CN114210727B - Preparation method of heavy metal contaminated soil phytoremediation enhancer - Google Patents
Preparation method of heavy metal contaminated soil phytoremediation enhancer Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
- B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/03—Algae
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- C09K17/00—Soil-conditioning materials or soil-stabilising materials
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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
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Abstract
The invention discloses a preparation method of a plant repair enhancer for heavy metal contaminated soil, belonging to the technical field of soil pollution treatment and repair and comprising the following steps: adding marine plants, hydrogen peroxide and dilute nitric acid into byproducts of the seaweed gel production process for heat preservation and digestion to obtain digestion solution I; adding the digestion solution I into a sodium bicarbonate aqueous solution for heat preservation and digestion to obtain a digestion solution II, and performing centrifugal separation on the digestion solution II to obtain a liquid I; and distilling and concentrating the liquid I until the water content is 40-60% to obtain the plant repair enhancer. The phytoremediation enhancer disclosed by the invention contains a large amount of mineral elements and organic acid, can promote the growth of the hyperaccumulator plants, effectively improve the biomass of the remediation plants, solve the problem of small biomass of the remediation plants, promote the activation of heavy metal elements in soil, improve the bioavailability of soil heavy metals, accelerate the absorption of the hyperaccumulator plants on the soil heavy metals, and shorten the phytoremediation period of the soil heavy metal pollution.
Description
Technical Field
The invention belongs to the technical field of soil pollution treatment and restoration, and particularly relates to a preparation method of a heavy metal polluted soil phytoremediation enhancer.
Background
A large amount of heavy metal pollutants discharged to the environment enter the soil through different ways every year, so that the soil is polluted by the heavy metals, wherein the heavy metal pollution of farmland soil is particularly serious, and the treatment of the heavy metal pollution of the soil is a big problem in the world at present.
At present, the methods for restoring the heavy metals in the soil are mainly divided into physical and physical chemical restoration, biological restoration and comprehensive restoration, and the methods commonly used for restoring the heavy metals in the farmland soil are chemical fixation and phytoremediation. The chemical fixation is mainly to passivate the heavy metals in the soil by chemical agents, but cannot completely remove the heavy metal pollution in the soil, and can cause secondary pollution when external conditions change. Phytoremediation is a green pollution remediation technology with potential and rapid development speed, and is always favored in soil pollution remediation in recent years. The phytoremediation technology belongs to an in-situ remediation technology, is low in cost, is easy to control secondary pollution, has the effects of protecting surface soil and reducing erosion and water and soil loss after vegetation is formed, can be applied to large-area reclamation of mines and vegetation and landscape remediation of heavy metal polluted sites, and has the advantages of low cost, no damage to soil and river ecological environment, no secondary pollution and the like.
However, plants used for soil heavy metal remediation have the characteristics of large biomass, fast growth and strong pest and disease resistance, and plants with over-accumulation capacity to heavy metals have the defects of small biomass, long growth cycle and the like, so that the effects are slow and the remediation time is long compared with some common engineering measures. When the concentration of the heavy metal in the soil is lower and the overproof effect is not serious, the phytoremediation effect is not obvious, and particularly after the phytoremediation reaches a certain degree, the phytoremediation effect is not obvious when the concentration of the heavy metal in the soil is reduced or the bioavailability is reduced. Therefore, in the soil heavy metal phytoremediation process, the improvement of the biomass of plants or the enrichment capacity of plants on heavy metals is urgently needed, so that a better phytoremediation effect is achieved.
The conventional plant repair enhancer has the problems of small biomass and the like, the plant repair effect is not obvious after heavy metals are aged in soil, and the heavy metals in the soil are released again. The phytoremediation for soil polluted by heavy metals is mainly plant extraction, so how to develop a phytoremediation enhancer, and the pollutants in soil or water are purified through the actions of absorption, volatilization, root filtration, degradation, stabilization and the like of plants, so that the aim of purifying the environment is achieved, and the technical problem to be solved by technical personnel in the field is urgently needed.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a heavy metal contaminated soil phytoremediation enhancer.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a heavy metal contaminated soil phytoremediation enhancer comprises the following steps:
(1) Adding marine plants, hydrogen peroxide and dilute nitric acid into byproducts of the seaweed gel production process for heat preservation and digestion to obtain digestion solution I;
(2) Adding the digestion solution I into a sodium bicarbonate aqueous solution for heat preservation and digestion to obtain a digestion solution II, and performing centrifugal separation on the digestion solution II to obtain a liquid I;
(3) And distilling and concentrating the liquid I until the water content is 40-60% to obtain the plant repair enhancer.
The invention has the beneficial effects that:
1. the invention takes the byproducts of the seaweed gel production process as main raw materials and is supplemented with a certain proportion of marine plants, and the raw materials contain a large amount of mineral elements and organic acids, so that the growth of hyper-accumulative plants can be promoted, the biomass of the restoration plants can be effectively improved, and the problem of small biomass of the restoration plants can be solved.
2. The phytoremediation enhancer contains a large amount of active ingredients and organic acid, can promote the activation of heavy metal elements in soil, improve the bioavailability of heavy metals in soil, accelerate the absorption of hyperaccumulator plants on the heavy metals in the soil, and shorten the phytoremediation period of heavy metal pollution of the soil.
3. The byproducts and marine plants of the seaweed gel production process are all from the sea, the raw materials are sufficient, cheap and easily available, and the problem that the raw material sources of the plant repair enhancer are limited is solved.
4. The plant repair enhancer is colorless viscous liquid, has the water content of 40-60%, can be mixed with water in any ratio, can be sprayed or used in irrigation according to requirements, is convenient and fast to apply, and does not increase other workload.
5. The plant repair enhancer is from the sea, belongs to a pure natural product, and not only can not bring adverse effect to the soil ecological environment, but also can not cause any damage to human bodies in the using process.
6. The phytoremediation enhancer is suitable for phytoremediation of low-level soil polluted by heavy metals, overcomes the problem that the phytoremediation effect of the soil is not ideal at a low level of the heavy metal concentration, and particularly can solve the problems that the soil heavy metal concentration is reduced and the phytoremediation efficiency is sharply reduced after the soil heavy metal phytoremediation is carried out for a certain period.
Further, in the step (1), the preparation method of the byproduct of the seaweed gel production process comprises the following steps:
soaking seaweed in dilute hydrochloric acid to obtain a soaking solution, taking out the soaked seaweed, adding a sodium bicarbonate aqueous solution, carrying out heat preservation digestion to obtain a digestion solution III, carrying out centrifugal separation on the digestion solution III to obtain a liquid II and filter residues, and standing the liquid II to obtain a supernatant and seaweed gel;
the byproduct of the seaweed gel production process is one or a mixture of more of soak solution, filter residue or supernatant.
Furthermore, the preparation method of the by-product of the seaweed gel production process comprises the following steps:
adding 10% dilute hydrochloric acid into seaweed for soaking at 25-30 ℃ for 15-20 minutes to obtain a soaking solution, taking out the soaked seaweed, adding 0.5-2mol/L sodium bicarbonate aqueous solution, preserving heat and digesting at 40-50 ℃ for 4-7 hours to obtain a digestion solution III, wherein the mass of the seaweed, the volume of the dilute hydrochloric acid and the volume ratio of the sodium bicarbonate aqueous solution are 1kg; the byproduct of the seaweed gel production process is one or a mixture of more of soak solution, filter residue or supernatant.
Further, in the step (1), the marine plant is one or more of seaweed, kelp, seaweed or gulfweed.
Adopt above-mentioned further beneficial effect: the marine plants are all from the sea, the raw materials are sufficient, cheap and easily available, and the problem that the raw material sources of the plant repair enhancer are limited is solved.
Further, in the step (1), the ratio of the mass of the by-products of the seaweed gel production process to the mass of the marine plants to the volume of the hydrogen peroxide to the volume of the dilute nitric acid is (5-10) kg:1L (5-10) L.
Adopt above-mentioned further beneficial effect: under the specific proportion, the byproducts of the seaweed gel production process and marine plants can be thoroughly digested, and the production efficiency is improved.
Further, in the step (1), the temperature of the heat preservation digestion is 40-50 ℃, and the time of the heat preservation digestion is 4-7 hours.
Adopt above-mentioned further beneficial effect: under the specific heat preservation and digestion parameters, the byproducts and the marine plants of the seaweed gel production process can be thoroughly digested, and the production efficiency is improved.
Further, in the step (1), the volume concentration of the hydrogen peroxide is 15-25%.
Further, in the step (1), the volume concentration of the dilute nitric acid is 30-65%.
Further, in the step (2), the molar concentration of the aqueous sodium bicarbonate solution is 0.5 to 2mol/L.
Adopt above-mentioned further beneficial effect: the thermal insulation digestion of the hydrogen peroxide solution, the dilute nitric acid solution and the sodium bicarbonate aqueous solution with the specific concentrations can improve the production efficiency of the phytoremediation enhancer, reduce the production cost and avoid unnecessary energy waste.
Further, in the step (2), the temperature of the heat preservation digestion is 40-50 ℃, and the time of the heat preservation digestion is 4-7 hours.
Adopt above-mentioned further beneficial effect: under the specific heat preservation and digestion parameters, byproducts and marine plants of the seaweed gel production process can be thoroughly digested, and the production efficiency is improved.
Further, in the step (2), the centrifugal rotating speed is 2000-3000r/min, and the centrifugal time is 10-30min.
Adopt above-mentioned further beneficial effect: under the specific centrifugal parameters, the digestion solution II can be completely subjected to solid-liquid centrifugation, so that the production efficiency of the plant repair enhancer is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the by-product of the seaweed gel production process comprises the following steps:
adding 10kg of seaweed into 10L of dilute hydrochloric acid with the volume concentration of 10% for soaking at the temperature of 28 ℃ for 18 minutes to obtain a soaking solution, taking out the soaked seaweed, adding 70L of sodium bicarbonate aqueous solution with the molar concentration of 1mol/L for heat preservation and digestion at the temperature of 45 ℃ for 5 hours to obtain a digestion solution III, carrying out centrifugal separation on the digestion solution III to obtain a liquid II and filter residues, carrying out centrifugal rotation at the speed of 2500r/min for 20 minutes, and standing the liquid II for 15 minutes to obtain a supernatant and seaweed gel.
(II) the preparation method of the plant repair enhancer for the heavy metal contaminated soil comprises the following steps:
(1) Adding 1kg of kelp, 1L of hydrogen peroxide with the volume concentration of 20% and 8L of dilute nitric acid with the volume concentration of 45% into 4kg of soak solution, 2kg of filter residue and 2kg of supernatant, and carrying out heat preservation and digestion at the temperature of 45 ℃ for 6 hours to obtain digestion solution I;
(2) Adding the digestion solution I into a sodium bicarbonate water solution with the molar concentration of 1mol/L, preserving heat and digesting for 5 hours at the temperature of 45 ℃ to obtain a digestion solution II, and carrying out centrifugal separation on the digestion solution II, wherein the centrifugal rotation speed is 2500r/min, and the centrifugal time is 20min to obtain a liquid I;
(3) And (3) distilling and concentrating the liquid I until the water content is 50% to obtain the phytoremediation enhancer.
Example 2
The preparation method of the by-product of the seaweed gel production process comprises the following steps:
soaking 10kg of seaweed in 10L of 10% dilute hydrochloric acid at 25 ℃ for 15 minutes to obtain a soaking solution, taking out the soaked seaweed, adding 50L of 0.5mol/L sodium bicarbonate solution at 40 ℃ for heat preservation and digestion for 4 hours to obtain a digestion solution III, carrying out centrifugal separation on the digestion solution III to obtain a liquid II and filter residues, carrying out centrifugal rotation at 2000r/min for 10 minutes, and standing the liquid II for 10 minutes to obtain a supernatant and seaweed gel.
(II) the preparation method of the heavy metal contaminated soil phytoremediation enhancer comprises the following steps:
(1) Adding 3kg of soak solution, 1kg of filter residue and 1kg of supernatant into 1kg of gulfweed, 1L of hydrogen peroxide with the volume concentration of 15% and 5L of dilute nitric acid with the volume concentration of 30%, and carrying out heat preservation and digestion at the temperature of 40 ℃ for 4 hours to obtain digestion solution I;
(2) Adding the digestion solution I into a sodium bicarbonate aqueous solution with the molar concentration of 0.5mol/L, preserving heat and digesting for 4 hours at the temperature of 40 ℃ to obtain a digestion solution II, and carrying out centrifugal separation on the digestion solution II, wherein the centrifugal rotation speed is 2000r/min, and the centrifugal time is 10min to obtain a liquid I;
(3) And (5) distilling and concentrating the liquid I until the water content is 40% to obtain the phytoremediation enhancer.
Example 3
The preparation method of the by-product of the seaweed gel production process comprises the following steps:
soaking 10kg of seaweed in 10L of 10% dilute hydrochloric acid with the volume concentration of 30 ℃ for 20 minutes to obtain a soaking solution, taking out the soaked seaweed, adding 100L of 2mol/L sodium bicarbonate aqueous solution with the molar concentration of 2mol/L, preserving heat and digesting at the temperature of 50 ℃ for 7 hours to obtain a digestion solution III, carrying out centrifugal separation on the digestion solution III to obtain a liquid II and filter residues, carrying out centrifugal rotation speed of 3000r/min for 30 minutes, and standing the liquid II for 20 minutes to obtain a supernatant and seaweed gel;
(II) the preparation method of the plant repair enhancer for the heavy metal contaminated soil comprises the following steps:
(1) Adding 5kg of soak solution, 3kg of filter residue and 2kg of supernatant into 1kg of seaweed, 1L of hydrogen peroxide with the volume concentration of 25% and 10L of dilute nitric acid with the volume concentration of 65%, and carrying out heat preservation digestion at the temperature of 50 ℃ for 7 hours to obtain digestion solution I;
(2) Adding the digestion solution I into a sodium bicarbonate aqueous solution with the molar concentration of 2mol/L, carrying out heat preservation digestion at the temperature of 50 ℃ for 7 hours to obtain a digestion solution II, and carrying out centrifugal separation on the digestion solution II, wherein the centrifugal rotation speed is 3000r/min, and the centrifugal time is 130min to obtain a liquid I;
(3) And (5) distilling and concentrating the liquid I until the water content is 60% to obtain the phytoremediation enhancer.
Effect test
Preparing polluted soil: taking clean surface farmland soil, and respectively adding NaH 2 AsO 4 And HgCl 2 Preparing the composite heavy metal contaminated soil containing 60mg/kg of As and 1mg/kg of Hg.
Pot experiment design: 1.0kg of polluted soil is contained in each pot, and 1 ciliate desert-grass seedling is planted in each pot.
Application of the enhancer: the phytoremediation enhancer prepared in example 1 was applied at 3 levels, 1. 50ml of the plant repair enhancer solution is applied every month, and water and fertilizer management is normally carried out.
Harvesting ciliate desert-grass after growing normally for 90 days, and respectively measuring the biomass of the upper parts and the lower parts of the four groups of ciliate desert-grass lawns; the biomass of the upper and lower parts of the four centipede grasslands and the enrichment conditions of As and Hg are shown in the table 1 and the table 2.
TABLE 1 Grateloupia filicina biomass (g/strain) treated differently
| Grouping | Overground part | Underground part |
| Blank control | 1.33 | 0.70 |
| 1:200 | 1.52 | 0.86 |
| 1:100 | 1.68 | 0.61 |
| 1:50 | 1.87 | 0.66 |
And (4) conclusion: as can be seen from table 1, the biomass of the underground part 1, 100, 1. The plant repair enhancer can promote the growth of hyperaccumulator plants, effectively improve the biomass of the repair plants and solve the problem of small biomass of the repair plants.
TABLE 2 content and enrichment of As and Hg in the lower part of grass land of centipede treated differently
And (4) conclusion: as shown in Table 2, the phytoremediation enhancer provided by the invention can promote the activation of heavy metal elements in soil, improve the bioavailability of heavy metals in soil, accelerate the absorption of heavy metals in soil by super-accumulator plants, and shorten the phytoremediation period of heavy metal pollution in soil.
The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (2)
1. The preparation method of the heavy metal contaminated soil phytoremediation enhancer is characterized by comprising the following steps:
(1) Adding marine plants, hydrogen peroxide and dilute nitric acid into byproducts of the seaweed gel production process for heat preservation and digestion to obtain digestion solution I;
(2) Adding the digestion solution I into a sodium bicarbonate aqueous solution for heat preservation digestion to obtain a digestion solution II, and performing centrifugal separation on the digestion solution II to obtain a liquid I;
(3) Distilling and concentrating the first liquid to 40-60% of water content to obtain a plant repair enhancer;
in the step (1), the ratio of the mass of the by-product of the seaweed gel production process to the mass of the marine plant to the volume of the hydrogen peroxide to the volume of the dilute nitric acid is (5-10) kg:1L (5-10) L;
in the step (1), the temperature of the heat preservation digestion is 40-50 ℃, and the time of the heat preservation digestion is 4-7 hours;
in the step (1), the volume concentration of the hydrogen peroxide is 15-25%;
in the step (1), the volume concentration of the dilute nitric acid is 30-65%;
in the step (2), the molar concentration of the sodium bicarbonate aqueous solution is 0.5-2mol/L;
in the step (2), the temperature of the heat preservation digestion is 40-50 ℃, and the time of the heat preservation digestion is 4-7 hours;
in the step (1), the preparation method of the byproduct of the seaweed gel production process comprises the following steps:
adding 10% dilute hydrochloric acid into seaweed for soaking at 25-30 ℃ for 15-20 minutes to obtain a soaking solution, taking out the soaked seaweed, adding 0.5-2mol/L sodium bicarbonate aqueous solution, preserving heat and digesting at 40-50 ℃ for 4-7 hours to obtain a digestion solution III, wherein the mass of the seaweed, the volume of the dilute hydrochloric acid and the volume ratio of the sodium bicarbonate aqueous solution are 1kg; the byproduct of the seaweed gel production process is one or a mixture of more of soak solution, filter residue or supernatant;
the marine plant is seaweed.
2. The preparation method of the plant repair enhancer for heavy metal contaminated soil according to claim 1, wherein in the step (2), the centrifugal rotation speed is 2000-3000r/min, and the centrifugal time is 10-30min.
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| CN202111553846.4A CN114210727B (en) | 2021-12-17 | 2021-12-17 | Preparation method of heavy metal contaminated soil phytoremediation enhancer |
| ZA2022/07029A ZA202207029B (en) | 2021-12-17 | 2022-06-24 | Method for preparing phytoremediation enhancer for heavy metal contaminated soil |
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| CN1513815A (en) * | 2003-03-28 | 2004-07-21 | 中国海洋大学 | Production process of seaweed fine fertilizer |
| CN1473798A (en) * | 2003-06-26 | 2004-02-11 | 中国海洋大学 | Process for producing seaweed liquid fertilizer |
| CN104355749B (en) * | 2014-11-11 | 2016-07-06 | 烟台嘉特生物技术有限公司 | A kind of production method of fermentable alga fertilizer |
| CN104892157B (en) * | 2015-05-29 | 2017-10-17 | 领先生物农业股份有限公司 | A kind of active alga fertilizer and its production method |
| CN109180387A (en) * | 2018-11-09 | 2019-01-11 | 中国农业科学院农业资源与农业区划研究所 | A kind of granular urea preparation method containing alginic acid synergistic carrier suitable for rice top dressing |
| CN110887724A (en) * | 2019-10-30 | 2020-03-17 | 汕头大学医学院 | Sample pretreatment method for detecting trace inorganic elements in biological sample |
| CN110819659A (en) * | 2019-11-15 | 2020-02-21 | 斯蒂芬·Y·周 | Preparation method of seaweed organic polymer |
| CN110681692B (en) * | 2019-11-15 | 2021-08-27 | 斯蒂芬·Y·周 | Method for repairing heavy metal contaminated soil |
| CN113109322A (en) * | 2021-04-15 | 2021-07-13 | 山东省海洋资源与环境研究院(山东省海洋环境监测中心、山东省水产品质量检验中心) | Method for determining main heavy metal elements in marine organisms |
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