CN114561218A - Cadmium-polluted soil conditioner prepared from waste biological straws and preparation method thereof - Google Patents

Cadmium-polluted soil conditioner prepared from waste biological straws and preparation method thereof Download PDF

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CN114561218A
CN114561218A CN202210207204.7A CN202210207204A CN114561218A CN 114561218 A CN114561218 A CN 114561218A CN 202210207204 A CN202210207204 A CN 202210207204A CN 114561218 A CN114561218 A CN 114561218A
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solid
straws
cadmium
mass
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CN114561218B (en
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张海涛
张磊
徐长青
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SHANDONG SANFANG CHEMICAL INDUSTRY GROUP 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
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00—Other organic fertilisers
    • C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/80—Soil conditioners
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/10—Solid or semi-solid fertilisers, e.g. powders
    • C05G5/12—Granules or flakes
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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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    • C09K2101/00—Agricultural use
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse

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Abstract

The invention discloses a cadmium-polluted soil conditioner prepared from waste biological straws and a preparation method thereof, and belongs to the technical field of environmental protection. The conditioner is prepared from the following raw materials in parts by weight: 200 parts of humic acid 100, 50-100 parts of biomass carbon, 10-20 parts of straw organic porous fiber, 10-20 parts of quick lime, 10-30 parts of urea, 10-20 parts of ammonium phosphate, 5-10 parts of potassium chloride, 1-5 parts of resistant dextrin, 1-5 parts of water retention agent and 1-5 parts of synergist. The soil conditioner provided by the invention can effectively reduce the content level of heavy metal particles in soil while providing abundant nutrient substances for crops, realizes the recycling of waste biological straws, is safe, environment-friendly and pollution-free, has low using amount, high cadmium removal efficiency and convenient use, is particularly suitable for treating acid cadmium-polluted soil, and has wide economic and social benefits.

Description

Cadmium-polluted soil conditioner prepared from waste biological straws and preparation method thereof
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a cadmium-polluted soil conditioner prepared from waste biological straws and a preparation method thereof.
Background
At present, the problem of soil pollution is getting worse, wherein the soil heavy metal pollution is difficult to decompose in material circulation and energy circulation due to difficult detection, and is easy to accumulate in soil, thus causing crop yield reduction, and the heavy metal pollution enters into the plant body through the root system absorption of the plant, and is harmful to human health through the transmission and enrichment of a food chain. The heavy metal pollution of soil is mainly lead and cadmium, the cadmium is a non-essential element in the biological growth and development process, and is one of the heavy metal species with the greatest harm to animals, plants and human bodies in nature. Cadmium has strong toxicity and biological mobility and is difficult to degrade, so that cadmium is easily absorbed and enriched by crops and enters a food chain along with the crops to further cause harm to human health.
The natural restoration of the land polluted by the heavy metal needs a long time, and the land is artificially treated by methods of changing and modifying soil and the like, although the effect is obvious, the investment is too large, the engineering quantity is huge, the cost is high, and the method is only suitable for the treatment of local pollution; the method comprises the steps of reducing the biological effectiveness of cadmium in soil by adjusting the pH value of the soil or Eh and the like through the soil by applying lime and the like, controlling the chemical adsorption, passivation and the like of cadmium accumulation of crops, wherein heavy metals such as cadmium in the soil are in dynamic balance, so long as the cadmium is in the soil, the cadmium can be activated again along with the change of the soil environment and enters a food chain under the condition that the cadmium is weakened by human intervention, and meanwhile, when the addition amount of substances for changing the soil environment is too large, the original ecological balance of the soil can be damaged, so that the risk of secondary pollution of the soil can be caused; although the plant restoration method is economical and environment-friendly, the popularization is still difficult due to the change of the planting habits and varieties on a large scale; the biological method has obvious benefit, but the treatment effect is often fluctuated greatly due to factors such as breeding and propagation of microorganisms, living environment of the microorganisms and the like. In these methods, the problem of crop yield reduction caused by heavy metal cadmium pollution treatment is also existed.
Biochar is a novel material, which is a product formed by thermal cracking of biomass under anoxic conditions. The biochar has smaller particles, fine distribution and lighter texture, is a black porous solid, mainly comprises carbon, oxygen and the like, the content of carbon in the biochar is generally over 70 percent, and the biochar prepared from the raw materials has wide sources, such as wood chips, straws, industrial organic wastes, municipal sludge, palm fibers, coconut fibers and the like can be used as the raw materials. The biochar has the characteristics of being loose and porous, large in specific surface area, large in negative charge on the surface and the like, has good adsorption property, can be used as a soil structure improver or a soil pollution repairing agent, can improve the pH value of acid soil and increase the cation exchange capacity, so that pollutants and heavy metals in the soil are adsorbed, the accumulation of Cd, Pb and Zn in the bodies of crops is reduced, the microbial metabolism is accelerated, the microbial biomass of the soil is improved, the soil fertility is improved, the yield of crops such as rice is increased, and the quality of agricultural products is improved.
However, the existing method for improving the cadmium-polluted soil by using the biochar still has unstable passivation effect and poor durability, and needs to be applied repeatedly for many times, so that the production efficiency and the cost are greatly increased, the removal efficiency is general, the cost performance is not high, and the method cannot be effectively popularized and applied.
Disclosure of Invention
Aiming at the problems in the prior art, the cadmium pollution conditioner is prepared from waste biological straws, can exert the effect stably for a long time after being applied once, and simultaneously can improve the cadmium pollution of the soil, adjust the physical and chemical properties and the nutritional level of the soil and promote the sustainable development of agriculture.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the cadmium-polluted soil conditioner prepared from waste biological straws comprises the following raw materials in parts by weight: 200 parts of humic acid 100, 50-100 parts of biomass carbon, 10-20 parts of straw organic porous fiber, 10-20 parts of quick lime, 10-30 parts of urea, 10-20 parts of ammonium phosphate, 5-10 parts of potassium chloride, 1-5 parts of resistant dextrin, 1-5 parts of water retention agent and 1-5 parts of synergist.
Further, the preparation method of the straw organic porous fiber comprises the following steps:
(1) crushing waste straws, adding water accounting for 50-80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 30-60min, and filtering to collect solid residues;
(2) treating the solid residue with 4-6% NaOH solution for 30-50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 36-72 hr;
(3) mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a mass ratio of 5: 1, dispersing in absolute methanol, and continuously magnetically stirring for 3-5 hours to obtain a pre-reaction mixed solution;
(4) and (3) carrying out freeze-drying on the solid obtained in the step (2) according to the solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating the mixture for 5 to 10min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 120-150MPa and the treatment temperature of 20 to 30 ℃, and fully drying to obtain the straw organic porous fiber.
Furthermore, the waste straws in the step (1) are corn straws, wheat straws or sorghum straws.
Further, in the step (3), the solid-to-liquid ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate to the absolute ethyl alcohol is 1 kg: 10L.
Further, the water-retaining agent is potassium polyacrylate.
Furthermore, the synergist is ethylenediamine tetraacetic acid or sodium dodecyl benzene sulfonate.
A cadmium-polluted soil conditioner prepared from waste biological straws comprises the following preparation steps:
(1) preparing straw organic porous fiber: crushing waste straws, adding water accounting for 50-80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 30-60min, and filtering to collect solid residues; treating the solid residue with 4-6% NaOH solution for 30-50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 36-72 hr; mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a molar ratio of 5: 1, dispersing in absolute methanol, and continuously magnetically stirring for 3-5 hours to obtain a pre-reaction mixed solution; and (3) mixing the solid obtained by freeze-drying according to the solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating the mixture for 5 to 10min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 120-150MPa and the treatment temperature of 20 to 30 ℃, and fully drying the mixture to obtain the straw organic porous fiber;
(2) weighing the raw materials according to the weight parts, sequentially adding biomass carbon, straw organic porous fiber and humic acid into a jet mill, adding quick lime, urea, ammonium phosphate, potassium chloride, resistant dextrin, a water-retaining agent and a synergist, simultaneously crushing, controlling the fineness to be 200-mesh and 300-mesh, granulating to obtain the solid particle soil conditioner, and packaging and warehousing.
Each of the raw materials of the present invention is commercially available.
The dosage of the conditioner is 100-200 kg/mu.
The soil conditioner provided by the invention reduces the addition of traditional inorganic fertilizers such as urea and monoammonium phosphate, and is replaced by novel fertilizer humic acid, and the humic acid contains a large amount of active nutrient substances, so that the soil nutrition level can be improved while comprehensive nutrient substances are provided for crops. In order to reduce the loss of nutrient substances, the biomass charcoal is added, and the loose and porous structure of the biomass charcoal can effectively adsorb and fix the nutrient substances, reduce the loss of the nutrient substances, and can adsorb heavy metal elements, but the adsorption force is not strong and the action is not lasting.
In order to assist the enhancement of the biomass charcoal to play a role, the waste biological straws are subjected to enzyme treatment to remove starch and cellulose, and then alkali liquor treatment is carried out to remove protein, so that an internal cavity is further formed; then 2-methylimidazole and cobalt nitrate hexahydrate are added for mixing modification, then high-pressure treatment is carried out, oxygen-containing functional groups are fully added, a loose and expanded form is finally formed and filled in the inner cavity of the biological straw, and after the biological straw and the biomass charcoal are mixed, the biological straw and the biomass charcoal are firmly adsorbed in the gap of the biomass charcoal through acting forces such as hydrogen bonds and the like, so that adsorption and fixation of heavy metal elements such as cadmium are greatly enhanced, and meanwhile, the slow release of nutrient substances is realized. Therefore, the recycling of the waste biological straws is realized, the heavy metal content level of the soil is realized, and the reduction of the fertilizer is realized, so that three purposes are achieved.
The invention also adds a synergist which is ethylene diamine tetraacetic acid or sodium dodecyl benzene sulfonate and can assist in complexing heavy metal particles in soil and further reduce the content level of heavy metal ions.
Advantageous effects
The soil conditioner provided by the invention can effectively reduce the content level of heavy metal particles in soil while providing abundant nutrient substances for crops, realizes the recycling of waste biological straws, is safe, environment-friendly and pollution-free, has low using amount, high cadmium removal efficiency and convenient use, is particularly suitable for treating acid cadmium-polluted soil, and has wide economic and social benefits.
Drawings
FIG. 1 is a graph showing the cadmium content of each part of wheat in example 4 and comparative examples 1 to 4 of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
The cadmium-polluted soil conditioner prepared from waste biological straws comprises the following raw materials in parts by weight: 100 parts of humic acid, 50 parts of biomass charcoal, 10 parts of straw organic porous fiber, 10 parts of quick lime, 10 parts of urea, 10 parts of ammonium phosphate, 5 parts of potassium chloride, 1 part of resistant dextrin, 1 part of water-retaining agent and 1 part of synergist.
The preparation method of the straw organic porous fiber comprises the following steps:
(1) crushing waste straws, adding water accounting for 50% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 30min, and filtering and collecting solid residues;
(2) treating the solid residue with 4% NaOH solution for 30min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 36 h;
(3) mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a mass ratio of 5: 1, dispersing the mixture in absolute methanol, and continuously magnetically stirring for 3 hours to obtain a pre-reaction mixed solution;
(4) and (3) carrying out freeze-drying on the solid obtained in the step (2) according to a solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating for 5min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 120Mpa and the treatment temperature of 20 ℃, and fully drying to obtain the straw organic porous fiber.
The waste straws in the step (1) are corn straws.
In the step (3), the solid-to-liquid ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate to the absolute ethyl alcohol is 1 kg: 10L.
The water-retaining agent is potassium polyacrylate.
The synergist is ethylenediamine tetraacetic acid.
A cadmium-polluted soil conditioner prepared from waste biological straws comprises the following preparation steps:
(1) preparing straw organic porous fiber: crushing waste straws, adding water accounting for 50% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 30min, and filtering and collecting solid residues; treating the solid residue with 4% NaOH solution for 30-50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 36 h; mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a molar ratio of 5: 1, dispersing the mixture in absolute methanol, and continuously magnetically stirring for 3 hours to obtain a pre-reaction mixed solution; and (3) mixing the solid obtained by freeze-drying according to the solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating for 5min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 120Mpa and the treatment temperature of 20-30 ℃, and fully drying to obtain the straw organic porous fiber;
(2) weighing the raw materials according to the weight parts, sequentially adding biomass carbon, straw organic porous fiber and humic acid into a jet mill, adding quick lime, urea, ammonium phosphate, potassium chloride, resistant dextrin, a water-retaining agent and a synergist, simultaneously crushing, controlling the fineness to be 200-mesh and 300-mesh, granulating to obtain the solid particle soil conditioner, and packaging and warehousing.
Each of the starting materials in this example is commercially available.
The dosage of the conditioner in the embodiment is 100-200 kg/mu.
Example 2
The cadmium-polluted soil conditioner prepared from waste biological straws comprises the following raw materials in parts by weight: 110 parts of humic acid, 80 parts of biomass charcoal, 13 parts of straw organic porous fiber, 15 parts of quick lime, 15 parts of urea, 15 parts of ammonium phosphate, 6 parts of potassium chloride, 4 parts of resistant dextrin, 3 parts of water-retaining agent and 2 parts of synergist.
The preparation method of the straw organic porous fiber comprises the following steps:
(1) crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues;
(2) treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr;
(3) mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a mass ratio of 5: 1, dispersing in absolute methanol, and continuously magnetically stirring for 5 hours to obtain a pre-reaction mixed solution;
(4) and (3) carrying out freeze-drying on the solid obtained in the step (2) according to a solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating for 10min in an ultrahigh pressure micro-jet homogenizing device at the treatment pressure of 150Mpa and the treatment temperature of 20-30 ℃, and fully drying to obtain the straw organic porous fiber.
The waste straws in the step (1) are wheat straws.
In the step (3), the solid-to-liquid ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate to the absolute ethyl alcohol is 1 kg: 10L.
The water-retaining agent is potassium polyacrylate.
The synergist is sodium dodecyl benzene sulfonate.
A cadmium-polluted soil conditioner prepared from waste biological straws comprises the following preparation steps:
(1) preparing straw organic porous fiber: crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues; treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr; mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a molar ratio of 5: 1, dispersing the mixture in absolute methanol, and continuously magnetically stirring for 5 hours to obtain a pre-reaction mixed solution; and (3) mixing the solid obtained by freeze-drying according to the solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating for 10min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 150Mpa and the treatment temperature of 20-30 ℃, and fully drying to obtain the straw organic porous fiber;
(2) weighing the raw materials according to the weight parts, sequentially adding biomass carbon, straw organic porous fiber and humic acid into a jet mill, adding quick lime, urea, ammonium phosphate, potassium chloride, resistant dextrin, a water-retaining agent and a synergist, simultaneously crushing, controlling the fineness to be 200-mesh and 300-mesh, granulating to obtain the solid particle soil conditioner, and packaging and warehousing.
Each of the starting materials in this example is commercially available.
The dosage of the conditioner in the embodiment is 100-200 kg/mu.
Example 3
The cadmium-polluted soil conditioner prepared from waste biological straws comprises the following raw materials in parts by weight: 115 parts of humic acid, 90 parts of biomass charcoal, 15 parts of straw organic porous fiber, 17 parts of quick lime, 25 parts of urea, 18 parts of ammonium phosphate, 8 parts of potassium chloride, 4 parts of resistant dextrin, 4 parts of water-retaining agent and 3 parts of synergist.
Further, the preparation method of the straw organic porous fiber comprises the following steps:
(1) crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues;
(2) treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr;
(3) mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a mass ratio of 5: 1, dispersing in absolute methanol, and continuously magnetically stirring for 5 hours to obtain a pre-reaction mixed solution;
(4) and (3) carrying out freeze-drying on the solid obtained in the step (2) according to a solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating for 10min in an ultrahigh pressure micro-jet homogenizing device at the treatment pressure of 150Mpa and the treatment temperature of 20-30 ℃, and fully drying to obtain the straw organic porous fiber.
The waste straws in the step (1) are sorghum straws.
In the step (3), the solid-to-liquid ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate to the absolute ethyl alcohol is 1 kg: 10L.
The water-retaining agent is potassium polyacrylate.
The synergist is ethylenediamine tetraacetic acid.
A cadmium-polluted soil conditioner prepared from waste biological straws comprises the following preparation steps:
(1) preparing straw organic porous fiber: crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues; treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr; mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a molar ratio of 5: 1, dispersing the mixture in absolute methanol, and continuously magnetically stirring for 5 hours to obtain a pre-reaction mixed solution; and (3) mixing the solid obtained by freeze-drying according to the solid-liquid ratio of 1 g: dispersing 10ml of the organic porous fiber in the pre-reaction mixed solution, treating for 10min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 150Mpa and the treatment temperature of 30 ℃, and then fully drying to obtain the straw organic porous fiber;
(2) weighing the raw materials according to the weight parts, sequentially adding biomass carbon, straw organic porous fiber and humic acid into a jet mill, adding quick lime, urea, ammonium phosphate, potassium chloride, resistant dextrin, a water-retaining agent and a synergist, simultaneously crushing, controlling the fineness to be 200-mesh and 300-mesh, granulating to obtain the solid particle soil conditioner, and packaging and warehousing.
Each of the starting materials in this example is commercially available.
The dosage of the conditioner in the embodiment is 100-200 kg/mu.
Example 4
The cadmium-polluted soil conditioner prepared from waste biological straws comprises the following raw materials in parts by weight: 200 parts of humic acid, 100 parts of biomass charcoal, 20 parts of straw organic porous fiber, 20 parts of quick lime, 30 parts of urea, 20 parts of ammonium phosphate, 10 parts of potassium chloride, 5 parts of resistant dextrin, 5 parts of water-retaining agent and 5 parts of synergist.
The preparation method of the straw organic porous fiber comprises the following steps:
(1) crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues;
(2) treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr;
(3) mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a mass ratio of 5: 1, dispersing the mixture in absolute methanol, and continuously magnetically stirring for 5 hours to obtain a pre-reaction mixed solution;
(4) and (3) carrying out freeze-drying on the solid obtained in the step (2) according to the solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating for 10min in an ultrahigh pressure micro-jet homogenizing device at 150Mpa and 30 ℃, and fully drying to obtain the straw organic porous fiber.
The waste straws in the step (1) are corn straws.
In the step (3), the solid-to-liquid ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate to the absolute ethyl alcohol is 1 kg: 10L.
The water-retaining agent is potassium polyacrylate.
The synergist is ethylenediamine tetraacetic acid.
A cadmium-polluted soil conditioner prepared from waste biological straws comprises the following preparation steps:
(1) preparing straw organic porous fiber: crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues; treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr; mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a molar ratio of 5: 1, dispersing the mixture in absolute methanol, and continuously magnetically stirring for 5 hours to obtain a pre-reaction mixed solution; and (3) mixing the solid obtained by freeze-drying according to the solid-liquid ratio of 1 g: dispersing 10ml of the organic porous fiber in the pre-reaction mixed solution, treating for 10min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 150Mpa and the treatment temperature of 30 ℃, and fully drying to obtain the straw organic porous fiber;
(2) weighing the raw materials according to the parts by weight, sequentially adding biomass carbon, straw organic porous fiber and humic acid into an airflow crusher, adding quicklime, urea, ammonium phosphate, potassium chloride, resistant dextrin, a water-retaining agent and a synergist, crushing at the same time, controlling the fineness to be 200 plus 300 meshes, granulating to obtain a solid particle soil conditioner, packaging and warehousing.
Each of the starting materials in this example is commercially available.
The dosage of the conditioner in the embodiment is 100-200 kg/mu.
Comparative example 1
The cadmium-polluted soil conditioner prepared from waste biological straws is prepared from the following raw materials in parts by weight: 200 parts of humic acid, 100 parts of biomass charcoal, 20 parts of straw organic porous fiber, 20 parts of quick lime, 30 parts of urea, 20 parts of ammonium phosphate, 10 parts of potassium chloride, 5 parts of resistant dextrin, 5 parts of water-retaining agent and 5 parts of synergist.
The preparation method of the straw organic porous fiber comprises the following steps:
(1) crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, and filtering and collecting solid residues;
(2) treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr;
(3) and (3) carrying out freeze-drying on the solid obtained in the step (2) according to the solid-liquid ratio of 1 g: dispersing 10ml of the organic porous fiber in deionized water, treating for 10min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 150Mpa and the treatment temperature of 30 ℃, and fully drying to obtain the straw organic porous fiber.
The waste straws in the step (1) are corn straws.
The water-retaining agent is potassium polyacrylate.
The synergist is ethylenediamine tetraacetic acid.
A cadmium-polluted soil conditioner prepared from waste biological straws comprises the following preparation steps:
(1) preparing straw organic porous fiber: crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues; treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr; and (3) mixing the solid obtained by freeze-drying according to the solid-liquid ratio of 1 g: dispersing 10ml of the organic porous fiber in deionized water, treating for 10min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 150MPa and the treatment temperature of 30 ℃, and then fully drying to obtain the straw organic porous fiber;
(2) weighing the raw materials according to the weight parts, sequentially adding biomass carbon, straw organic porous fiber and humic acid into a jet mill, adding quick lime, urea, ammonium phosphate, potassium chloride, resistant dextrin, a water-retaining agent and a synergist, simultaneously crushing, controlling the fineness to be 200-mesh and 300-mesh, granulating to obtain the solid particle soil conditioner, and packaging and warehousing.
This comparative example was conducted in the same manner as example 4 except that the modification with 2-methylimidazole and cobalt nitrate hexahydrate was not conducted.
Comparative example 2
The cadmium-polluted soil conditioner prepared from waste biological straws is prepared from the following raw materials in parts by weight: 200 parts of humic acid, 100 parts of biomass charcoal, 20 parts of straw organic porous fiber, 20 parts of quick lime, 30 parts of urea, 20 parts of ammonium phosphate, 10 parts of potassium chloride, 5 parts of resistant dextrin, 5 parts of water-retaining agent and 5 parts of synergist.
The preparation method of the straw organic porous fiber comprises the following steps:
(1) crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, and filtering and collecting solid residues;
(2) treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr;
(3) mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a mass ratio of 5: 1, dispersing the mixture in absolute methanol, and continuously magnetically stirring for 5 hours to obtain a pre-reaction mixed solution;
(4) and (3) carrying out freeze-drying on the solid obtained in the step (2) according to a solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, and fully drying to obtain the straw organic porous fiber.
The waste straws in the step (1) are corn straws.
In the step (3), the solid-to-liquid ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate to the absolute ethyl alcohol is 1 kg: 10L.
The water-retaining agent is potassium polyacrylate.
The synergist is ethylenediamine tetraacetic acid.
A cadmium-polluted soil conditioner prepared from waste biological straws comprises the following preparation steps:
(1) preparing straw organic porous fiber: crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues; treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72 hr; mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a molar ratio of 5: 1, dispersing the mixture in absolute methanol, and continuously magnetically stirring for 5 hours to obtain a pre-reaction mixed solution; and (3) mixing the solid obtained by freeze-drying according to the solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, and then fully drying to obtain straw organic porous fiber;
(2) weighing the raw materials according to the weight parts, sequentially adding biomass carbon, straw organic porous fiber and humic acid into a jet mill, adding quick lime, urea, ammonium phosphate, potassium chloride, resistant dextrin, a water-retaining agent and a synergist, simultaneously crushing, controlling the fineness to be 200-mesh and 300-mesh, granulating to obtain a solid particle soil conditioner, packaging and warehousing
This comparative example was the same as example 4 except that the treatment was not carried out using the ultrahigh pressure microfluidizer.
Comparative example 3
The cadmium-polluted soil conditioner prepared from waste biological straws comprises the following raw materials in parts by weight: 200 parts of humic acid, 100 parts of biomass charcoal, 20 parts of straw organic porous fiber, 20 parts of quick lime, 30 parts of urea, 20 parts of ammonium phosphate, 10 parts of potassium chloride, 5 parts of resistant dextrin, 5 parts of water-retaining agent and 5 parts of synergist.
The preparation method of the straw organic porous fiber comprises the following steps:
(1) crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues;
(2) and treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, washing with ethanol and acetone for 3 times, filtering, and vacuum freeze-drying the solid at-50 deg.C for 72h to obtain the straw organic porous fiber.
The waste straws in the step (1) are corn straws.
The water-retaining agent is potassium polyacrylate.
The synergist is ethylenediamine tetraacetic acid.
A cadmium-polluted soil conditioner prepared from waste biological straws comprises the following preparation steps:
(1) preparing straw organic porous fiber: crushing waste straws, adding water accounting for 80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 60min, filtering and collecting solid residues; treating the solid residue with 6% NaOH solution for 50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 72h to obtain straw organic porous fiber;
(2) weighing the raw materials according to the weight parts, sequentially adding biomass carbon, straw organic porous fiber and humic acid into a jet mill, adding quick lime, urea, ammonium phosphate, potassium chloride, resistant dextrin, a water-retaining agent and a synergist, simultaneously crushing, controlling the fineness to be 200-mesh and 300-mesh, granulating to obtain the solid particle soil conditioner, and packaging and warehousing.
The comparative example is the same as example 4 except that the modification of 2-methylimidazole and cobalt nitrate hexahydrate and the treatment of an ultrahigh pressure micro-jet homogenizing device are not carried out.
Performance test
Test soil: the method is characterized in that cadmium-contaminated soil collected from the Junan county of Linyi city, Shandong province is collected, a 0-20cm mixed soil sample is collected according to a quincunx method, the soil type is brown soil, and the soil is powder loam. The soil to be tested is subjected to impurity removal, natural air drying and grinding, is sieved by a 0.85mm aperture sieve and is put into a self-sealing bag for storage and standby.
A sample to be tested: the soil conditioners obtained in examples 1 to 4 of the present invention and comparative examples 1 to 3 were applied at an application rate of 100 kg/mu, in terms of a soil weight of about 50 g/kg.
The detection method comprises the following steps:
alkaline hydrolysis nitrogen of soil: the basic physicochemical properties of the soil were determined by a conventional method. 1 mol. L NaOH alkaline hydrolysis diffusion method; 0.5 mol.L of quick-acting phosphorus in soil-1NaHCO3Leaching-colorimetric method; quick-acting potassium 1 mol.L-1NH4OAC leaching-flame photometry; measuring pH value with electrode method (soil-water mass ratio of 1: 2.5), and measuring with pH meter; sample Cd concentrationThe atomic absorption spectrophotometer is adopted; determining the total Cd content of the plants by HNO3-HClO4Digestion, extracting the content of Cd in the soil active state by a DTPA leaching method, and extracting the Cd in the soil in morphological grading by a Tessier method.
The test method comprises the following steps: a pot experiment is used, 0-20cm surface soil sample is filled in each pot, 8kgCd polluted soil is filled in each pot, meanwhile, a soil conditioner with a corresponding amount is mixed in each pot, and the container is a cylindrical flowerpot. The quantitative watering maintains about 60 percent of the field water capacity of the soil. The winter wheat planting variety is vortex wheat 66. Sowing the seeds in 2020, 11 months and 15 days, and respectively collecting wheat plants and corresponding rhizosphere soil samples in a wheat seedling stage, a jointing stage and a mature stage. And naturally drying the rhizosphere soil sample in a shady and cool indoor place, grinding, and sieving by using a sieve with the aperture of 2mm and 0.15mm for later use. And (3) deactivating enzyme of the plant sample at 105 ℃ for 30min, drying the plant sample to constant weight at 75 ℃, dividing the plant sample into roots, stems and leaves, seeds and glumes according to test requirements, and crushing the plant sample for later use.
TABLE 1 initial soil physicochemical Properties
Figure BDA0003531359830000111
TABLE 2 soil characteristics after completion of the experiment
Figure BDA0003531359830000112
As can be seen from the data in Table 1 and FIG. 1, Cd is distributed regularly in each organ of wheat, and the content of Cd is expressed as root > other leaves > stem sheath > sword leaf > wheat husk and grain, the content of Cd in the upper part of the wheat is obviously lower than that of Cd in the lower part, Cd in the soil is mainly enriched in the root system of wheat, and the content of Cd in the wheat husk and grain is lower than that in other organs.
In addition, the conditioner provided by the invention has the advantages that the physical and chemical properties of soil are obviously improved, the double modification of straw fibers is a guarantee for realizing the high-efficiency cadmium removal effect of the conditioner, and the effect is weak in the absence of the conditioner.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.

Claims (7)

1. The cadmium-polluted soil conditioner prepared from waste biological straws is characterized by being prepared from the following raw materials in parts by weight: 200 parts of humic acid 100, 50-100 parts of biomass carbon, 10-20 parts of straw organic porous fiber, 10-20 parts of quick lime, 10-30 parts of urea, 10-20 parts of ammonium phosphate, 5-10 parts of potassium chloride, 1-5 parts of resistant dextrin, 1-5 parts of water retention agent and 1-5 parts of synergist.
2. The cadmium-polluted soil conditioner prepared from the waste biological straws of claim 1, wherein the preparation method of the straw organic porous fiber comprises the following steps:
(1) crushing waste straws, adding water accounting for 50-80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 30-60min, and filtering to collect solid residues;
(2) treating the solid residue with 4-6% NaOH solution for 30-50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 36-72 hr;
(3) mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a mass ratio of 5: 1, dispersing in absolute methanol, and continuously magnetically stirring for 3-5 hours to obtain a pre-reaction mixed solution;
(4) and (3) carrying out freeze-drying on the solid obtained in the step (2) according to a solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating the mixture for 5 to 10min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 120-150MPa and the treatment temperature of 20 to 30 ℃, and fully drying to obtain the straw organic porous fiber.
3. The cadmium-polluted soil conditioner prepared from the waste biological straws in the step (1) is characterized in that the waste straws in the step (1) are corn straws, wheat straws or sorghum straws.
4. The cadmium-polluted soil conditioner prepared from the waste biological straws as claimed in claim 2, wherein the solid-to-liquid ratio of the 2-methylimidazole, the cobalt nitrate hexahydrate and the absolute ethyl alcohol in the step (3) is 1 kg: 10L.
5. The cadmium-polluted soil conditioner prepared from the waste biological straws as claimed in claim 1, wherein the water retention agent is potassium polyacrylate.
6. The cadmium-polluted soil conditioner prepared from the waste biological straws as claimed in claim 1, wherein the synergist is ethylenediamine tetraacetic acid or sodium dodecyl benzene sulfonate.
7. The cadmium-polluted soil conditioner prepared from the waste biological straws of any one of claims 1-6, which is characterized by comprising the following preparation steps:
(1) preparing straw organic porous fiber: crushing waste straws, adding water accounting for 50-80% of the mass of the straws, adding amylase accounting for 0.5% of the mass of the solid mixture and cellulase accounting for 0.5% of the mass of the solid mixture, continuously stirring for 30-60min, and filtering to collect solid residues; treating the solid residue with 4-6% NaOH solution for 30-50min, repeatedly washing with deionized water to adjust pH to 7-8, cleaning with ethanol and acetone for 3 times, filtering, and vacuum lyophilizing the solid at-50 deg.C for 36-72 hr; mixing 2-methylimidazole and cobalt nitrate hexahydrate according to a molar ratio of 5: 1, dispersing in absolute methanol, and continuously magnetically stirring for 3-5 hours to obtain a pre-reaction mixed solution; and (3) mixing the solid obtained by freeze-drying according to the solid-liquid ratio of 1 g: dispersing 10ml of the mixture in the pre-reaction mixed solution, treating the mixture for 5 to 10min in ultrahigh pressure micro-jet homogenizing equipment at the treatment pressure of 120-150MPa and the treatment temperature of 20 to 30 ℃, and fully drying the mixture to obtain the straw organic porous fiber;
(2) weighing the raw materials according to the weight parts, sequentially adding biomass carbon, straw organic porous fiber and humic acid into a jet mill, adding quick lime, urea, ammonium phosphate, potassium chloride, resistant dextrin, a water-retaining agent and a synergist, simultaneously crushing, controlling the fineness to be 200-mesh and 300-mesh, granulating to obtain the solid particle soil conditioner, and packaging and warehousing.
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