental site: sichuan province ren shou county
Experiment time: 2020 to
And (3) experimental crops: rice (Oryza sativa L.) with improved resistance to stress
Experimental treatment: 5 treatments were set, with the soil conditioner of example 1, comparative example 2 applied and a blank control (no soil conditioner applied), respectively; each treatment set 3 replicates;
the experiment is designed as a random block experiment, and each cell area is 20m 2 Each treated soil conditioner was mechanically applied with the base fertilizer at an application rate of 100 kg/acre, with all other fertilization operations and field operations being identical for each plot. During the harvest period, the yield of each cell and the cadmium content in rice (gb5009.15g) were measured. The results obtained after data processing are shown in table 3:
TABLE 3 crop yield and cadmium content after application of acidic soil conditioner
Experimental group Yield (kg/mu) Cadmium (mg/kg)
Control group 614 0.18
Example 1 718 0.09
Comparative example 1 655 0.16
Comparative example 2 673 0.13
Comparative example 3 689 0.11
The above results show that: compared with comparative examples 1-3, the soil conditioner can remarkably improve the yield and effectively reduce the content of the paddy.
In conclusion, the soil conditioner prepared by the method can effectively reduce soil acidity, further reduce adverse effects of acid soil on crop growth, and promote crop yield and quality.
The present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the protection scope of the present invention, which has the same or similar technical solutions as the present invention.

Claims (4)

1. The granular acid soil conditioner is characterized by comprising the following components in parts by weight: 10 to 20 parts of alkaline blast furnace slag; 15 to 25 parts of phosphate rock powder; 15 to 25 portions of superfine powder; 10 to 15 parts of regenerated collagen fiber powder; 30 to 45 parts of a crumb accelerator; the superfine powder is prepared from biomass carbon;
the grain size of the superfine powder is less than 1000 meshes; the regenerated collagen fiber powder is prepared from tanning solid waste; the pellet accelerator is a graft copolymer of acrylamide and cellulose, and the graft copolymer is loaded with alkaline blast furnace slag;
the preparation method of the granular acid soil conditioner comprises the following steps:
s1, weighing the phosphorite powder and the superfine powder in proportion, and dry-mixing;
s2, mixing the mixture obtained in the step S1 and the regenerated collagen fiber powder, adding the mixture into a rotary drum granulator, heating, adding water, controlling granulation time, and preparing base particles with the average particle size of 1-2cm;
s3, weighing the alkaline blast furnace slag and the pellet accelerant according to the proportion, mixing the alkaline blast furnace slag and the pellet accelerant with the basic particles prepared in the step S2, adding the mixture into a rotary drum granulator again, heating, adding water, controlling the granulation time, drying and screening after granulation is finished to obtain particles of 2-4 cm;
the preparation method of the crumb accelerating agent comprises the following steps:
(1) Straw treatment: crushing straws, performing alkali treatment, removing lignin, drying the treated straw fibers, and crushing the straw fibers until the particle size is less than 60 meshes;
(2) Graft copolymerization: adding the straw fiber and acrylamide treated in the step (1) into a reaction container in proportion, dropwise adding sodium hydroxide into the reactor, adding deionized water, and uniformly stirring; then adding N, N-methylene bisacrylamide and introducing nitrogen, and stirring until the mixture is uniformly mixed to obtain a mixed solution; adding alkaline blast furnace slag into the mixed solution, uniformly stirring, adding potassium persulfate, heating to 60-70 ℃, and reacting for 2-4 hours with stirring; drying and crushing to obtain the product;
the mass ratio of the straw fiber to the acrylamide to the alkaline blast furnace slag is 1 to 2 to 3, and 0.8 to 1.2; the particle size of the alkaline blast furnace slag is 30 to 50 meshes;
the preparation method of the regenerated collagen fiber powder comprises the following steps:
A. mechanically crushing the leather solid waste to enable the particle size of the leather solid waste to be smaller than 20 meshes;
B. b, performing alkali treatment on the crushed material obtained in the step A, and drying to obtain regenerated collagen fiber powder;
and B, stirring and soaking the crushed material in the step A for 1 to 2h by using 0.5mol/L sodium hydroxide.
2. The granular acid soil conditioner of claim 1, wherein the straw is selected from one or both of rice straw and wheat straw.
3. The granular acid soil conditioner according to claim 1, wherein the powdered rock phosphate is a medium-low grade powdered rock phosphate, and the particle size of the powdered rock phosphate is less than 30 meshes.
4. The granular acidic soil conditioner according to claim 1, wherein the granulation temperature is controlled to 60 to 70 ℃ in step S2 and 90 to 120 ℃ in step S3.
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