CN110157451B - Preparation method of arsenic-containing soil stabilizer compounded by modified lignocellulose and inorganic powder through ball mill - Google Patents
Preparation method of arsenic-containing soil stabilizer compounded by modified lignocellulose and inorganic powder through ball mill Download PDFInfo
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- CN110157451B CN110157451B CN201910500090.3A CN201910500090A CN110157451B CN 110157451 B CN110157451 B CN 110157451B CN 201910500090 A CN201910500090 A CN 201910500090A CN 110157451 B CN110157451 B CN 110157451B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention discloses a preparation method of an arsenic-containing soil stabilizer compounded by modified lignocellulose and inorganic powder by using a ball mill. The arsenic-containing soil stabilizer is prepared by taking lignocellulose (wood chips) and inorganic powder as raw materials and loading metal oxide, wherein the mass ratio of the lignocellulose to the inorganic powder is (7-12): 1. The method comprises the following specific steps: (1) taking 50g of the processed hemlock fir sawdust and illite, and putting the processed hemlock fir sawdust and illite into a ball mill; (2) taking the aluminum modified lignocellulose and inorganic powder composite material as an example, Al is prepared according to the mass percentage of 20 percent of the mass of the metal aluminum and the mass of the adsorption material2(SO4)3Solution and NaOH solution, and Al (OH) produced by mixing and stirring the solution and the NaOH solution3Pouring the suspension into a ball mill, mixing and grinding; (3) and (3) carrying out vacuum freeze drying on the adsorbent ground by the ball mill to obtain the arsenic-containing soil stabilizer compounded by the aluminum modified lignocellulose and the inorganic powder. During the ball milling process, the lignocellulose and the inorganic powder are refined, and simultaneously, the dual effects of modification and blending are achieved.
Description
Technical Field
The invention belongs to the technical field of biological planting, and particularly relates to an arsenic-containing soil stabilizer, and a preparation method and application thereof.
Background
Arsenic and its compounds are mainly used in alloy smelting, pesticide and medicine, pigment and other industries, and may be combined with mercapto enzyme in cell to inhibit cell oxidation, paralyze blood vessel motion center and paralyze capillary vessel. Arsenic in soil is accumulated to a certain degree to poison soil-plant systems, which not only causes degradation of soil and reduction of crop yield and quality, but also pollutes surface water and underground water through runoff and leaching action, deteriorates hydrological environment, and may endanger human life and health through direct contact with food chains and other ways. Therefore, it is necessary to develop a product and a method which can avoid serious harm to human beings caused by the above problems.
Disclosure of Invention
The first purpose of the invention is to provide an arsenic-containing soil stabilizer; the second purpose is to provide a preparation method of the arsenic-containing soil stabilizer, and the third purpose is to provide application of the arsenic-containing soil stabilizer.
The first purpose of the invention is realized by that the arsenic-containing soil stabilizer is prepared by taking lignocellulose and inorganic powder as raw materials and loading metal oxide, and the mass ratio of the lignocellulose to the inorganic powder is (7-12): 1.
The second purpose of the invention is realized by putting raw materials of lignocellulose and inorganic powder in a formula ratio into a ball mill, adding hydroxide suspension, mixing, grinding for 10-120 min, carrying out vacuum freeze drying for 10-15 h, and drying to obtain the target arsenic-containing soil stabilizer.
The third purpose of the invention is realized by the application of the arsenic-containing soil stabilizer in stabilizing arsenic in soil.
Cellulose is the most abundant and cheapest renewable resource in the world, and is mainly derived from cotton, wood, grass, straw and the like. The modified cellulose adsorbent has the advantages of large adsorption capacity, high stability, reproducibility and the like, and has selective adsorption capacity on heavy metal ions. Illite is a clay mineral, has fine granularity, large surface area and excellent heavy metal adsorption capacity. The lignocellulose and the illite are mixed for use, so that the adsorption performance of the lignocellulose and the illite on arsenic can be obviously improved, the migration, the conversion and the enrichment of heavy metal elements are influenced, and the harm of heavy metals to human bodies is reduced.
The invention provides a preparation method of an arsenic-containing soil stabilizer compounded by modified cellulose and inorganic powder, aiming at overcoming the existing arsenic pollution condition of soil. The raw materials used in the invention are cheap and easily available, and are nontoxic and harmless, the prepared stabilizer is natural and degradable, the renewable resources of illite and cellulose are fully utilized, and the stabilizer has a good stabilizing effect on arsenic in soil.
The method for preparing the arsenic-containing soil stabilizer by taking hemlock wood chips as an example comprises the following specific operation steps:
(1) taking 50g of processed hemlock fir sawdust and illite, putting the processed hemlock fir sawdust and illite into a ball mill, wherein the hemlock fir sawdust comprises the following components in parts by weight: the mass ratio of illite is 9: 1;
(2) taking the aluminum modified cellulose illite composite material as an example, Al is prepared according to the proportion that the mass of aluminum and the mass percentage of the adsorption material are 20 percent2(SO4)3Mixing the solution with NaOH solution, stirring for 10min to obtain Al (OH)3Pouring the suspension into a ball mill, mixing and grinding for 10-120 min;
(3) and (3) carrying out vacuum freeze drying on the adsorbent ground by the ball mill to obtain the modified lignocellulose and illite composite material.
Preferably, the preparation method of the arsenic-containing soil stabilizer by compounding lignocellulose modified by a ball mill with inorganic powder comprises the step (1) of preparing the lignocellulose, wherein the lignocellulose comprises but is not limited to hemlock, poplar, catalpa bungei, white gourd and toona sinensis.
Preferably, the preparation method of the arsenic-containing soil stabilizer compounded by modifying cellulose and inorganic powder by using a ball mill is not limited to illite in the step (1), and other inorganic or mineral powder such as clay, attapulgite, sepiolite, fly ash and the like can also be used.
Preferably, the preparation method of the arsenic-containing soil stabilizer compounded by modifying lignocellulose and inorganic powder by using a ball mill comprises the step (2) of preparing Al2(SO4)3AlCl may be used3、FeCl3、Ce(NO3)3、KMnO4One or more of them are compositely substituted.
The invention has the following advantages:
1. the arsenic-containing soil stabilizer provided by the invention uses hemlock wood cellulose, illite, sodium hydroxide, aluminum sulfate, cerium nitrate, ferric chloride and potassium permanganate as raw materials, and has the advantages of wide source and low price.
2. The arsenic-containing soil stabilizer provided by the invention is short in ball milling time and mild in preparation conditions.
3. The arsenic-containing soil stabilizer provided by the invention has the advantages of extremely small water addition amount, direct drying after ball milling treatment, simple operation and suitability for industrial mass production.
4. The arsenic-containing soil stabilizer provided by the invention adopts lignocellulose and illite as raw materials, is convenient to obtain, belongs to an environment-friendly material, is used for removing heavy metals in water, and is easy to separate; the fertilizer is used for stabilizing heavy metals in soil, realizes the returning of crops to the field and has no secondary pollution.
5. The preparation method has the advantages of simple preparation process, no toxicity, easy operation and high product efficiency. The method is remarkably characterized in that the double effects of modification and blending are achieved while refining the lignocellulose and the inorganic powder. The process is easy to industrialize and industrialize.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
The arsenic-containing soil stabilizer is prepared by taking lignocellulose and inorganic powder as raw materials and loading metal oxide, wherein the mass ratio of the lignocellulose to the inorganic powder is (7-12): 1.
The mass ratio of the lignocellulose to the inorganic powder is (8-10): 1.
The mass ratio of the lignocellulose to the inorganic powder is 9: 1.
The lignocellulose is one or more of hemlock fir, poplar, catalpa bungei, white gourd and Chinese toon.
The inorganic powder is one or more of illite, clay, attapulgite, sepiolite and fly ash.
The metal oxide is Al2(SO4)3、AlCl3、FeCl3、Ce(NO3)3、KMnO4One or more of the above-mentioned materials are compositely transformed.
The metal oxide is prepared from the following components in percentage by mass: the mass percentage of the arsenic-containing soil stabilizer is 10-30%.
The preparation method of the arsenic-containing soil stabilizer comprises the steps of putting lignocellulose and inorganic powder which are raw materials in a formula ratio into a ball mill, adding hydroxide suspension, mixing, grinding for 10-120 min, carrying out vacuum freeze drying for 10-15 h, and drying to obtain the target arsenic-containing soil stabilizer.
The hydroxide suspension is prepared by adding NaOH, KOH and Ca (OH) in the preparation process2、Fe(OH)2、Fe(OH)3One or more of them.
The arsenic-containing soil stabilizer is applied to stabilizing arsenic in soil.
The ball mill applied by the invention has the working principle that: when the rotary disc rotates, the ball milling tanks revolve around the main disc shaft and perform planetary rotation motion around the main disc shaft in opposite directions, and the grinding balls and the material in the tanks produce mutual collision, shearing and friction in high speed motion to crush, grind, mix and disperse the material. The equipment can grind various solid particles, suspensions and pastes with different particle sizes and different materials by a dry method and a wet method, and the minimum particle size of a grinding product can be 0.1 micron.
The invention is further illustrated by the following specific examples:
example 1
And (3) building a test device table, taking 50g of lignocellulose and illite according to the mass ratio of 9:1, and putting the mixture into a ball mill. According to the mass of the metal aluminum: the mass percent of the adsorbing material is 20 percent, and the concentration of the adsorbing material is 0.5mol/LAl to 360mL2(SO4)3To the solution, 40mL of concentrated NaOH solution were added dropwise, while maintaining magnetic stirring, to form Al (OH)3And pouring the suspension into a ball mill, mixing and grinding the suspension with an adsorption material for 10-120 min, and carrying out vacuum freeze drying for 12h by using a freeze dryer to obtain the arsenic-containing soil stabilizer compounded by the modified cellulose and the inorganic powder.
In a laboratory, high-concentration arsenic-containing soil is provided by Yunnan, the arsenic-containing soil is sieved by a 20-mesh sieve, and 100g of the arsenic-containing soil is weighed and put into a basin. The effective arsenic content measured by the acid leaching method is 180 mg/kg. 2-6% of soil stabilizer, CaCO3The adding amount is 0.5-1.5%, the water content is 70%, after the stabilization time is 14 days, the effective arsenic content in the soil is measured by an acid leaching method, and the arsenic concentration is measured by an atomic fluorescence photometer. The stability rate of the prepared composite soil stabilizer reaches 30-45%.
Example 2
And (3) building a test device table, taking 50g of lignocellulose and illite according to the mass ratio of 9:1, and putting the mixture into a ball mill. According to the mass of the metal aluminum: the mass percent of the adsorbing material is 20 percent, and the concentration of the adsorbing material is 0.5mol/LAl to 360mL2(SO4)3To the solution, 40mL of concentrated NaOH solution were added dropwise, while maintaining magnetic stirring, to form Al (OH)3And pouring the suspension into a ball mill, mixing and grinding the suspension with an adsorption material for 10-120 min, and carrying out vacuum freeze drying for 12h by using a freeze dryer to obtain the arsenic-containing soil stabilizer compounded by the modified cellulose and the inorganic powder.
In a laboratory, high-concentration arsenic-containing soil is provided by Yunnan, the arsenic-containing soil is sieved by a 20-mesh sieve, and 100g of the arsenic-containing soil is weighed and put into a basin. The effective arsenic content measured by the acid leaching method is 180 mg/kg. The dosage of the soil stabilizer is 5-10 percent, CaCO3Adding 1% of water, keeping water content 70%, stabilizing for 14 days, measuring effective arsenic content in soil by acid leaching method, and performing atomic fluorescenceThe arsenic concentration is measured by a photometer. The stability rate of the prepared composite soil stabilizer reaches 30-55%.
Example 3
And (3) building a test device table, taking 50g of lignocellulose and illite according to the mass ratio of 9:1, and putting the mixture into a ball mill. According to the total mass of metal iron and cerium: the mass percent of the adsorbing material is 30 percent, and the concentration of the adsorbing material is 0.3-0.9mol/L Ce (NO) to 100mL3)3、0.3-0.9mol/L FeCl3To the solution, 20mL of concentrated NaOH solution were added dropwise, while maintaining magnetic stirring, yielding Fe (OH)3、Ce(OH)3And pouring the suspension into a ball mill, mixing and grinding the suspension with an adsorption material for 10-120 min, and drying the suspension for 12h in a forced air drying oven at 40 ℃ to obtain the arsenic-containing soil stabilizer compounded by the modified cellulose and the inorganic powder.
In a laboratory, high-concentration arsenic-containing soil is provided by Yunnan, the arsenic-containing soil is sieved by a 20-mesh sieve, and 100g of the arsenic-containing soil is weighed and put into a basin. The effective arsenic content measured by the acid leaching method is 180 mg/kg. 2-6% of soil stabilizer, CaCO3The adding amount is 0.5-1.5%, the water content is 70%, after the stabilization time is 14 days, the effective arsenic content in the soil is measured by an acid leaching method, and the arsenic concentration is measured by an atomic fluorescence photometer. The stability rate of the prepared composite soil stabilizer reaches 15-40%.
Example 4
And (3) building a test device table, taking 50g of lignocellulose and illite according to the mass ratio of 9:1, and putting the mixture into a ball mill. According to the total mass of metal iron and cerium: the mass percent of the adsorbing material is 30 percent, and the concentration of the adsorbing material is 0.3-0.9mol/L Ce (NO) to 100mL3)3、0.3-0.9mol/L FeCl3To the solution, 20mL of concentrated NaOH solution were added dropwise, while maintaining magnetic stirring, yielding Fe (OH)3、Ce(OH)3And pouring the suspension into a ball mill, mixing and grinding the suspension with an adsorption material for 10-120 min, and drying the suspension for 12h in a forced air drying oven at 40 ℃ to obtain the arsenic-containing soil stabilizer compounded by the modified cellulose and the inorganic powder.
In a laboratory, high-concentration arsenic-containing soil is provided by Yunnan, the arsenic-containing soil is sieved by a 20-mesh sieve, and 100g of the arsenic-containing soil is weighed and put into a basin. The effective arsenic content measured by the acid leaching method is 180 mg/kg. The dosage of the soil stabilizer is 5-15%, CaCO3The adding amount is 0.5-1.5%, the water content is 70%, after the stabilization time is 14 days, the effective arsenic content in the soil is measured by an acid leaching method, and the arsenic concentration is measured by an atomic fluorescence photometer. The stability rate of the prepared composite soil stabilizer reaches 25-45%.
Example 5
And (3) building a test device table, taking 50g of lignocellulose and illite according to the mass ratio of 9:1, and putting the mixture into a ball mill. According to the total mass of metal cerium and manganese: the mass percent of the adsorbing material is 20 percent, and the concentration of the adsorbing material is 0.3-0.8mol/L Ce (NO) to 100mL3)3、0.2-0.7mol/L KMnO4To the solution, 10mL of concentrated NaOH solution were added dropwise while maintaining magnetic stirring, and the resultant Ce (OH)3And pouring the suspension into a ball mill, mixing and grinding the suspension with an adsorption material for 10-120 min, and drying the suspension for 12h in a forced air drying oven at 40 ℃ to obtain the arsenic-containing soil stabilizer compounded by the modified cellulose and the inorganic powder.
In a laboratory, high-concentration arsenic-containing soil is provided by Yunnan, the arsenic-containing soil is sieved by a 20-mesh sieve, and 100g of the arsenic-containing soil is weighed and put into a basin. The effective arsenic content measured by the acid leaching method is 180 mg/kg. 2-6% of soil stabilizer, CaCO3The adding amount is 0.5-1.5%, the water content is 70%, after the stabilization time is 14 days, the effective arsenic content in the soil is measured by an acid leaching method, and the arsenic concentration is measured by an atomic fluorescence photometer. The stability rate of the prepared composite soil stabilizer reaches 15-40%.
Example 6
And (3) building a test device table, taking 50g of lignocellulose and illite according to the mass ratio of 9:1, and putting the mixture into a ball mill. According to the total mass of metal cerium and manganese: the mass percent of the adsorbing material is 20 percent, and the concentration of the adsorbing material is 0.3-0.8mol/L Ce (NO) to 100mL3)3、0.2-0.7mol/L KMnO4To the solution, 10mL of concentrated NaOH solution were added dropwise while maintaining magnetic stirring, and the resultant Ce (OH)3And pouring the suspension into a ball mill, mixing and grinding the suspension with an adsorption material for 10-120 min, and drying the suspension for 12h in a forced air drying oven at 40 ℃ to obtain the arsenic-containing soil stabilizer compounded by the modified cellulose and the inorganic powder.
In laboratory, high-concentration arsenic-containing soil is provided from Yunnan, and sieved by a 20-mesh sieve, and weighed100g of the mixture is taken and potted. The effective arsenic content measured by the acid leaching method is 180 mg/kg. The dosage of the soil stabilizer is 10 percent, CaCO3The adding amount is 1 percent, the water content is 70 percent, after the stabilization time is 14 days, the effective arsenic content in the soil is measured by an acid leaching method, and the arsenic concentration is measured by an atomic fluorescence photometer. The stability rate of the prepared composite soil stabilizer reaches 20-40%.
Claims (1)
1. The application of the arsenic-containing soil stabilizer in stabilizing arsenic in soil is characterized in that the dosage of the arsenic-containing soil stabilizer is 2-6%, and CaCO3The adding amount is 0.5-1.5%, the water content is 70%, and the stabilizing time is 14 days; the preparation method of the arsenic-containing soil stabilizer comprises the following steps: building a test device table, taking 50g of lignocellulose and illite according to the mass ratio of 9:1 to prepare an adsorption material, and putting the adsorption material into a ball mill; then the solution is added to 360mL of a solution with a concentration of 0.5mol/LAl2(SO4)340mL of concentrated NaOH solution were added dropwise to the solution, while maintaining magnetic stirring, to yield Al (OH)3And pouring the suspension into a ball mill, mixing and grinding the suspension with an adsorbing material for 10-120 min, and carrying out vacuum freeze drying for 12h by using a freeze dryer to obtain the arsenic-containing soil stabilizer.
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| CN111282985A (en) * | 2020-02-20 | 2020-06-16 | 广东省生态环境技术研究所 | Method for treating soil cadmium-arsenic combined pollution by using multifunctional manganese-based material |
| CN111253950A (en) * | 2020-03-26 | 2020-06-09 | 圣清环保股份有限公司 | Modified cellulose passivator and preparation method and application thereof |
| CN111363556A (en) * | 2020-03-26 | 2020-07-03 | 圣清环保股份有限公司 | Iron and cerium modified cellulose soil stabilizer and preparation method and application thereof |
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