CN106631490B - Cadmium-reducing selenium-rich organic fertilizer for crops and preparation method and application thereof - Google Patents
Cadmium-reducing selenium-rich organic fertilizer for crops and preparation method and application thereof Download PDFInfo
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- C05—FERTILISERS; MANUFACTURE THEREOF
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- C05D9/00—Other inorganic fertilisers
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- 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
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Abstract
The invention relates to the technical field of agricultural production, in particular to a cadmium-reducing selenium-rich organic fertilizer applied to treatment and remediation of soil heavy metal pollution and a preparation method thereof. The invention adopts the unique combination of the chemical adsorption effect of functional groups on tea polyphenol and humic acid contained in camellia seed meal and camellia plant residues on cadmium and the physical adsorption effect of grease spent bleaching clay and medical stone on cadmium, greatly reduces the content of effective cadmium in soil, and adopts the means that selenium-containing compounds, especially selenoprotein, can form cadmium-selenium-protein compounds with cadmium elements, and the like, thereby achieving the obvious effect of reducing cadmium; meanwhile, the selenium has competitive antagonism on cadmium, and the cadmium element is prevented from migrating and enriching to plants by providing a large amount of selenium to inhibit the plants from absorbing the cadmium. The invention has wide raw material source and low cost, changes waste into valuable by utilizing production and processing wastes, has simple preparation method, is environment-friendly and is easy for industrialized large-scale production.
Description
Technical Field
The invention relates to the technical field of agricultural production, in particular to a cadmium-reducing selenium-rich organic fertilizer applied to treatment and remediation of soil heavy metal pollution and a preparation method thereof.
Background
The soil pollution is called invisible pollution and pollution with the longest latency time, the soil pollution of China is more and more serious at present, cultivated land, urban soil, soil around industrial bases and soil of industrial and mining areas are polluted to different degrees, and the heavy metal pollution is severe, which threatens the sustainable development of ecological environment, food safety and agriculture. Cadmium is one of elements with the strongest biological toxicity in soil heavy metal pollution, has strong chemical activity and lasting toxicity in soil, and is easy to harm human health through the enrichment effect of a food chain. The published 2014 national soil pollution condition survey bulletin shows that the cadmium point position overproof rate is the highest, and the cadmium point position overproof rate is formally determined as the first treatment pollutant of the Chinese soil, so that an effective soil cadmium pollution treatment and remediation technology is urgently needed.
At present, researches on how to reduce the content of cadmium in soil environment and reduce the pollution of cadmium to crop products are mainly focused on the following aspects. One is to reduce Cd by increasing the pH of the soil with an alkaline substance such as limestone2+The activity and mobility of the soil conditioner play a role in passivation, but strong alkaline substances can destroy the acid-base level of the soilBalance and ecological environment. And secondly, the cadmium in the water is fixed by utilizing the physical adsorption capacity of the active adsorption material, such as activated carbon, but the materials have high manufacturing cost and are difficult to apply in a large area, and meanwhile, the physical adsorption is a weak acting force, and the stability of the adsorbed cadmium is poor. And thirdly, the cadmium pollution in the soil is eliminated by the special enrichment capacity of some plants on cadmium, but the plants are not suitable for being planted in all soils, and the period of phytoremediation is long.
Selenium is an element which is recognized in the world to have the functions of improving the immunity of a human body and resisting tumors, is an indispensable trace element for the human body, cannot be synthesized in the human body, and is mainly supplemented by ingesting selenium-enriched food. Therefore, the selenium fertilizer is applied to improve the selenium content in crops by utilizing the enrichment effect of plants, and the development of series selenium-enriched foods on the basis is an effective way for solving the problem of selenium deficiency.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide the cadmium-reducing selenium-enriched organic fertilizer and the preparation method thereof, wherein the cadmium-reducing selenium-enriched organic fertilizer can inhibit the movement of cadmium in soil, prevent the cadmium from migrating from the soil to plants and enriching in the plants, reduce the pollution of the cadmium to crops, simultaneously improve the content of selenium in the soil and enhance the soil fertility.
The above object of the present invention is achieved by the following technical solutions:
a cadmium-reducing selenium-rich organic fertilizer is prepared by mixing oil tea seed meal, grease waste clay and plant residues in a proportion of 40-60: 5-10: 12-28, and mixing the organic rotten clinker obtained by composting and fermenting the mixture with humic acid, plant ash and medical stone powder.
Further preferably, the cadmium-reducing selenium-rich organic fertilizer is prepared from organic rotting clinker, humic acid, plant ash and medical stone powder in a weight ratio of 70-85: 6-10: 8-15: 10-18 by weight ratio.
The preparation method of the cadmium-reducing selenium-rich organic fertilizer comprises the following steps:
(1) material preparation and mixing process
(2) fermentation process
(3) after ripening process
Stacking the mixture after the fermentation process into a stack, covering and sealing the stack by using a plastic film, and stacking the stack for 15 to 30 days until the mixture has no peculiar smell to obtain the organic rotten clinker;
(4) preparation process
The organic rotten clinker, humic acid, plant ash and medical stone powder are stirred and mixed evenly according to a certain proportion, and the organic fertilizer capable of reducing cadmium and enriching selenium is prepared after drying, extrusion and granulation.
Wherein the plant residue is Theaceae plant residue, and is further optimized to be one or more of oil tea fruit shell, oil tea flower, tea tree and tea leaf residue.
Wherein the content of sodium selenite in the sodium selenite aqueous solution is 2-10 g/kg.
In a further preferable embodiment, the particle size of the humic acid and the medical stone powder is 200 meshes or more.
The selenium content of the cadmium-reducing selenium-rich organic fertilizer is more than 10 g/100 kg.
The oil-containing activated clay used in the technical scheme is an oil-containing activated clay which is used in a decoloring process of an oil refining process and adsorbs a certain amount of oil, and is solid waste generated in an oil processing process. In the scheme, the grease in the grease spent bleaching clay provides energy and nutrients for the propagation and growth of microorganisms so as to be consumed, and along with the consumption of the grease, the porous structure of the activated bleaching clay is reappeared, so that the activated bleaching clay has stronger adsorption capacity due to larger specific surface area and pore volume.
The humic acid in the technical scheme is animal and plant remains, particularly plant remains, and is an organic substance formed in a series of processes of microbial decomposition and transformation and geochemistry. The humic acid contains a large amount of functional groups, and the functional groups can form a coordination complex with metal ions to achieve the effects of adsorbing and absorbing the metal ions.
The medical stone in the technical scheme is a natural aluminosilicate mineral substance, contains magnesium, iron, zinc, copper and other trace elements, and has a loose and porous internal structure so as to have a good adsorption effect.
The plant residue in the technical scheme is a Theaceae plant residue, and is further optimized to be one or more of oil tea fruit shells, oil tea leaves, oil tea flowers, tea trees and tea leaves. The camellia seed meal and the camellia plants contain rich active ingredients such as tea polyphenol, tea saponin and the like, the tea polyphenol can perform a complex reaction with metal ions, and the coordination action of the tea polyphenol chelates the metal ions to precipitate the tea polyphenol. The tea saponin is a nonionic surfactant and a natural antibacterial agent, has good surface activity, has the capability of carrying and transferring substances, and has excellent antibacterial capability to resist the corrosion of plant diseases and insect pests.
The technical principle of the technical scheme of the invention is mainly embodied as follows:
1. by adding plant ash and other substances, the alkaline state of the cadmium-reducing selenium-rich organic fertilizer is maintained, the pH value of soil is improved, active cadmium ions are promoted to be converted to cadmium hydroxide, the activity of cadmium elements is reduced, meanwhile, the biological activity of functional groups on tea polyphenol and humic acid can be activated in a weak alkaline environment, the functional groups on the tea polyphenol and the humic acid and the cadmium ions form a coordination complex, exchangeable cadmium is converted to organically combined cadmium, and the aim of chemically adsorbing the cadmium elements is fulfilled.
2. The surface activity capability of a surfactant tea saponin existing in the cadmium-reducing selenium-rich organic fertilizer is utilized to pull cadmium elements and combined cadmium to be gathered on the surfaces of the oil waste argil and the medical stone with porous structures. The grease waste clay and the medical stone have huge surface areas and developed microporous structures, and cadmium elements are fixed in the microporous structures of the grease waste clay and the medical stone in a physical adsorption and ion exchange adsorption mode.
3. The method utilizes the propagation and growth of microorganisms in the production of the cadmium-reducing selenium-rich organic fertilizer to convert inorganic selenium (sodium selenite) into organic selenium such as selenium-containing compounds such as selenoprotein, and the selenium-containing compounds in the soil, particularly the selenoprotein can form a cadmium-selenium-protein compound with cadmium elements, so that the content of effective cadmium in the soil is reduced. Meanwhile, selenium has an antagonistic effect, and can competitively inhibit the absorption of plants to cadmium and prevent the cadmium from migrating and enriching to the plants.
Compared with the prior art, the invention has the advantages that:
1. the invention adopts the unique combination of the chemical adsorption effect of functional groups on tea polyphenol and humic acid contained in camellia seed meal and camellia plant residues on cadmium and the physical adsorption effect of grease spent bleaching clay and medical stone on cadmium, greatly reduces the content of effective cadmium in soil, and adopts the means that selenium-containing compounds, especially selenoprotein, can form cadmium-selenium-protein compounds with cadmium elements, and the like, thereby achieving the obvious effect of reducing cadmium; meanwhile, the selenium has competitive antagonism on cadmium, and the cadmium element is prevented from migrating and enriching to plants by providing a large amount of selenium to inhibit the plants from absorbing the cadmium.
2. The selenium source provided by the invention is organic selenium which is easier to be absorbed and utilized by plants, and overcomes the toxic and side effects of inorganic selenium.
3. The organic fertilizer provided by the invention effectively improves the organic matter content of soil, improves the soil hardening and acidification conditions and enhances the soil fertility.
4. The organic fertilizer provided by the invention is suitable for various crops, and can improve the disease resistance of the crops and the quality of the crops.
5. The invention has wide raw material source and low cost, changes waste into valuable by utilizing production and processing wastes, has simple preparation method, is environment-friendly and is easy for industrialized large-scale production.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1:
in a fermentation tank, mixing plant residues consisting of camellia seed meal, waste oil white clay, camellia seed shells and tea leaves residues in a ratio of 50: 8: 20 weight percent to prepare a mixture, spraying an aqueous solution with the sodium selenite content of 5 g/kg on the mixture, and measuring the water content of the mixture to be 55 percent after uniformly stirring; stacking the mixture into a stack shape with the height of 1.5-2 m and the width of 2-3 m for composting fermentation, and performing primary pile turning treatment by using turning equipment when the temperature is raised to 60-65 ℃; when the temperature of the turned mixture is reduced to room temperature, the mixture is piled again, when the temperature is increased to 60-65 ℃, the pile is turned again, meanwhile, sodium selenite aqueous solution is sprayed to ensure that the water content of the mixture is 50-60%, after the process is repeated for 6 times, the temperature of the pile body is reduced to room temperature and does not rise any more, and the fermentation process is finished; stacking the mixture after fermentation, covering and sealing the mixture by using a plastic film, and obtaining organic rotting clinker after the mixture is stacked for 24 days and no peculiar smell exists in the mixture; mixing the organic rotten material with humic acid, plant ash and medical stone powder according to the weight ratio of 80: 8: 12: 10, stirring and mixing uniformly, drying, extruding and granulating to obtain the cadmium-reducing selenium-rich organic fertilizer.
Example 2:
in a fermentation tank, mixing plant residues consisting of camellia seed meal, waste oil white clay, oil tea and camellia flower in a ratio of 48: 7: 18 to obtain a mixture, spraying an aqueous solution with the sodium selenite content of 8 g/kg on the mixture, and uniformly stirring to obtain a mixture with the water content of 58 percent; stacking the mixture into a stack shape with the height of 1.5-2 m and the width of 2-3 m for composting fermentation, and performing primary pile turning treatment by using turning equipment when the temperature is raised to 60-65 ℃; when the temperature of the turned mixture is reduced to room temperature, the mixture is piled again, when the temperature is increased to 60-65 ℃, the pile is turned again, meanwhile, sodium selenite aqueous solution is sprayed to ensure that the water content of the mixture is 50-60%, after the process is repeated for 7 times, the temperature of the pile body is reduced to room temperature and does not rise any more, and the fermentation process is finished; stacking the mixture after fermentation, covering and sealing the mixture by using a plastic film, and obtaining organic rotting clinker after the mixture is stacked for 20 days and no peculiar smell exists in the mixture; mixing the organic rotten clinker with humic acid, plant ash and medical stone powder according to a ratio of 78: 6: 10: 14, stirring and mixing uniformly, drying, extruding and granulating to obtain the cadmium-reducing selenium-rich organic fertilizer.
Example 3:
in a fermentation tank, mixing plant residues consisting of camellia seed meal, waste oil white clay, tea trees and tea leaves residues in a ratio of 55: 8: 25 weight percent to prepare a mixture, spraying an aqueous solution with the sodium selenite content of 6 g/kg on the mixture, and measuring the water content of the mixture to be 60 percent after uniformly stirring; stacking the mixture into a stack shape with the height of 1.5-2 m and the width of 2-3 m for composting fermentation, and performing primary pile turning treatment by using turning equipment when the temperature is raised to 60-65 ℃; when the temperature of the turned mixture is reduced to room temperature, the mixture is piled again, when the temperature is increased to 60-65 ℃, the pile is turned again, meanwhile, sodium selenite aqueous solution is sprayed to ensure that the water content of the mixture is 50-60%, after the process is repeated for 10 times, the temperature of the pile body is reduced to the room temperature and does not rise any more, and the fermentation process is finished; stacking the mixture after fermentation, covering and sealing by using a plastic film, and obtaining organic rotting clinker after finding that the mixture has no peculiar smell after stacking for 27 days; mixing the organic rotten material with humic acid, plant ash and medical stone powder according to a weight ratio of 82: 8: 8: 12, stirring and mixing uniformly, drying, extruding and granulating to obtain the cadmium-reducing selenium-rich organic fertilizer.
Example 4:
the cadmium-reducing selenium-rich organic fertilizer prepared in the examples 1, 2 and 3 were sampled and indicated as test samples 1, 2 and 3, respectively. Weighing the fresh weight of the sample to be tested, putting the sample into a blast drier for drying until the weight is constant, weighing the quantitative dry weight, putting the dry weight into a crusher for crushing to more than 60 meshes. Accurately weighing 0.5g of a sample to be tested, digesting according to a set microwave digestion program, then accurately sucking a digested sample solution, and determining the content of selenium in the sample to be tested according to the fluorescence value of the digested sample solution by adopting a hydride generation atomic fluorescence method. The results of the experiment are shown in table 1 below:
example 5:
the soil used in the experiment of this example was collected from the cadmium-contaminated subtropical red soil from Yongan town of Liuyang city, and sieved with a 20-mesh sieve. The cadmium-reducing selenium-rich organic fertilizer prepared in the examples 1, 2 and 3 is added into soil according to the proportion of 20%, and a blank comparison group is set up at the same time (namely, no organic fertilizer is added). And after the soil is balanced and aged for 2 months, the pot is filled for carrying out a pot experiment.
The plants selected in the experiment are pepper and corn, seedlings of the pepper and the corn with good growth vigor are selected and transplanted into pots, the experimental group of each plant is 20 plants, 2 similar plants are loaded into each pot, the daily management of the plants in the growth period is conventional management, and after the plants grow to the maturity period, the edible parts are harvested to serve as experimental samples.
Washing an experimental sample with deionized water, drying, crushing with a plant crusher, sieving with a 40-mesh sieve, precisely weighing 5g of the sample into a conical flask, adding mixed acid, soaking overnight, digesting at low temperature with an electric hot plate until complete digestion, heating to drive acid, cooling, and transferring to a constant volume. And (3) determining the contents of cadmium and selenium in the sample by adopting an atomic absorption spectrometry. The results of the experiment are shown in table 2 below:
as can be seen from the table 2, the selenium content of the plant fruits produced by the cadmium-reducing selenium-rich organic fertilizer is 1.472-3.015 mg/kg, and the selenium-rich effect is obvious; meanwhile, the reduction capability of cadmium is 48.8-55.3%, and the reduction capability is outstanding.
Claims (6)
1. The cadmium-reducing selenium-rich organic fertilizer is characterized in that camellia seed meal, oil waste clay and plant residues are mixed by a mixing ratio of 40-60: 5-10: 12-28, spraying a sodium selenite aqueous solution on the mixture, and mixing the organic rotten clinker obtained after composting and fermentation with humic acid, plant ash and medical stone powder to prepare the organic rotten clinker;
wherein the plant residue is Theaceae plant residue, and is one or more of oil Camellia shell, oil Camellia flower, tea tree, and tea leaf residue.
2. The preparation method of the cadmium-reducing selenium-rich organic fertilizer as claimed in claim 1, wherein the preparation method comprises the following steps:
material preparation and mixing process
Firstly, mixing oil tea seed meal, grease spent bleaching clay and plant residues in a fermentation tank in a ratio of 40-60: 5-10: 12-28, and mixing uniformly to obtain a mixture;
secondly, spraying a sodium selenite aqueous solution on the mixture, and uniformly stirring to ensure that the water content of the mixture is 50-60%;
fermentation process
Stacking the mixture into a strip stack shape with the height of 1.5-2 meters and the width of 2-3 meters for composting fermentation, and performing primary pile turning treatment by using turning equipment when the temperature is raised to 60-65 ℃;
secondly, the mixture to be turned is re-stacked after the temperature of the mixture is reduced to room temperature, the mixture is turned again when the temperature is increased to 60-65 ℃, meanwhile, sodium selenite aqueous solution is sprayed to ensure that the water content of the mixture is 50-60%, the steps are repeated for 5-10 times until the temperature of the stack is reduced to room temperature and does not rise any more, and the fermentation process is finished;
(3) after ripening process
Stacking the mixture after the fermentation process into a stack, covering and sealing the stack by using a plastic film, and stacking the stack for 15 to 30 days until the mixture has no peculiar smell to obtain the organic rotten clinker;
preparation process
The organic rotten clinker, humic acid, plant ash and medical stone powder are stirred and mixed evenly according to a certain proportion, and the organic fertilizer capable of reducing cadmium and enriching selenium is prepared after drying, extrusion and granulation.
3. The cadmium-reducing selenium-rich organic fertilizer as claimed in claim 1, wherein the cadmium-reducing selenium-rich organic fertilizer is prepared from organic rotten clinker, humic acid, plant ash and medical stone powder, wherein the organic rotten clinker, the humic acid, the plant ash and the medical stone powder are mixed in a ratio of 70-85: 6-10: 8-15: 10-18 by weight ratio.
4. The preparation method of the cadmium-reducing selenium-rich organic fertilizer as claimed in claim 2, wherein the content of sodium selenite in the sodium selenite aqueous solution is 2-10 g/kg.
5. The cadmium-reducing selenium-rich organic fertilizer as claimed in claim 1, wherein the particle size of the humic acid and the medical stone powder is more than 200 meshes.
6. The cadmium-reducing selenium-rich organic fertilizer is characterized in that the selenium content of the cadmium-reducing selenium-rich organic fertilizer prepared by the preparation method of claim 2 is more than 10 g/100 kg.
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| CN107474855A (en) * | 2017-09-01 | 2017-12-15 | 展亚男 | A kind of composite for restoration of the ecosystem and its preparation method and application |
| CN113973644B (en) * | 2021-10-27 | 2022-11-01 | 贵州省土壤肥料研究所(贵州省生态农业工程技术研究中心)(贵州省农业资源与环境研究所) | Low-cadmium selenium-rich dictyophora textilis planting method |
| CN113979811A (en) * | 2021-12-09 | 2022-01-28 | 广东富晞生物科技有限公司 | Selenium-rich cadmium-reducing lead-reducing mineral substance bio-organic fertilizer and preparation method thereof |
| CN116530375A (en) * | 2023-05-11 | 2023-08-04 | 宜春市科学院(江西富硒产业研究院) | Planting method of selenium-enriched vegetables |
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| CN102584464B (en) * | 2012-03-05 | 2014-01-15 | 叶长东 | Fertilizer containing alkyl glycoside, humic acid and tea saponin |
| CN103766182B (en) * | 2013-10-20 | 2016-05-04 | 湘潭顺天农业科技开发有限公司 | A kind of rice cultivating method of effective reduction paddy cadmium content |
| CN103964937B (en) * | 2014-01-25 | 2016-07-20 | 湖南奇异生物科技有限公司 | A kind of special tea seed cake fertilizer of Oryza sativa L. |
| CN103804091A (en) * | 2014-02-21 | 2014-05-21 | 湖南大学 | Nutrition modifier rich in selenium for lowering content of heavy metals in food crops and application thereof |
| CN104557340A (en) * | 2015-02-09 | 2015-04-29 | 刘备 | Special microbial organic fertilizer for selenium-enriched rice |
| CN104844375A (en) * | 2015-06-03 | 2015-08-19 | 中国科学院地理科学与资源研究所 | Compound fertilizer for repairing cadmium contaminated soil as well as preparation method and application of compound fertilizer |
| CN105819986A (en) * | 2016-05-27 | 2016-08-03 | 广西壮族自治区农业科学院农业资源与环境研究所 | Preparation method and application of selenium-enriched cadmium-resistant foliar fertilizer special for rice |
| CN106045714A (en) * | 2016-07-11 | 2016-10-26 | 浏阳市聚康茶油专业合作社 | Organic fertilizer produced from tea seed meal and tea seed shells and preparing method thereof |
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