CN111470914A - Microbial compound fertilizer for heavy metal pollution and preparation method thereof - Google Patents
Microbial compound fertilizer for heavy metal pollution and preparation method thereof Download PDFInfo
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- CN111470914A CN111470914A CN202010556698.0A CN202010556698A CN111470914A CN 111470914 A CN111470914 A CN 111470914A CN 202010556698 A CN202010556698 A CN 202010556698A CN 111470914 A CN111470914 A CN 111470914A
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
Abstract
The invention discloses a microbial compound fertilizer for heavy metal pollution, which comprises the following raw materials in parts by weight: 10-25% of humic acid, 10-15% of biochar, 20-30% of chitosan grafted polyacrylic acid/attapulgite, 5-10% of microbial agent, 10-25% of urea, 5-15% of diammonium phosphate, 5-15% of potassium sulfate, 5-9% of sodium silicate, 2-5% of calcium chloride, 3-6% of ferrous sulfate and 1-3% of boric acid. The invention has the beneficial effects that: the chitosan grafted polyacrylic acid/attapulgite has a porous structure with folds on the surface and a loose surface, the loose surface structure is favorable for water molecule infiltration, the resistance in the adsorption process is reduced, the adsorption quantity of heavy metals is improved, the heavy metals in soil can be effectively adsorbed by matching with a microbial agent, an organic fertilizer and an inorganic fertilizer, the accumulation quantity of the heavy metals in plants is greatly reduced, nutrient elements in insoluble minerals in the soil can be released, the stress resistance of the plants is improved, pollutants are degraded, the soil is improved, and the growth of the plants is promoted.
Description
Technical Field
The invention belongs to the field of fertilizers, and particularly relates to a microbial compound fertilizer for heavy metal pollution and a preparation method thereof.
Background
With the rapid development of science and technology, heavy metal products are widely applied in the society, but due to improper treatment of the heavy metal products after use, heavy metal pollutants continuously enter the environment, the quantity of the pollutants is continuously accumulated, serious pollution is caused to the environment in which people live, the heavy metal pollutants can be retained in the environment for a long time, are difficult to degrade, have high toxicity, can continuously enter animals and plants through media such as water, soil, atmosphere and the like, and then enter human bodies through a food chain, and cause great harm to human health.
At present, the main soil heavy metal pollution remediation technologies include physical remediation, chemical remediation and biological remediation. Wherein the physical remediation method comprises the following steps of soil dressing engineering, electric remediation method, electric heating remediation, heat treatment method and soil leaching method; chemical remediation methods include soil stabilization, photocatalytic degradation, and improvement; bioremediation methods are phytoremediation, animal remediation and microbial remediation. The principle of the microbial remediation technology is that the microbes (such as algae, bacteria, fungi and the like) in the soil environment are used for absorbing, precipitating, oxidizing, reducing and the like heavy metal pollutants to reduce the toxicity of the heavy metals in the soil. Compared with the traditional physical and chemical remediation technologies, the microbial remediation technology has the advantages that the heavy metal polluted soil is remediated by the biological remediation technology, the generated product cannot damage the growing environment of plants, and meanwhile, the biological remediation technology has the characteristics of low cost, high efficiency, no secondary pollution, simplicity in operation, wide application range and the like. Compared with the microbial repair technology and the animal and plant repair technology, the microorganism has the characteristics of small individual, large specific surface area, quick propagation, strong metabolic capability, multiple varieties, wide distribution, strong adaptability, easy culture and the like. However, the microbial remediation techniques have the disadvantages that: the microorganism has certain capacity limitation on the adsorption and other effects of heavy metal pollutants.
Disclosure of Invention
In order to solve the problems, the invention provides a microbial compound fertilizer for heavy metal pollution and a preparation method thereof, which repairs the heavy metal pollution by using the dual functions of a heavy metal adsorbent and microbes.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a microbial compound fertilizer for heavy metal pollution comprises the following raw materials in parts by weight: 10-25% of humic acid, 10-15% of biochar, 20-30% of chitosan grafted polyacrylic acid/attapulgite, 5-10% of microbial agent, 10-25% of urea, 5-15% of diammonium phosphate, 5-15% of potassium sulfate, 5-9% of sodium silicate, 2-5% of calcium chloride, 3-6% of ferrous sulfate and 1-3% of boric acid.
Preferably, the total effective viable count of the microbial agent is 80-120 hundred million cfu/g.
Preferably, the microbial agent comprises one or more of bacillus subtilis, sulfate reducing bacteria, zoogloea, pseudomonas, cyanobacteria, citric acid bacteria and rhodobacter sphaeroides.
Preferably, the mass ratio of the bacillus subtilis to the sulfate reducing bacteria to the pseudomonas is 3:3:1:1: 2.
Preferably, the mass ratio of the bacillus subtilis, the sulfate reducing bacteria, the zoogloea, the citric acid bacteria and the rhodobacter sphaeroides is 3:2:1:2: 2.
Preferably, the content of active humic acid in the humic acid is not less than 10%, and the content of organic matter is not less than 40%.
In addition, the invention also provides a preparation method of the microbial compound fertilizer for heavy metal pollution, which comprises the following steps:
(1) preparing chitosan grafted polyacrylic acid/attapulgite, namely, using 4 mol/L hydrochloric acid solution to carry out magnetic stirring and acidification for 1h at the temperature of 60 ℃ on the attapulgite, cooling and carrying out suction filtration, washing a filter cake to be neutral by deionized water, placing the washed filter cake in a 95 ℃ oven for drying for 24h to obtain the acidified attapulgite, crushing for later use, taking acrylic acid into a 250m L beaker, adding N, N' -methylene bisacrylamide, adding deionized water, carrying out mechanical stirring, slowly adding chitosan under the stirring state, continuously stirring for 1h at the room temperature and in the air atmosphere, adding the prepared acidified attapulgite, carrying out ultrasonic dispersion for 30min, then adding ascorbic acid, carrying out mechanical stirring, dropwise and slowly adding 3% hydrogen peroxide solution, after continuously reacting for 1h, transferring a granular product into the prepared 4 mol/L sodium hydroxide solution, soaking for 4h, dehydrating by using anhydrous ethanol, and placing in a vacuum drier for drying for 24h to obtain the chitosan grafted polyacrylic acid/attapulgite;
(2) urea, diammonium phosphate, potassium sulfate, sodium silicate, calcium chloride, ferrous sulfate and boric acid are dissolved in water, and then are uniformly mixed with humic acid, biochar, chitosan grafted polyacrylic acid/attapulgite and a biological agent, and then are granulated to obtain the microbial fertilizer.
Preferably, the mass ratio of the attapulgite to the hydrochloric acid solution in the step (1) is 1: 13.
Preferably, the mass ratio of the acrylic acid, the N, N' -methylene bisacrylamide, the deionized water, the chitosan, the acidified attapulgite, the ascorbic acid, the hydrogen peroxide solution and the sodium hydroxide solution in the step (1) is 24: 1: 300: 2: 5.5: 0.7:23: 560.
the invention has the beneficial effects that: the chitosan grafted polyacrylic acid/attapulgite has a porous structure with folds on the surface and a loose surface, the loose surface structure is favorable for water molecule infiltration, the resistance in the adsorption process is reduced, the heavy metal adsorption capacity is improved, and the heavy metal in soil can be effectively adsorbed by matching with a microbial agent, a compound fertilizer and an inorganic fertilizer, so that the heavy metal accumulation capacity in plants is greatly reduced. Can release nutrient elements in insoluble minerals in soil, improve the stress resistance of plants, degrade pollutants, improve soil and promote the growth of plants.
Drawings
FIG. 1: the chitosan grafted polyacrylic acid/attapulgite in the invention is SEM picture;
FIG. 2: the invention discloses a synthetic schematic diagram of chitosan grafted polyacrylic acid/attapulgite.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to these examples.
Example 1
A microbial compound fertilizer for heavy metal pollution comprises the following raw materials in parts by weight: 12% of humic acid, 12% of biochar, 21% of chitosan grafted polyacrylic acid/attapulgite, 8% of microbial agent, 11% of urea, 12% of diammonium phosphate, 7% of potassium sulfate, 8% of sodium silicate, 3% of calcium chloride, 4% of ferrous sulfate and 2% of boric acid.
Wherein the microbial agent comprises bacillus subtilis, sulfate reducing bacteria, pseudomonas, cyanobacteria and citric acid bacteria in a mass ratio of 3:3:1:1: 2.
The humic acid biological compound fertilizer for potted chives is prepared by the following method:
(1) preparing chitosan grafted polyacrylic acid/attapulgite, namely, using 4 mol/L hydrochloric acid solution to carry out magnetic stirring and acidification for 1h at the temperature of 60 ℃ on the attapulgite, cooling and carrying out suction filtration, washing a filter cake to be neutral by deionized water, placing the washed filter cake in a 95 ℃ oven for drying for 24h to obtain the acidified attapulgite, crushing for later use, taking acrylic acid into a 250m L beaker, adding N, N' -methylene bisacrylamide, adding deionized water, carrying out mechanical stirring, slowly adding chitosan under the stirring state, continuously stirring for 1h at the room temperature and in the air atmosphere, adding the prepared acidified attapulgite, carrying out ultrasonic dispersion for 30min, then adding ascorbic acid, carrying out mechanical stirring, dropwise and slowly adding 3% hydrogen peroxide solution, after continuously reacting for 1h, transferring a granular product into the prepared 4 mol/L sodium hydroxide solution, soaking for 4h, dehydrating by using anhydrous ethanol, and placing in a vacuum drier for drying for 24h to obtain the chitosan grafted polyacrylic acid/attapulgite;
(2) urea, diammonium phosphate, potassium sulfate, sodium silicate, calcium chloride, ferrous sulfate and boric acid are dissolved in water, and then are uniformly mixed with humic acid, biochar, chitosan grafted polyacrylic acid/attapulgite and a biological agent, and then are granulated to obtain the microbial fertilizer.
Wherein the mass ratio of the attapulgite to the hydrochloric acid solution in the step (1) is 1: 13.
Wherein in the step (1), the mass ratio of acrylic acid, N' -methylene bisacrylamide, deionized water, chitosan, acidified attapulgite, ascorbic acid, hydrogen peroxide solution and sodium hydroxide solution is 24: 1: 300: 2: 5.5: 0.7:23: 560.
example 2
A microbial compound fertilizer for heavy metal pollution comprises the following raw materials in parts by weight: 18% of humic acid, 10% of biochar, 23% of chitosan grafted polyacrylic acid/attapulgite, 7% of microbial agent, 13% of urea, 8% of diammonium phosphate, 9% of potassium sulfate, 6% of sodium silicate, 2% of calcium chloride, 3% of ferrous sulfate and 1% of boric acid.
Wherein the microbial agent comprises bacillus subtilis, sulfate reducing bacteria, pseudomonas, cyanobacteria and citric acid bacteria in a mass ratio of 3:3:1:1: 2.
The microbial compound fertilizer for heavy metal pollution of the present invention was prepared according to the method of example 1.
Example 3
A microbial compound fertilizer for heavy metal pollution comprises the following raw materials in parts by weight: humic acid 10%, biochar 15%, chitosan grafted polyacrylic acid/attapulgite 18%, microbial inoculum 9%, urea 19%, diammonium phosphate 6%, potassium sulfate 7%, sodium silicate 5%, calcium chloride 3%, ferrous sulfate 5%, and boric acid 3%.
Wherein the microbial agent comprises bacillus subtilis, sulfate reducing bacteria, zoogloea, citric acid bacteria and spherical rhodobacter by the mass ratio of 3:2:1:2: 2.
The microbial compound fertilizer for heavy metal pollution of the present invention was prepared according to the method of example 1.
Example 4
A microbial compound fertilizer for heavy metal pollution comprises the following raw materials in parts by weight: 16% of humic acid, 5% of biochar, 25% of chitosan grafted polyacrylic acid/attapulgite, 10% of microbial agent, 15% of urea, 7% of diammonium phosphate, 6% of potassium sulfate, 6% of sodium silicate, 5% of calcium chloride, 3% of ferrous sulfate and 2% of boric acid.
Wherein the microbial agent comprises bacillus subtilis, sulfate reducing bacteria, zoogloea, citric acid bacteria and spherical rhodobacter by the mass ratio of 3:2:1:2: 2.
The microbial compound fertilizer for heavy metal pollution of the invention is prepared according to the method of example 1. The test method comprises the following steps: the soil that adopts to be contaminated by heavy metal is 40cm, and the area is 100m 2's soil as the experimental area to divide the monoblock experimental area into 4 prescriptions, the length and width is 5m, leaves the ridge that the width is 0.5m between every prescription, and every prescription sets up 5 sampling points according to the diagonal principle. And (4) adopting 0-40 cm soil on the surface layer of the test field, cooling in the shade, ventilating and drying, and removing impurities. The concentrations of the effective states of heavy metals Cd, As, Ni, Cu, Hg, Pb and Cr in the soil pH are measured, and the application amount of the microbial compound fertilizer applied to 4 experiments in the embodiments 1 to 4 of the invention is 2300kg/hm2And (5) ploughing, and after 30 days, setting 5 sampling points for each sample according to a diagonal principle. Soil with the surface layer of 0-40 cm of the test field is adopted, the soil is cooled in the shade and aired in a ventilating way, impurities are removed, the pH value of the soil and the effective state concentrations of heavy metals Cd, As, Ni, Cu, Hg, Pb and Cr are measured, and the measurement results are shown in table 1.
TABLE 1 determination of the pH of the soil and the available states of the heavy metals Cd, As, Ni, Cu, Hg, Pb and Cr
According to the determination results, the microbial compound fertilizer for heavy metal pollution prepared by the invention can effectively adsorb heavy metals in soil and greatly reduce the accumulation of the heavy metals in plants.
Claims (9)
1. A microbial compound fertilizer for heavy metal pollution is characterized by comprising the following raw materials in parts by weight: 10-25% of humic acid, 10-15% of biochar, 20-30% of chitosan grafted polyacrylic acid/attapulgite, 5-10% of microbial agent, 10-25% of urea, 5-15% of diammonium phosphate, 5-15% of potassium sulfate, 5-9% of sodium silicate, 2-5% of calcium chloride, 3-6% of ferrous sulfate and 1-3% of boric acid.
2. The microbial compound fertilizer for heavy metal pollution according to claim 1, wherein the total effective viable count of the microbial agent is 80-120 hundred million cfu/g.
3. The microbial compound fertilizer for heavy metal pollution according to claim 1, wherein the microbial agent comprises one or more of bacillus subtilis, sulfate reducing bacteria, zoogloea, pseudomonas, cyanobacteria, citric acid bacteria and rhodobacter sphaeroides.
4. The microbial compound fertilizer for heavy metal pollution according to claim 3, wherein the mass ratio of the bacillus subtilis to the sulfate reducing bacteria to the pseudomonas, the cyanobacteria to the citric acid bacteria is 3:3:1:1: 2.
5. The microbial compound fertilizer for heavy metal pollution according to claim 3, wherein the mass ratio of the bacillus subtilis, the sulfate reducing bacteria, the zoogloea, the citric acid bacteria and the rhodobacter sphaeroides is 3:2:1:2: 2.
6. The microbial compound fertilizer for heavy metal pollution according to claim 1, wherein the content of active humic acid in the humic acid is not less than 10%, and the content of organic matter is not less than 40%.
7. A method for preparing the microbial compound fertilizer for heavy metal pollution according to any one of claims 1 to 6, which comprises the following steps:
(1) preparing chitosan grafted polyacrylic acid/attapulgite, namely, using 4 mol/L hydrochloric acid solution to carry out magnetic stirring and acidification for 1h at the temperature of 60 ℃ on the attapulgite, cooling and carrying out suction filtration, washing a filter cake to be neutral by deionized water, placing the washed filter cake in a 95 ℃ oven for drying for 24h to obtain the acidified attapulgite, crushing for later use, taking acrylic acid into a 250m L beaker, adding N, N' -methylene bisacrylamide, adding deionized water, carrying out mechanical stirring, slowly adding chitosan under the stirring state, continuously stirring for 1h at the room temperature and in the air atmosphere, adding the prepared acidified attapulgite, carrying out ultrasonic dispersion for 30min, then adding ascorbic acid, carrying out mechanical stirring, dropwise and slowly adding 3% hydrogen peroxide solution, after continuously reacting for 1h, transferring a granular product into the prepared 4 mol/L sodium hydroxide solution, soaking for 4h, dehydrating by using anhydrous ethanol, and placing in a vacuum drier for drying for 24h to obtain the chitosan grafted polyacrylic acid/attapulgite;
(2) urea, diammonium phosphate, potassium sulfate, sodium silicate, calcium chloride, ferrous sulfate and boric acid are dissolved in water, and then are uniformly mixed with humic acid, biochar, chitosan grafted polyacrylic acid/attapulgite and a biological agent, and then are granulated to obtain the microbial fertilizer.
8. The method for preparing a microbial compound fertilizer for heavy metal pollution according to claim 7, wherein the mass ratio of the attapulgite to the hydrochloric acid solution in the step (1) is 1: 13.
9. The method for preparing a microbial compound fertilizer for heavy metal pollution according to claim 8, wherein the mass ratio of the acrylic acid, the N, N' -methylene bisacrylamide, the deionized water, the chitosan, the acidified attapulgite, the ascorbic acid, the hydrogen peroxide solution and the sodium hydroxide solution in the step (1) is 24: 1: 300: 2: 5.5: 0.7:23: 560.
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| CN202010556698.0A CN111470914A (en) | 2020-06-18 | 2020-06-18 | Microbial compound fertilizer for heavy metal pollution and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135806A (en) * | 2021-04-14 | 2021-07-20 | 遵义市农村发展服务中心 | Heavy metal polluted microbial compound fertilizer and preparation method thereof |
| CN114436709A (en) * | 2022-02-25 | 2022-05-06 | 贵州全福祥环保科技有限公司 | Attapulgite biological agent for repairing soil heavy metal and preparation method thereof |
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2020
- 2020-06-18 CN CN202010556698.0A patent/CN111470914A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135806A (en) * | 2021-04-14 | 2021-07-20 | 遵义市农村发展服务中心 | Heavy metal polluted microbial compound fertilizer and preparation method thereof |
| CN114436709A (en) * | 2022-02-25 | 2022-05-06 | 贵州全福祥环保科技有限公司 | Attapulgite biological agent for repairing soil heavy metal and preparation method thereof |
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