CN114749141B - Environment heavy metal pollution repairing agent and preparation method and application thereof - Google Patents

Environment heavy metal pollution repairing agent and preparation method and application thereof Download PDF

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CN114749141B
CN114749141B CN202210526942.8A CN202210526942A CN114749141B CN 114749141 B CN114749141 B CN 114749141B CN 202210526942 A CN202210526942 A CN 202210526942A CN 114749141 B CN114749141 B CN 114749141B
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ball milling
tourmaline
heavy metal
ball
biochar
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CN114749141A (en
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王翠苹
梁亚峰
朱青
高越
甄凯
薛亚楠
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Nankai University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00—In situ
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The application provides a preparation method of an environment heavy metal pollution repairing agent, which comprises the following steps: step one, mixing tourmaline or modified tourmaline with biochar for performing first ball milling treatment to obtain ball milling products; the first ball milling treatment is wet ball milling treatment, and the mass ratio of tourmaline or modified tourmaline to biochar is 1:1-3; and step two, drying the product obtained by the first ball milling treatment to obtain the environment heavy metal pollution repairing agent. The preparation method provided by the application adopts a ball milling treatment process, is simple, and can obtain a ball milling tourmaline-biochar composite material product with better performance, and particularly, after sodium stearate ball milling is adopted to modify tourmaline, the ball milling treatment is carried out with the biochar, so that the repairing agent capable of efficiently repairing heavy metal pollution can be prepared under the conditions of lower ball material ratio and shorter ball milling time, and the problems that the effect of adsorbing heavy metal by a biochar single material in an acidic water body is poor and the adsorption capacity of Cd by using the tourmaline single material in a low dosage are solved.

Description

Environment heavy metal pollution repairing agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of environmental pollution control, and relates to an environmental heavy metal pollution repairing agent, a preparation method and application thereof.
Background
Under the background of rapid development of industrial economy, heavy metal pollution in water and soil environments has become an important environmental problem restricting sustainable development in the fields of agriculture, economy, ecology and the like, and needs to be solved. The half-life of heavy metals is long, the heavy metals are not easy to biodegrade, can remain for a long time after entering soil, are harmful to human health and ecosystem through food chain transmission, and can be converted into an organic metal form through biological methylation to enhance the toxicity of the heavy metals. Meanwhile, the soil with higher heavy metal content can enter the underground water body under the environmental effect, so that the underground water body is polluted. There is a need to develop more efficient remediation technologies for heavy metal pollution characteristics that can be used to control heavy metal pollution in water and/or soil. The in-situ chemical remediation technology is one of research hotspots for heavy metal pollution remediation, has small soil disturbance, low cost and simple operation, can realize high-efficiency removal of heavy metal, and is characterized by selection of a remediation agent.
The existing repairing agents are mainly divided into inorganic and organic two kinds, wherein the inorganic substances mainly comprise phosphates, minerals and the like, the organic substances mainly comprise organic compost, biochar and the like, and although the repairing agents can relieve the pollution of environmental heavy metals, some of the repairing agents have problems in the preparation and use processes: the preparation process of the repairing agent is complicated, and the cost is high; (2) The repairing agent has low use efficiency and may cause secondary pollution; (3) The removal effect of the repairing agent on heavy metals is easily influenced by environmental conditions, for example, when the repairing agent is used in an extremely acidic or alkaline environment, the removal efficiency of the repairing agent on the heavy metals is obviously reduced; (4) The reusability of the restored soil is poor, for example, the restored soil is easy to alkalize and agglomerate, and the recycling of soil resources is difficult to ensure.
The field is urgently required to develop an economic, efficient, green and wide-application-range repairing agent so as to realize the safe use of water and land resources.
Disclosure of Invention
The application aims to provide an environment heavy metal pollution repairing agent and a preparation method and application thereof, so as to at least solve one of the following technical problems of the existing repairing agent: complicated preparation process, high cost, easy influence of environmental conditions on the removal effect, and the like.
In order to achieve the above purpose, the present application adopts the following technical scheme:
in a first aspect, the present application provides a method for preparing an environmental heavy metal pollution remediation agent, including:
step one, mixing tourmaline or modified tourmaline with biochar for performing first ball milling treatment to obtain ball milling products; the first ball milling treatment is wet ball milling treatment, and the mass ratio of the tourmaline to the biochar is 1:1-3 (such as 1:1.2, 1:1.5, 1:2, 1:2.5, 1:2.8, etc.);
and step two, drying the product obtained by the first ball milling treatment to obtain the environment heavy metal pollution repairing agent.
In the preparation method of the environment heavy metal pollution repairing agent, as a preferred embodiment, in the first step, the ball milling medium is ultrapure water, the ball material ratio of the first ball milling treatment is 10-20:1 (such as 12:1, 15:1, 18:1, etc.), the ball milling time is 5-24h (such as 6h, 8h, 10h, 12h, 15h, 18h, 20h, 22h, etc.), and the rotating speed is 1000-1500rmp (such as 1050rmp, 1100rmp, 1200rmp, 1300rmp, 1400rmp, 1450rmp, etc.); more preferably, the ball milling time is 6 to 12 hours. The materials in the ball-material ratio in the application are tourmaline or modified tourmaline and biochar, and ball milling media such as water are not included.
Further preferably, the material to water ratio (m: v) in the first ball milling process is 1g:2mL-1g:5mL (e.g., 1g:2.5mL, 1g:3mL, 1g:4mL, 1g:4.5mL, etc.). The material water ratio is the ratio of the total mass of tourmaline and biochar to the volume of ultrapure water.
In the preparation method of the repairing agent for environmental heavy metal pollution, as a preferred embodiment, in the first step, the mass ratio of the tourmaline to the biochar is 1:3, the ball-material ratio of the first ball milling treatment is 20:1, and the ball milling time is 1-24h (such as 2h, 3h, 6h, 12h, 15h, 18h, 20h, 22h, etc.).
In the above method for preparing the repairing agent for environmental heavy metal pollution, as a preferred embodiment, in the first step, the particle size of the tourmaline or modified tourmaline is less than 50 μm (for example, it is sieved with 320 mesh).
In the above method for preparing the repairing agent for environmental heavy metal pollution, in the first step, the particle size of the biochar is less than 75 μm (for example, by passing through a 200 mesh sieve), and the biochar may be a commercially available product or may be self-made.
In the above method for preparing the agent for repairing environmental heavy metal pollution, as a preferred embodiment, in the second step, the drying treatment is performed at a temperature of 50-60 ℃ (e.g. 52 ℃, 55 ℃, 58 ℃ and the like) for 8-12 hours (e.g. 9 hours, 10 hours, 11 hours and the like).
In the preparation method of the environment heavy metal pollution repairing agent, as a preferred embodiment, in the first step, the modified tourmaline is sodium stearate modified tourmaline prepared by performing a second ball milling treatment on sodium stearate and tourmaline; more preferably, the mass ratio of tourmaline to sodium stearate is 80:1-120:1 (such as 85:1, 90:1, 95:1, 100:1, 105:1, 110:1, 115:1, etc.). Experiments prove that the dispersibility of tourmaline can be improved by introducing sodium stearate, and the adsorption capacity of heavy metal cations is promoted by introducing stearate on the surface of the tourmaline.
In the preparation method of the repairing agent for environmental heavy metal pollution, as a preferred embodiment, the ball-material ratio of the second ball-milling treatment is 3:1-5:1 (such as 3.5:1, 4:1, 4.5:1, etc.), the ball-milling time is 30-90min (such as 40min, 50min, 60min, 70min, 80min, 90min, etc.), and the rotation speed is 1000-1500rpm (such as 1050rmp, 1100rmp, 1200rmp, 1300rmp, 1400rmp, 1450rmp, etc.).
In the above method for preparing an environmental heavy metal pollution repairing agent, as a preferred embodiment, in the first step, the second ball milling treatment is wet ball milling treatment, the ball milling medium is water, and preferably the material water ratio (m: v) is 1g:2ml-1g:4ml (e.g. 1g:2.5ml, 1g:3ml, 1g:3.5ml, etc.).
In the above method for preparing an environmental heavy metal pollution repairing agent, as a preferred embodiment, in the first step, the mass ratio of the sodium stearate modified tourmaline to the biochar is 1:1-3 (for example, 1:1.2, 1:1.5, 1:2, 1:2.5, 1:2.8, etc.).
In the above method for preparing the repairing agent for environmental heavy metal pollution, as a preferred embodiment, in the first step, the first ball milling treatment is wet ball milling treatment, the ball milling medium is ultrapure water, preferably the ratio of feed water (m: v) is 1g to 2ml-1g to 5ml, and the ratio of feed water is the ratio of total mass of sodium stearate modified tourmaline to biochar to the volume of ultrapure water.
In the preparation method of the environmental heavy metal pollution repairing agent, as a preferred embodiment, in the first step, the ball-material ratio of the first ball milling treatment is 10-20:1 (such as 12:1, 15:1, 18:1, etc.), and the ball milling time is 5-24h (such as 2h, 3h, 6h, 12h, 15h, 18h, 20h, 22h, etc.); preferably, the ball milling time of the first ball milling treatment is 6-12 hours.
In the preparation method of the environmental heavy metal pollution repairing agent, as a preferred embodiment, in the first step, the mass ratio of the modified tourmaline to the biochar is 1:3, the ball-material ratio of the first ball milling treatment is 10-20:1, and the ball milling time is 1-24 hours (such as 2 hours, 3 hours, 6 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, etc.); preferably, the ball milling time of the first ball milling treatment is 3-6 hours.
In a second aspect, the application also provides an environmental heavy metal pollution remediation agent, which is prepared by adopting the method.
In a third aspect, the application further provides an application of the environmental heavy metal pollution remediation agent in water/soil heavy metal pollution remediation, which comprises the following steps: and carrying out in-situ chemical treatment on the heavy metal polluted water or soil by using the environmental heavy metal pollution restoration agent.
Preferably, if the heavy metal polluted water is treated, the ph=4-8 of the heavy metal polluted water, the mass ratio of the sodium stearate modified tourmaline to the biochar in the repairing agent is 1:3, the using amount of the repairing agent is 1-8g/L (such as 1.5g/L, 2g/L, 4g/L, 6g/L, 7g/L, 7.5g/L, etc.), the treatment time is 480-2880min (such as 540min, 720min, 960min, 1200min, 1440min, 1800min, 2400min, etc.), and the treatment temperature is 15-35 ℃ (such as 18 ℃, 20 ℃, 25 ℃, 30 ℃, 32 ℃ etc.); preferably, the treatment time is 700-1450min.
Preferably, if the heavy metal contaminated soil is treated, the mass ratio of the sodium stearate modified tourmaline to the biochar in the repairing agent is 1:3, the dosage ratio of the repairing agent to the soil is 20-100g/kg (such as 25g/kg, 30g/kg, 40g/kg, 50g/kg, 60g/kg, 70g/kg, 80g/kg, 90g/kg, etc.), water is poured during the treatment process to keep the moisture of the soil at 60% of the maximum field water holding capacity (such as adding 60mL of water to 400g of soil, namely, the water-soil ratio is 3:20), and the treatment time is 30 days.
Tourmaline is a cyclic borosilicate mineral material with wide distribution, has five characteristics of infrared radiation characteristic, anion release characteristic, natural electric polarity, piezoelectricity and pyroelectric property, and spontaneous and permanent electrodes can automatically adjust the pH value of a solution, so that the environment of strong acid or strong alkali finally tends to be neutral, and the removal effect of heavy metal ions is hardly influenced by the acidity and alkalinity of an environment medium. However, tourmaline per unit mass has low efficiency in removing heavy metals. The biochar is a material obtained by carrying out high-temperature pyrolysis on biomass under anaerobic or oxygen-limited conditions, has the characteristics of stability, high aromaticity, large specific surface area, rich surface oxygen-containing functional groups and the like, can be used for efficiently removing heavy metals in neutral environments, and has the removal efficiency easily influenced by the environmental acid-base conditions. The scheme of the application combines the advantages of the two, and further improvement of efficiency is realized.
Compared with the prior art, the beneficial effects of the application include, but are not limited to:
1) The preparation method of the repairing agent adopts a ball milling treatment process, is simple, and has better performance of the ball milling tourmaline-biochar composite material product, and has better heavy metal adsorption effect compared with the non-ball milling tourmaline-biochar composite material (synthesized by magnetic stirring); in particular, after the tourmaline is modified by sodium stearate ball milling, the modified tourmaline is subjected to ball milling treatment with biochar, so that the repairing agent capable of efficiently repairing heavy metal pollution can be prepared under the conditions of lower ball-to-material ratio and shorter ball milling time.
2) The method can solve the problems that the biochar single material has poor effect of absorbing heavy metals in acidic water (such as pH=4, 5) and the tourmaline single material has low absorption capacity to Cd when being used in low dosage, and firstly develops the ball-milling sodium stearate modified tourmaline-biochar composite material.
3) The ball-milling sodium stearate modified tourmaline-biochar composite material provided by the application is used for heavy metal adsorption treatment of groundwater in an Ningxia industrial park and heavy metal restoration treatment in soil of Ningxia and Nanjing sites, and the ball-milling sodium stearate modified tourmaline-biochar composite material can achieve the purpose of high-efficiency restoration of heavy metal pollution (including Cd, cu, pb and the like) through analysis, and has important scientific research value and practical application significance. The ball-milling sodium stearate modified tourmaline-biochar composite material provided by the application has higher adsorption rates for Cd, cu and Pb in groundwater in Ningxia industrial park, and particularly for Cd and Pb in groundwater, the adsorption rates can reach more than 93%; the effective state content of heavy metal in the soil of Ningxia and Nanjing sites can be reduced by 13.1%, and the residue state content can be increased by 21.5%.
Drawings
Fig. 1 is an SEM image of a ball-milled sodium stearate modified tourmaline-biochar composite material. Wherein (a), (b), (c), (d), (e) and (f) are tourmaline, ball-milled sodium stearate modified tourmaline, biochar, ball-milled biochar, non-ball-milled fine tourmaline-biochar composite material (NBM-UTBC) 1/3-1h ) Ball-milling sodium stearate modified tourmaline-biochar composite material (BM-STBC) 10-1/3-6h ) SEM images of (a).
FIG. 2 is a comparison of the adsorption performance of tourmaline and biochar on heavy metals of different composite materials. Wherein (a), (b), (c) and (d) are respectively synthesized non-ball-milled tourmaline-biochar composite material, ball-milled tourmaline-biochar composite material and non-ball-milled hard under different parameter conditionsAnd comparing the performance of the sodium stearate modified tourmaline-biochar composite material and the ball-milled sodium stearate modified tourmaline-biochar composite material for absorbing heavy metals. The adsorption conditions are as follows: [ Cd ] 2+ ]=50mg/L, ph=6, [ adsorbent ]]=1 g/L, adsorption time=24 h, adsorption temperature=25 ℃;
fig. 3 is a graph of optimization of parameters of technical conditions of ball milling sodium stearate modified tourmaline-biochar composite material for adsorbing heavy metals in water: (a) is adsorption time; (b) is the dose of adsorbent; (c) is temperature; (d) is pH; (e) Concentration of heavy metal (experimental conditions are [ Cd ] 2+ ]=50mg/L, ph=6, [ adsorbent ]]=1 g/L, adsorption time=24 h, adsorption temperature=25 ℃, when optimizing a certain parameter, only the value of this parameter is changed and the other parameters are kept fixed).
FIG. 4 is a FTIR chart showing the condition of [ Cd ] before and after heavy metal adsorption by ball milling of sodium stearate modified tourmaline-biochar composite material 2+ ]=50mg/L, [ adsorbent ]]=1 g/L, reaction time=24 h, adsorption temperature=25 ℃, ph=4.0, 6.0, 8.0.
In fig. 5, (a) is an SEM image of ball-milled sodium stearate modified tourmaline-biochar composite material before heavy metal adsorption; (b) SEM images after heavy metals are adsorbed in a solution with pH=6 of the ball-milling sodium stearate modified tourmaline-biochar composite material; (c) Under different initial pH conditions, the pH change of the solution after the ball-milling sodium stearate modified tourmaline-biochar composite material absorbs heavy metal and is balanced (the experimental condition is [ Cd ] 2+ ]=50mg/L, [ adsorbent ]]=1 g/L, adsorption time=24 h, reaction temperature=25 ℃, ph=2, 3, 4,5, 6, 7, 8).
FIG. 6 shows the Zeta potential of ball-milled sodium stearate modified tourmaline-biochar composite materials in aqueous solution under different initial pH conditions.
FIG. 7 shows the application of ball-milling sodium stearate modified tourmaline-biochar composite material in heavy metal adsorption in underground water of Ningxia industrial park, (a) is the background value of heavy metal in underground water of Ningxia industrial park; (b) The adsorption rate of heavy metals is improved when ball-milling sodium stearate is added into the tourmaline-biochar composite material at the dosage of 1 g/L.
Fig. 8 shows the application of ball-milling sodium stearate modified tourmaline-biochar composite material in repairing heavy metal pollution in field soil, (a) the background value distribution of Cd in certain industrial parks (field soil 1 and field soil 2) of Ningxia back autonomous region and certain chemical enterprises production fields (field soil 3 and field soil 4) of Nanjing city of Jiangsu province; (b) The repairing effect of ball milling sodium stearate modified tourmaline-biochar composite material on Cd in the field soil is achieved at different doses, and the repairing time is 30d; (c) The impact of ball milling sodium stearate modified tourmaline-biochar composite materials on the pH value of the field soil under different doses is realized. CK, 20 and 100 in the graph represent the dosages of the ball-milled sodium stearate modified tourmaline-biochar composite material of 0, 20 and 100g/kg respectively.
Fig. 9 shows the effect of the ball-milled sodium stearate modified tourmaline-biochar composite material on the partial physicochemical properties of the field soil 1 and the field soil 2 in the Ningxia industrial park, (a), (b), (c), (d), (e) and (f) are the effect of the ball-milled sodium stearate modified tourmaline-biochar composite material on the cation concentration, cation exchange capacity and organic matter concentration in the field soil 1 and the field soil 2, respectively, wherein different lower case letters in the figure represent the significant level of difference between different treatments, and p <0.05.
Detailed Description
The following examples facilitate a better understanding of the present application, but are not intended to limit the present application.
The experimental methods in the following examples are conventional methods unless otherwise specified.
Other test materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
In the following examples, the original tourmaline is a commercial product, namely, the iron tourmaline purchased from Hebei's life mineral powder factory, the particle size is 320 mesh sieve, and the code is T; the fine tourmaline is obtained by ball milling original tourmaline which is sieved by a 320-mesh sieve at 60 ℃ until the weight is constant, wherein the ball-milling time is 3h and the rotating speed is 1200rpm, and the raw tourmaline is sieved by the 320-mesh sieve and the code number is UT; the biochar is a commercial product, and is rice straw biochar (obtained by pyrolysis at 500 ℃) purchased from Henan Lize environmental protection technology company, and is sieved by a 200-mesh sieve, and the code number is BC; the sodium stearate is a commercial product and is purchased from Tianjin Xingjing complex fine chemical engineering institute, and the code number is S.
Example 1 preparation example
Preparation of sodium stearate modified tourmaline:
(1) The preparation method of the unground sodium stearate modified tourmaline (NBM-ST, NBM-SUT) comprises the following steps: 3g of original tourmaline or fine tourmaline, 0.039g of sodium stearate and 150mL of ultrapure water are sequentially added into a 500mL beaker, the mixture is stirred for 60min at 80 ℃ by a magnetic stirrer at the speed of 300rpm, the suspension is centrifuged and washed for three times to remove unreacted sodium stearate, then the suspension is dried to constant weight at 60 ℃, ground and sieved by a 320-mesh sieve, and the product codes of NBM-ST and NBM-SUT are respectively stored in a drier for standby in a dark place.
(2) The preparation method of ball-milling sodium stearate modified tourmaline (BM-ST) comprises the following steps: accurately weighing a certain amount of original tourmaline, ball milling for 1h under the conditions that the dosage of sodium stearate is 1% of the tourmaline mass, the material water ratio (m: v) is 2:5, the rotating speed is 1200rpm, the ball material ratio is 4, drying to constant weight at 60 ℃, grinding, sieving with 320 mesh sieve, and storing in a dryer in a dark place for standby, wherein the product code is BM-ST.
(II) preparation of tourmaline-biochar composite materials:
(1) The preparation method of the non-ball-milled tourmaline-biochar composite material (NBM-TBC and NBM-UTBC) comprises the following steps: a proper amount of biochar and ultrapure water were added to a 500mL beaker at a ratio of 1g:30mL (m: v), and stirred at 60℃for 15 minutes using a magnetic stirrer at a rotation speed of 200rpm, so that the biochar was uniformly dispersed in the aqueous solution. The original tourmaline/fine tourmaline with the mass ratio of 1:0.3-3 (such as 3:1, 1:1, 1:3, etc.) with biochar is uniformly dispersed in the aqueous solution according to the same method. Then, the original tourmaline/micro tourmaline suspension is slowly added into the biochar aqueous solution, and magnetically stirred at a rotation speed of 300rpm for 0.5-12h (e.g., 0.5h, 1h, 3h, 6h, 12h, etc.). After the reaction is finished, the suspension is centrifuged and washed for three times, and then dried to constant weight at 60 ℃ and ground, thus obtaining the non-ball-milled tourmaline-biochar (code NBM-TBC) composite material and the non-ball-milled superfine tourmaline-biochar composite material (code NBM-UTBC) respectively.
(2) The preparation method of the non-ball-milled sodium stearate modified tourmaline-biochar composite material (NBM-STBC, NBM-SUTBC) comprises the following steps: the method comprises the steps of respectively preparing a non-ball-milled sodium stearate modified tourmaline-biochar composite material (with the code of NBM-STBC) and a non-ball-milled sodium stearate modified micro tourmaline-biochar composite material (with the code of NBM-SUTBC) by using sodium stearate modified tourmaline/micro tourmaline and biochar through magnetic stirring treatment; the specific operation method refers to the preparation of the unground tourmaline-biochar composite material (namely the part (1) above).
(3) The preparation method of the ball milling tourmaline-biological carbon composite material (BM-TBC) comprises the following steps: firstly, weighing a certain amount of zirconia grinding balls with different particle sizes into a zirconia ball milling tank according to the ball material ratio of 10 and 20 (phi 8mm:5mm:3 mm=2:5:3), then weighing 10 percent and 20 percent of the zirconia grinding balls according to the mass ratio of 1:0.3-3 (such as 3:1, 1:1 and 1:3) of tourmaline and biochar, adding into the ball milling tank, fully mixing, and adding a certain amount of ultrapure water into the ball milling tank according to the material water ratio (m: v) of 1g:2 mL. After all the components required are added, the ball milling pot is sealed and placed in a ball mill, the rotating speed is set to 1200rpm, and the ball milling time is 1-24 hours (such as 1 hour, 3 hours, 6 hours, 12 hours and 24 hours). After ball milling, the prepared material is dried to constant weight at 50-60 ℃ and ground and sieved, and the product code is BM-TBC.
(4) The preparation method of ball-milling sodium stearate modified tourmaline-biochar composite material (BM-STBC) comprises the following steps: referring to the preparation method of the ball milling tourmaline-biochar composite material (namely the part (3) above), the product code number is BM-STBC.
The raw materials used in this example and the names, codes and process summaries of the composite materials produced are shown in Table 1.
Figure BDA0003644749600000091
(III) characterization of materials:
the surface topography of the samples was analyzed using a Scanning Electron Microscope (SEM) (model: SU3500, japan).
In FIG. 1, a, b, c, d, e and f are tourmaline, ball-milled sodium stearate modified tourmaline, biochar, ball-milled biochar, non-ball-milled fine tourmaline-biochar composite material (NBM-UTBC) 1/3-1h Namely UT: BC=1:3, magnetic stirring for 1h, and ball milling sodium stearate modified tourmaline-biochar composite material (BM-STBC) 10-1/3-6h I.e. ST: bc=1:3, ball to charge ratio 10, ball milling 6 h). A, b, c and d in fig. 1 show that the ball milling process can significantly reduce the particle size of the tourmaline and biochar single material, and sodium stearate is irregularly loaded on the surface of the tourmaline. In fig. 1 e and f show that the tourmaline and biochar in the non-ball-milled composite material are more physically doped, the two still keep their own shapes, while SEM images of the ball-milled sodium stearate modified tourmaline-biochar composite material show that most of the sodium stearate modified tourmaline still keeps the original structure, but the surface of the sodium stearate modified tourmaline is already loaded with the biochar, and the particle size of the ball-milled composite material is obviously lower than that of the non-ball-milled composite material.
(IV) tourmaline-biochar composite material performance screening
The various composites prepared in this example were added to a concentration of 50mg/L Cd at a pH of 6 at a dose of 1g/L 2+ And (3) uniformly mixing the solutions, performing constant-temperature vibration adsorption at 25 ℃ for 48 hours, filtering, and determining the concentration of heavy metals in the filtrate. According to different composite materials, cd in aqueous solution 2+ The adsorption rate of the composite material is evaluated to evaluate the modification effect of the composite material, and the higher the adsorption rate of the material to heavy metal is, the better the performance of the material is.
A in fig. 2 shows NBM-UTBC obtained when the mass ratio of the fine tourmaline to the biochar is 1:3 and the magnetic stirring synthesis time is 1h 1/3-1h For Cd 2+ The highest adsorption rate of (2) was 75.78%. B in FIG. 2 shows BM-TBC obtained when tourmaline and biochar are mixed at a mass ratio of 1:3, a ball material ratio of 10 and a ball milling time of 12 hours 10-1/3-12h For Cd 2+ The highest adsorption rate of (2) was 97.10%. FIG. 2 c shows that when stearic acidNBM-SUTBC obtained by magnetically stirring sodium modified micro tourmaline and biochar at mass ratio of 1:3 for 1h 1/3-1h For Cd 2+ The highest adsorption rate of (2) was 66.01%. D in FIG. 2 shows BM-STBC obtained when sodium stearate modified tourmaline and biochar are mixed in the conditions of a mass ratio of 1:3, a ball-to-material ratio of 10 and a ball milling time of 6 hours 10-1/3-6h For Cd 2+ The adsorption rate of (C) was 97.26% higher than that of the non-ball-milled material (NBM-STBC) 1/3-6h ) For Cd 2+ The adsorption rate of the material is higher by more than 2 times, is nearly 4 times higher than that of a ball-milling tourmaline single material, and can realize the optimal adsorption in a shorter time and at a lower ball-material ratio compared with the ball-milling tourmaline-biochar composite material, thus being a material with optimal performance.
Example 2 Effect example-Water remediation
The ball-milled sodium stearate modified tourmaline-biochar composite material used in the embodiment is a composite material BM-STBC obtained under the conditions of a mass ratio of 1:3, a ball-material ratio of 10 and a ball-milling time of 6 hours of sodium stearate modified tourmaline and biochar 10-1/3-6h . Detecting the performance of ball-milling sodium stearate modified tourmaline-biochar composite material in absorbing heavy metals in water, and selecting cadmium (Cd) as a representative for carrying out.
Ball milling sodium stearate modified tourmaline-biochar composite material is used for adsorbing heavy metals in water body:
(1) Adsorption time: the dosage of the ball-milling sodium stearate modified tourmaline-biochar composite material is 1g/L, and Cd is the same as that of the ball-milling sodium stearate modified tourmaline-biochar composite material 2+ The initial concentration was 50mg/L, pH 6, adsorption temperature was 25℃and adsorption was carried out by shaking at 180rpm, and sampling was carried out as adsorption was carried out for 5, 15, 30, 60, 120, 240, 360, 480, 720, 960, 1200, 1440 and 2880min, respectively. The content of the target pollutant in the sample was measured by using a continuous light source atomic absorption spectrometer, and the result is shown in fig. 3 (a).
(2) Ball milling sodium stearate modified tourmaline-biochar composite material dosage: the dosage of the ball-milling sodium stearate modified tourmaline-biochar composite material is respectively 0.5, 1, 2, 4 and 8g/L, and Cd 2+ The initial concentration was 50mg/L,the sample was taken after adsorption at pH 6 at 25℃and 180rpm for 24 hours, and the results are shown in FIG. 3 (b).
(3) Adsorption temperature: the dosage of the ball-milling sodium stearate modified tourmaline-biochar composite material is 1g/L, and Cd is the same as that of the ball-milling sodium stearate modified tourmaline-biochar composite material 2+ The initial concentration was 50mg/L, the pH was 6, and the sample was taken after adsorption was carried out by shaking at 180rpm for 24 hours at adsorption temperatures of 15, 25 and 35℃respectively, and the results were shown in FIG. 3 (c).
(4) Reaction system pH: adding ball-milled sodium stearate modified tourmaline-biochar composite material into Cd with initial concentration of 50mg/L and pH of 2, 3, 4,5, 6, 7 and 8 respectively at a dosage of 1g/L 2+ In the solution, the sample was taken after adsorption at 25℃for 24 hours with shaking at 180rpm, and the results are shown in FIG. 3 (d).
(5) Concentration of contaminants: the dosage of ball-milling sodium stearate modified tourmaline-biochar composite material is set to be 1g/L, and the pH value is 6, cd 2+ The initial concentrations were 25, 50, 100, 150, 200, 250, 300, 350 and 400mg/L, respectively, and the sample was sampled and tested after adsorption at 25℃with shaking at 180rpm, as shown in FIG. 3 (e).
Fig. 3 shows the influence of various technical parameters on the effect of ball milling sodium stearate modified tourmaline-biochar composite material on heavy metal adsorption in water. Finally, the adsorption equilibrium time is determined to be 24 hours, the optimal dosage of the ball-milling sodium stearate modified tourmaline-biochar composite material is 1g/L, the optimal adsorption temperature is 25 ℃, the pH is 4-8, and the Cd is obtained 2+ Can realize high-efficiency removal in the concentration range of 25-400 mg/L. When the dosage of the ball-milling sodium stearate modified tourmaline-biochar composite material is 1g/L, the adsorption time is 24 hours, the adsorption temperature is 25 ℃, the pH is 6, and the Cd is 2+ When the initial concentration of (2) is 50mg/L, ball milling the Cd of the sodium stearate modified tourmaline-biochar composite material 2+ The adsorption rate of the catalyst can reach 98.08 percent, and the equilibrium adsorption capacity can reach 49.04mg/L.
(II) ball milling a way of absorbing heavy metals by the sodium stearate modified tourmaline-biochar composite material:
in this example, the concentration of cations and pH in the solution before and after adsorption were measured by ball millingSodium stearate modified tourmaline-biochar composite material BM-STBC 10-1/3-6h The surface functional group of (2) is changed and the Zeta potential of (3) is used for exploring the heavy metal adsorption mechanism of the water body.
(1) Cation exchange: ball-milling sodium stearate modified tourmaline-biochar composite material for adsorbing Cd 2+ In the course of (a) a large amount of Na is released + (429.40 mg/L) accompanied by a small amount of K + (0.19 Mg/L) and Mg 2+ (0.24 mg/L), which shows that heavy metal cations in the water body can be removed by exchanging with metal cations on the surface of the ball-milled sodium stearate modified tourmaline-biochar composite material.
(2) Complexing functional groups: ball-milling sodium stearate modified tourmaline-biochar composite material for adsorbing Cd under different pH conditions 2+ After that, the surface of the product had-OH (3425 cm -1 )、C＝O(1635cm -1 )、-CH 2 (711cm -1 ) Characteristic peaks of (2) and characteristic peaks of sodium stearate (2920 cm -1 ) The intensity of (c) is significantly changed and also partially shifted (see fig. 4). In addition, the surface functional group of the ball-milling sodium stearate modified tourmaline-biochar composite material is 1442 cm-783 cm -1 The abundance of (C) is obviously changed, which indicates that Cd is absorbed in the process 2+ Enters the inside of the structure of the ball-milling sodium stearate modified tourmaline-biochar composite material and is combined with the functional group.
(3) Hydroxide precipitation: compared with the SEM image of the original ball-milled sodium stearate modified tourmaline-biochar composite material, see (a) in FIG. 5, the Cd is adsorbed 2+ The surface of the ball-milled sodium stearate modified tourmaline-biochar composite material is provided with more newly formed small round particles, see (b) in fig. 5, which probably is that heavy metals form precipitates on the surface of the ball-milled sodium stearate modified tourmaline-biochar composite material. According to Cd 2+ K of (2) sp Calculate at the initial Cd 2+ Cd was brought to a concentration of 50mg/L 2+ The maximum pH at which precipitation occurs is 8.8. FIG. 5 (c) shows the adsorption of Cd by the ball-milled sodium stearate modified tourmaline-biochar composite material in solutions of different initial pH values 2+ The pH was measured after equilibrium was reached. When the initial pH of the solution is more than or equal to 6, the pH after the reaction is alreadyAbove 8.8, this indicates that Cd can appear during adsorption when the initial pH of the solution is greater than or equal to 6 2+ Is a hydroxide precipitate of (a). The product can adjust the pH of the solution, convert the acidic solution into neutral or weak alkaline solution, and the adjusted pH is favorable for converting heavy metals into stable forms, such as generating a precipitation form.
(4) Electrostatic adsorption: zeta potential measurement is carried out on the ball-milled sodium stearate modified tourmaline-biochar composite material, and the result shows that the pH value of the isoelectric point is shown zpc =3.38 (see fig. 6). Thus, when the initial pH of the solution>And 3.38, the surface of the ball-milling sodium stearate modified tourmaline-biochar composite material is electronegative, and heavy metal cations in the solution can be removed through electrostatic adsorption.
EXAMPLE 3 application example-adsorption of heavy metals in Industrial park groundwater
(1) And (3) measuring background values of heavy metals in underground water of an industrial park: groundwater used in the experiment of this example was collected from an industrial park in Ningxia-Hui municipality, and its heavy metal background value was measured by ICP-MS, as shown in FIG. 7 (a).
(2) Heavy metal adsorption of underground water in industrial park: ball-milling sodium stearate modified tourmaline-biochar composite material BM-STBC is added into the underground water of the industrial park at the dosage of 1g/L 10-1/3-6h After adsorption for 24 hours at 25℃with shaking at 180rpm, the suspension was filtered and the concentration of heavy metals in the filtrate was determined by ICP-MS.
The background values of the heavy metals Cd, cu and Pb contained in the groundwater of the Ningxia industrial park are shown in fig. 7 (a). According to GB/T14848-2017, the content of Cd exceeds the water standard of the second class. Fig. 7 (b) shows the adsorption effect of the ball-milled sodium stearate modified tourmaline-biochar composite material on groundwater heavy metals in the Ningxia industrial park. After the adsorption is finished, the removal rate of Cd and Pb in the underground water is high (both are more than 93 percent), and then Cu is the second. Meanwhile, the pH of the groundwater after adsorption is increased by 0.46 unit and is 7.90, which indicates that the BM-STBC composite material is added 10-1/3-6h Is favorable for stabilizing the heavy metal form, and prevents the reduction of the environmental pH value so as to lead part of the heavy metal which has generated precipitation to recover the dissolutionAnd (5) solving the state.
EXAMPLE 4 application example-construction of heavy metal contaminated site soil remediation System
(1) And (3) measuring the background value of the heavy metal in the field soil: the soil used in the experiment of this example was collected from some industrial park (field soil 1 and field soil 2) of Ningxia Hui autonomous region and some chemical industry production field (field soil 3 and field soil 4) of Nanjing city, jiangsu province, and the above-mentioned field pollution was mainly heavy metal pollution according to the investigation result. Naturally air-drying the soil, sieving with a 2mm sieve, removing impurities, and placing in a shade place for standby. The method for measuring the concentration of heavy metals in soil comprises the following steps: the air-dried soil sample is screened by a 100-mesh sieve, 0.10g of sample is accurately weighed into a polytetrafluoroethylene digestion tank, and 6mL of HNO is added 3 And 2mL of HF, uniformly mixing, standing for 10min to finish the primary reaction, uniformly mixing, adding a cover for sealing, digesting, and measuring the concentration of heavy metals in the digested soil by ICP-MS. The results are shown in fig. 8 (a).
(2) Ball-milling sodium stearate modified tourmaline-biochar composite material BM-STBC 10-1/3-6h Repairing heavy metal contaminated site soil: the ball-milled sodium stearate modified tourmaline-biochar composite material was applied to the site soil at dosages corresponding to 0, 2% and 10% of the site soil mass, i.e., dosages of 0g/kg, 20g/kg and 100g/kg, for 30 days (d) of repair, and distilled water was watered for a period of time by weighing to maintain the water content of the site soil at 60% of the maximum water holding capacity of the field. Meanwhile, the pH of the soil of four sites before and after restoration is measured.
(3) Ball-milling sodium stearate modified tourmaline-biochar composite material BM-STBC 10-1/3-6h Influence on physicochemical properties of soil in a heavy metal contaminated site: and measuring the metal cation concentration, cation exchange capacity and organic matter concentration in the field soil 1 and the field soil 2 before and after restoration.
As shown in fig. 8 (a), according to GB 15618-2018, the Cd content in the field soil 1 exceeds the risk control value, and the Cd content in the field soil 2 exceeds the risk screening value. According to GB36600-2018, cd content in Nanjing site soil 3 and site soil 4 exceeds the risk screening value of the first type of site.
As shown in (b) of FIG. 8, when the ball-milled sodium stearate modified tourmaline-biochar composite material is applied at a dosage of 20g/kg, the effective state content of Cd in the soil of the hair site can be reduced by 6.73% at the highest, and the residue state content can be increased by 5.95-9.35%. When the ball-milling sodium stearate modified tourmaline-biochar composite material is applied at the dosage of 100g/kg, the effective state content of Cd in the field soil can be reduced by 13.1 percent, and the residue state content can be increased by 13.5 to 21.5 percent. In addition, the pH of the site soil after restoration increases by 0.05 to 0.35 units (see c in fig. 8).
Ball milling of the sodium stearate modified tourmaline-biochar composite material can increase the metal cation concentration in Ningxia field soil 1 (see (a) in fig. 9) and field soil 2 (see (b) in fig. 9), which are positively correlated. Dosage and K of ball-milling sodium stearate modified tourmaline-biochar composite material in field soil 1 + 、Na + The correlation coefficient r of the concentration of total cations is 0.958,0.771 and 0.924 respectively, and the dosage and K of the ball-milling sodium stearate modified tourmaline-biochar composite material in the field soil 2 are as follows + 、Na + 、Mg 2+ The correlation coefficient r with the total cation concentration was 0.710,0.974,0.989 and 0.903, respectively. After the material is added, the concentration of metal cations is increased, which indicates that cations in the material are exchanged with heavy metal cations in soil and released into the soil, thereby being beneficial to repair.
The ball milling of the sodium stearate modified tourmaline-biochar composite material can increase cation exchange amount in Ningxia field soil 1 and field soil 2, wherein the cation exchange amount in the field soil 1 is increased by 0.18-0.59 cmol/kg, see (c) in fig. 9, the cation exchange amount in the field soil 2 is increased by 0.82-0.91 cmol/kg, see (d) in fig. 9, and the increase of the cation exchange amount can promote the material to remove heavy metal cations in the soil through cation exchange.
The ball-milling sodium stearate modified tourmaline-biochar composite material can increase the organic matter content in Ningxia field soil 1 and field soil 2. Specifically, the organic matter content in the field soil 1 is obviously increased by 1.24-8.35 g/kg, see (e) in fig. 9, the organic matter content in the field soil 2 is obviously increased by 1.93-8.51 g/kg, see (f) in fig. 9, and the increase of the organic matter concentration can promote the heavy metal to be converted into a stable form through organic complexation.
Finally, it is also noted that in this application the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
While the application has been disclosed in the context of specific embodiments thereof, it will be appreciated that those skilled in the art may devise various modifications, adaptations, or equivalents of the application within the spirit and scope of the appended claims. Such modifications, improvements, or equivalents are intended to be included within the scope of the present application.

Claims (13)

1. The preparation method of the environment heavy metal pollution repairing agent is characterized by comprising the following steps of:
step one, mixing tourmaline or modified tourmaline with biochar for performing first ball milling treatment to obtain ball milling products; the first ball milling treatment is wet ball milling treatment, the ball-material ratio of the first ball milling treatment is 10-20:1, the ball milling time is 5-24h, and the rotating speed is 1000-1500 rmp; the mass ratio of the tourmaline or the modified tourmaline to the biochar is 1:1-3; the modified tourmaline is sodium stearate modified tourmaline prepared from sodium stearate and tourmaline through a second ball milling treatment, wherein the mass ratio of the tourmaline to the sodium stearate is 80:1-120:1, the ball-material ratio of the second ball milling treatment is 3:1-5:1, the ball milling time is 30-90min, and the rotating speed is 1000-1500rpm;
and step two, drying the product obtained by the first ball milling treatment to obtain the environment heavy metal pollution repairing agent.
2. The method according to claim 1, wherein in the first ball milling step, the ball milling time of the first ball milling treatment is 6 to 12h.
3. The method according to claim 1, wherein in the first step, the ball milling medium for the first ball milling treatment is ultrapure water, and the material-water ratio is 1 g/2 ml-1 g/5 ml.
4. The preparation method according to claim 1, wherein in the first step, the mass ratio of the tourmaline to the biochar is 1:3, the ball-to-material ratio of the first ball milling treatment is 20:1, and the ball milling time is 5-24 hours.
5. The method according to claim 1, wherein in the first step, the particle size of the tourmaline or modified tourmaline is 50 μm or less and the particle size of the biochar is 75 μm or less.
6. The method according to any one of claims 2 to 5, wherein in the second step, the drying treatment is performed at a temperature of 50 to 60 ℃ for a time of 8 to 12h.
7. The method according to claim 1, wherein in the first step, the second ball milling process is a wet ball milling process, and the ball milling medium is water.
8. The method according to claim 7, wherein in the first step, the water ratio of the material subjected to the second ball milling is 1g:2ml to 1g:4ml.
9. An environmental heavy metal pollution remediation agent prepared by the method of any one of claims 1-8.
10. An application of an environmental heavy metal pollution remediation agent in water/soil heavy metal pollution treatment comprises the following steps: in situ chemical treatment of heavy metal contaminated water or soil with the environmental heavy metal pollution remediation agent of claim 9.
11. The application of the environment heavy metal pollution remediation agent in the aspect of water/soil heavy metal pollution treatment according to claim 10, wherein the heavy metal pollution water is treated, the pH value of the heavy metal pollution water is=4-8, the mass ratio of the sodium stearate modified tourmaline to the biochar in the remediation agent is 1:3, the consumption of the remediation agent is 1-8g/L, the treatment time is 480-2880min, and the treatment temperature is 15-35 ℃.
12. The use of the environmental heavy metal pollution remediation agent according to claim 11 in water/soil heavy metal pollution remediation, wherein the treatment time is 700-1450min.
13. The application of the environment heavy metal pollution remediation agent in the aspect of water/soil heavy metal pollution treatment according to claim 10, wherein the heavy metal pollution soil is treated, the mass ratio of sodium stearate modified tourmaline to biochar in the remediation agent is 1:3, the dosage ratio of the remediation agent to the soil is 20-100g/kg, and water is poured during the treatment process to keep the water content of the soil at 60% of the maximum water holding capacity of the field, and the treatment time is 30 days.
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