CN114749141A - Environmental heavy metal pollution repairing agent and preparation method and application thereof - Google Patents

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

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CN114749141A
CN114749141A CN202210526942.8A CN202210526942A CN114749141A CN 114749141 A CN114749141 A CN 114749141A CN 202210526942 A CN202210526942 A CN 202210526942A CN 114749141 A CN114749141 A CN 114749141A
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ball
tourmaline
heavy metal
biochar
ball milling
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CN114749141B (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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    • 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
    • B01J20/10—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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • 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
    • C02F2101/00—Nature of the contaminant
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Abstract

The application provides a preparation method of an environmental heavy metal pollution remediation agent, which comprises the following steps: mixing tourmaline or modified tourmaline and biochar, and performing first ball milling treatment to obtain a ball-milled product; 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 environmental heavy metal pollution remediation agent. The preparation method provided by the application adopts a ball milling treatment process, is simple, the obtained ball-milled tourmaline-biochar composite material has good product performance, particularly, after the tourmaline is ball-milled and modified by sodium stearate, the restoring agent capable of efficiently restoring heavy metal pollution can be prepared under the conditions of a low ball-to-material ratio and short ball milling time through ball milling treatment with the biochar, and the problems that the effect of adsorbing heavy metal in an acidic water body by a biochar single material is poor and the adsorption amount of Cd is low when the tourmaline single material is used at a low dosage are solved.

Description

Environmental heavy metal pollution repairing agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of environmental pollution treatment, and relates to an environmental heavy metal pollution remediation agent and a preparation method and application thereof.
Background
Under the background of rapid development of industrial economy, heavy metal pollution in water and soil environments becomes an important environmental problem restricting sustainable development in the fields of agriculture, economy, ecology and the like, and urgent solution is needed. Heavy metals have long half-life and are not easily biodegradable, can remain for a long time after entering soil and cause harm to human health and ecological systems through food chain transmission, and can be converted into organic metal forms through biological methylation to enhance the toxicity. Meanwhile, the soil with high heavy metal content can enter the underground water body under the action of the environment, so that the environment pollution of the underground water body is caused. There is a need to develop more efficient remediation techniques 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 the advantages of small soil disturbance, low cost and simple operation, can realize high-efficiency removal of heavy metals, and is mainly characterized by selection of a remediation agent.
The existing repairing agents are mainly divided into two categories, namely inorganic and organic, wherein the inorganic category mainly comprises phosphates, minerals and the like, the organic category mainly comprises organic compost, biochar and the like, and although the repairing agents can relieve the heavy metal pollution to the environment, some problems also exist in the preparation and use processes of part of the repairing agents: (1) the preparation process of the repairing agent is complicated, and the cost is high; (2) the repairing agent has low use efficiency and can generate secondary pollution; (3) the removal effect of the repairing agent on the heavy metal 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 heavy metal is obviously reduced; (4) the recyclability of the repaired soil is poor, for example, the repaired soil is easy to alkalize and agglomerate, and the recycling of soil resources is difficult to ensure.
The development of an economic, efficient, green and wide-application-range remediation agent is urgently needed in the field to realize the safe use of water body land resources.
Disclosure of Invention
The application aims to provide an environmental 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: the preparation process is complicated, the cost is high, the removal effect is easily influenced by environmental conditions, and the like.
In order to achieve the purpose, the following technical scheme is adopted in the application:
in a first aspect, the application provides a method for preparing an environmental heavy metal pollution remediation agent, comprising the following steps:
mixing tourmaline or modified tourmaline and biochar and carrying out first ball milling treatment to obtain a ball milling product; 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 and the like);
and step two, drying the product obtained by the first ball milling treatment to obtain the environment heavy metal pollution repairing agent.
In the above preparation method of the environmental heavy metal pollution remediation agent, as a preferred embodiment, in the step one, the ball milling medium is ultrapure water, the ball-to-material ratio of the first ball milling treatment is 10-20:1 (e.g., 12:1, 15:1, 18:1, etc.), the ball milling time is 5-24h (e.g., 6h, 8h, 10h, 12h, 15h, 18h, 20h, 22h, etc.), and the rotation speed is 1000-1500rmp (e.g., 1050rmp, 1100rmp, 1200rmp, 1300rmp, 1400rmp, 1450rmp, etc.); more preferably, the ball milling time is 6-12 h. In the application, the materials in the ball-to-material ratio are tourmaline or modified tourmaline and biochar, and ball-milling media such as water are not included.
Further preferably, the water ratio (m: v) of the material in the first ball milling treatment is 1g:2mL to 1g:5mL (e.g., 1g:2.5mL, 1g:3mL, 1g:4mL, 1g:4.5mL, etc.). The water ratio of the material is the ratio of the total mass of the tourmaline and the biochar to the volume of the ultrapure water.
In the above method for preparing the agent for restoring heavy metal pollution to the environment, as a preferred embodiment, 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 1 to 24 hours (e.g., 2 hours, 3 hours, 6 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, etc.).
In the above method for preparing the agent for restoring heavy metal pollution to the environment, as a preferred embodiment, in the first step, the particle size of the tourmaline or modified tourmaline is 50 μm or less (for example, 320 mesh sieve).
In the above method for preparing the agent for remediating environmental heavy metal pollution, as a preferred embodiment, in the first step, the particle size of the biochar is less than 75 μm (for example, 200-mesh sieve), and the biochar may be a commercially available product or a self-made product.
In the above method for preparing the agent for remedying the environmental heavy metal pollution, as a preferred embodiment, in the second step, the drying treatment temperature is 50-60 ℃ (e.g. 52 ℃, 55 ℃, 58 ℃) for 8-12h (e.g. 9h, 10h, 11h, etc.).
In the above method for preparing the agent for restoring heavy metal pollution to the environment, as a preferred embodiment, in the first step, the modified tourmaline is a sodium stearate modified tourmaline prepared by performing a second ball milling treatment on sodium stearate and tourmaline; more preferably, the mass ratio of the tourmaline and the sodium stearate is 80:1-120:1 (such as 85:1, 90:1, 95:1, 100:1, 105:1, 110:1, 115:1, etc.). Tests prove that the introduction of sodium stearate can improve the dispersibility of the tourmaline, and the introduction of stearate on the surface of the tourmaline can promote the adsorption capacity of heavy metal cations.
In the above method for preparing the agent for remedying the environmental heavy metal pollution, as a preferred embodiment, the ball-to-material ratio of the second ball milling treatment is 3:1 to 5:1 (e.g., 3.5:1, 4:1, 4.5:1, etc.), the ball milling time is 30 to 90min (e.g., 40min, 50min, 60min, 70min, 80min, 90min, etc.), and the rotation speed is 1000-1500rpm (e.g., 1050 rpm, 1100rmp, 1200rmp, 1300rmp, 1400rmp, 1450rmp, etc.).
In the above method for preparing a remediation agent for heavy metal pollution in the environment, 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 the water-to-water ratio (m: v) is preferably 1g:2mL to 1g:4mL (e.g., 1g:2.5mL, 1g:3mL, 1g:3.5mL, etc.).
In the above method for preparing an agent for remediating environmental heavy metal pollution, as a preferred embodiment, in the first step, the mass ratio of the sodium stearate-modified tourmaline to the biochar is 1:1-3 (e.g., 1:1.2, 1:1.5, 1:2, 1:2.5, 1:2.8, etc.).
In the above method for preparing the environmental heavy metal pollution remediation agent, as a preferred embodiment, in the step one, the first ball milling treatment is wet ball milling treatment, the ball milling medium is ultrapure water, and the preferred material-water ratio (m: v) is 1g:2mL-1g:5mL, where the material-water ratio is the ratio of the total mass of the sodium stearate modified tourmaline and the biochar to the volume of the ultrapure water.
In the above preparation method of the environmental heavy metal pollution remediation agent, as a preferred embodiment, in the step one, the ball-to-material ratio of the first ball milling treatment is 10-20:1 (e.g., 12:1, 15:1, 18:1, etc.), and the ball milling time is 5-24h (e.g., 2h, 3h, 6h, 12h, 15h, 18h, 20h, 22h, etc.); preferably, the ball milling time of the first ball milling treatment is 6-12 h.
In the above method for preparing the agent for restoring heavy metal pollution to the environment, as a preferred embodiment, in the first step, the mass ratio of the modified tourmaline to the biochar is 1:3, the ball-to-material ratio of the first ball-milling treatment is 10-20:1, and the ball-milling time is 1-24h (e.g., 2h, 3h, 6h, 12h, 15h, 18h, 20h, 22h, etc.); preferably, the ball milling time of the first ball milling treatment is 3-6 h.
In a second aspect, the application also provides an environmental heavy metal pollution repairing agent prepared by the method.
In a third aspect, the application further provides an application of the above environmental heavy metal pollution remediation agent in the aspect of water/soil heavy metal pollution remediation, including: the environment heavy metal pollution repairing agent is used for carrying out in-situ chemical treatment on the heavy metal polluted water body or soil.
Preferably, if the heavy metal polluted water body is treated, the pH value of the heavy metal polluted water body is 4-8, 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 and the like), the treatment time is 480-2880min (such as 540min, 720min, 960min, 1200min, 1440min, 1800min, 2400min and the like), and the treatment temperature is 15-35 ℃ (such as 18 ℃, 20 ℃, 25 ℃, 30 ℃, 32 ℃ and the like); preferably, the treatment time is 700-.
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 and the like), the water content of the soil is kept at 60% of the maximum field water capacity by watering in the treatment process (for example, 60mL of water is added into 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, is widely distributed, has five characteristics of infrared radiation characteristic, negative ion release characteristic, natural electric polarity, piezoelectricity and pyroelectric property, can automatically adjust the pH value of a solution by a spontaneous and permanent electrode, enables a strong acid or strong alkali environment to finally tend to be neutral, and has almost no influence on the removal effect of heavy metal ions by the acid-base property of an environment medium. However, the removal efficiency of heavy metals by tourmaline per unit mass is low. The biochar is a material obtained by carrying out high-temperature pyrolysis on biomass under an anaerobic or oxygen-limited condition, generally has the characteristics of stability, high aromatizing degree, large specific surface area, rich surface oxygen-containing functional groups and the like, can be used for efficiently removing heavy metals in a neutral environment, and is easily influenced by environmental acid-base conditions. The scheme of this application unites two into one the two advantage, and has realized the further promotion of efficiency.
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 provided by the application adopts a ball milling treatment process, is simple, and the obtained ball-milled tourmaline-biochar composite material has good product performance and has a good heavy metal adsorption effect compared with a composite material (synthesized by magnetic stirring) of non-ball-milled tourmaline and biochar; particularly, after the tourmaline is ball-milled and modified by sodium stearate, 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 through ball-milling treatment with the charcoal, besides, the stearate modified by the sodium stearate is adsorbed by the cationic metal on the surface of the tourmaline, and the adsorption sites on the surface of the material can be increased.
2) The application can solve the problems that the effect of adsorbing heavy metals by a biochar single material in an acidic water body is poor (such as pH 4 and 5) and the adsorption capacity of a tourmaline single material to Cd is low when the tourmaline single material is used at a low dose, firstly, a ball-milled sodium stearate modified tourmaline-biochar composite material is developed, and compared with the traditional biochar or tourmaline single material, the tourmaline-biochar composite material can be suitable for efficiently removing heavy metals in a wider pH range, and particularly can realize the efficient adsorption of the heavy metals in the wider pH range in the water body.
3) The ball-milling sodium stearate modified tourmaline-biochar composite material provided by the application is used for heavy metal adsorption treatment of underground water in Ningxia industrial park and heavy metal restoration treatment in Ningxia and Nanjing field soil, and the purpose of high-efficiency restoration of heavy metal pollution (including Cd, Cu, Pb and the like) can be realized by analyzing and discovering the ball-milling sodium stearate modified tourmaline-biochar composite material, so that the ball-milling sodium stearate modified tourmaline-biochar composite material has important scientific research value and practical application significance. The ball-milled sodium stearate modified tourmaline-biochar composite material provided by the application has higher adsorption rate to Cd, Cu and Pb in groundwater of Ningxia industrial park, and especially has adsorption rate to Cd and Pb in groundwater of more than 93%; the content of the heavy metal in the soil in Ningxia and Nanjing fields can be reduced by 13.1 percent, and the content of the residue can be increased by 21.5 percent.
Drawings
Fig. 1 is an SEM image of a ball-milled sodium stearate modified tourmaline-biochar composite. 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) respectively1/3-1h) And ball-milled sodium stearate modified tourmaline-biochar composite (BM-STBC)10-1/3-6h) SEM image of (d).
Fig. 2 is a comparison of the adsorption performance of different composite materials of tourmaline and biochar on heavy metals. Wherein, (a), (b), (c) and (d) are the results of comparing the performance of the ball-milled tourmaline-biochar composite material, the ball-milled 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 were: [ Cd ]2+]50mg/L, pH 6, [ adsorbent ]]The adsorption time is 24h and the adsorption temperature is 25 ℃ under the condition of 1 g/L;
FIG. 3 is a technical condition parameter optimization curve diagram of ball-milling sodium stearate modified tourmaline-biochar composite material for adsorbing heavy metals in water: (a) is the adsorption time; (b) is the dose of the adsorbent; (c) is the temperature; (d) is pH; (e) is the heavy metal concentration (experimental conditions are [ Cd ]2+]50mg/L, pH 6, [ adsorbent ]]1g/L, 24h, 25 ℃ adsorption temperature, and when one parameter is optimized, only changing the parameter value and keeping the other parameters fixed).
FIG. 4 is an FTIR chart before and after the ball-milled sodium stearate modified tourmaline-biochar composite material absorbs heavy metals, and the absorption condition is [ Cd ]2+]50mg/L, [ adsorbent ]]The reaction time was 24h, the adsorption temperature was 25 ℃, and the pH was 4.0, 6.0, 8.0.
In fig. 5, (a) is an SEM image of the ball-milled sodium stearate modified tourmaline-biochar composite material before heavy metal adsorption; (b) is an SEM image of the ball-milled sodium stearate modified tourmaline-biochar composite material after absorbing heavy metals in a solution with the pH value of 6; (c) ball milling under different initial pH conditionsThe pH value of the solution is changed after the sodium stearate modified tourmaline-biochar composite material absorbs heavy metal and balances (the experimental condition is Cd2+]50mg/L, [ adsorbent ]]Adsorption time 24h, reaction temperature 25 ℃, pH 2, 3, 4,5, 6, 7, 8) 1 g/L.
FIG. 6 shows Zeta potential of ball-milled sodium stearate modified tourmaline-biochar composite material in aqueous solution under different initial pH conditions.
Fig. 7 shows the application of the ball-milled sodium stearate modified tourmaline-biochar composite material in heavy metal adsorption in underground water of Ningxia industrial park, wherein (a) is the background value of heavy metal in underground water of Ningxia industrial park; (b) the adsorption rate of heavy metals is 1g/L when the ball-milled sodium stearate modified tourmaline-biochar composite material is added.
Fig. 8 shows the application of the ball-milled sodium stearate modified tourmaline-biochar composite material in remediation of heavy metal pollution in field soil, wherein (a) is the background value distribution of Cd in a certain industrial park (field soil 1 and field soil 2) in Ningxia Hui autonomous region and a certain chemical industry production field (field soil 3 and field soil 4) in Nanjing City of Jiangsu province; (b) the repairing effect of the ball-milled sodium stearate modified tourmaline-biochar composite material on Cd in the field soil under different dosages is realized, and the repairing time is 30 d; (c) is the influence of the ball-milling sodium stearate modified tourmaline-biochar composite material on the pH value of the field soil under different dosages. CK, 20 and 100 in the figure represent the dosages of the ball-milled sodium stearate modified tourmaline-biochar composite material as 0, 20 and 100g/kg, respectively.
Fig. 9 shows the influence of the ball-milled sodium stearate modified tourmaline-biochar composite on the physicochemical properties of the site soil 1 and the site soil 2 in Ningxia Industrial park, wherein (a), (b), (c), (d), (e) and (f) respectively show the influence of the ball-milled sodium stearate modified tourmaline-biochar composite on the cation concentration, the cation exchange amount and the organic matter concentration in the site soil 1 and the site soil 2, different lowercase letters in the figure show the significant level of the difference between different treatments, and p is less than 0.05.
Detailed Description
The following examples are presented to facilitate a better understanding of the present application and are not intended to limit the present application.
The experimental procedures in the following examples are conventional unless otherwise specified.
Other test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the following examples, the original tourmaline is a commercial product, namely iron tourmaline purchased from Hubei Lingshou mineral powder factories, the particle size is 320 meshes of sieve, and the code is T; the superfine tourmaline is obtained by drying original tourmaline which is sieved by a 320-mesh sieve at 60 ℃ to constant weight, and then performing ball milling treatment under the conditions of ball-material ratio of 10, ball milling time of 3h and rotation speed of 1200rpm, wherein the original tourmaline is sieved by the 320-mesh sieve and has the code of UT; the biochar is a commercial product, is rice straw biochar (prepared by pyrolysis at 500 ℃) purchased from Rize environmental protection technology company in Henan, and is sieved by a 200-mesh sieve, and the code is BC; the sodium stearate is a commercial product, purchased from Xingjin' S Xingqian fine chemical research institute, and analyzed and purified, and the code is S.
Example 1 preparation example
Firstly, preparing sodium stearate modified tourmaline:
(1) the preparation method of the non-ball-milled sodium stearate modified tourmaline (NBM-ST and NBM-SUT) comprises the following steps: adding 3g of original tourmaline or fine tourmaline, 0.039g of sodium stearate and 150mL of ultrapure water into a 500mL beaker in sequence, stirring for 60min at 80 ℃ by using a magnetic stirrer at the rotation speed of 300rpm, centrifuging and washing the suspension for three times to remove unreacted sodium stearate, drying to constant weight at 60 ℃, grinding and sieving by using a 320-mesh sieve, placing into a dryer and storing in a dark place for later use, wherein the product codes are NBM-ST and NBM-SUT respectively.
(2) The preparation method of the ball-milled 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 amount of sodium stearate is 1% of the tourmaline, the water ratio (m: v) of the materials is 2:5, the rotation speed is 1200rpm and the ball-material ratio is 4, then drying at 60 ℃ to constant weight, grinding and sieving with a 320-mesh sieve, placing in a drier and keeping out of the sun for later use, wherein the product code is BM-ST.
(II) tourmaline-biologyPreparing a carbon composite material:
(1) the preparation method of the non-ball-milled tourmaline-biochar composite material (NBM-TBC, NBM-UTBC) comprises the following steps: an appropriate amount of biochar and ultrapure water was added in a 500mL beaker at a ratio of 1g:30mL (m: v), and stirred at 60 ℃ for 15min at a rotation speed of 200rpm with a magnetic stirrer to uniformly disperse the biochar in the aqueous solution. The original tourmaline/fine tourmaline with the mass ratio of biochar of 1:0.3-3 (such as 3:1, 1:3, etc.) is uniformly dispersed in the water solution by the same method. Then, the original tourmaline/fine tourmaline suspension is slowly added into the water solution of biochar, and is magnetically stirred at 300rpm for 0.5-12h (such as 0.5h, 1h, 3h, 6h and 12 h). After the reaction is finished, the suspension is centrifuged and washed for three times, dried to constant weight at 60 ℃ and ground, and then the unground tourmaline-biochar (NBM-TBC) composite material and the unground superfine tourmaline-biochar composite material (NBM-UTBC) can be respectively obtained.
(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 non-ball-milled sodium stearate modified tourmaline-biochar composite (the code is NBM-STBC) and the non-ball-milled sodium stearate modified fine tourmaline-biochar composite (the code is NBM-SUTBC) are respectively prepared by using the sodium stearate modified tourmaline/fine tourmaline and biochar through magnetic stirring treatment; the specific operation method refers to the preparation of the non-ball-milled tourmaline-biochar composite material (i.e. the above part (1)).
(3) The preparation method of the ball-milled tourmaline-biochar composite (BM-TBC) comprises the following steps: firstly, weighing a certain amount of grinding balls with different particle sizes in a zirconium oxide ball-milling tank according to ball-to-material ratios of 10 to 20 (phi 8mm:5mm:3mm ═ 2:5:3), then weighing 10% and 20% of the mass of the zirconium oxide grinding balls together by tourmaline and biochar according to mass ratios of 1:0.3 to 3 (such as 3:1, 1:1 and 1:3), adding the mixture into the ball-milling tank, fully mixing the mixture, and adding a certain amount of ultrapure water into the ball-milling tank according to a material-to-water ratio (m: v) of 1g:2 mL. After all the required components are added, the ball milling tank is sealed and placed into a ball mill, the rotating speed is set to be 1200rpm, and the ball milling time is set to be 1-24h (such as 1h, 3h, 6h, 12h and 24 h). After the ball milling is finished, the prepared material is dried to constant weight at 50-60 ℃, and is ground and sieved, and the product code is BM-TBC.
(4) The preparation method of the ball-milled sodium stearate modified tourmaline-biochar composite material (BM-STBC) comprises the following steps: referring to the preparation method of the ball-milled tourmaline-biochar composite material (namely part (3) above), the product code is BM-STBC.
The names and codes of the raw materials used in the examples and the prepared composite materials and the process thereof are summarized in Table 1.
Figure BDA0003644749600000091
(III) material characterization:
the surface morphology of the sample 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 (NBM-UTBC) respectively1/3-1hUT, BC 1:3, magnetic stirring 1h) and ball-milled sodium stearate modified tourmaline-biochar composite (BM-STBC)10-1/3-6hI.e. ST: BC 1:3, ball to material ratio 10, ball milled 6 h). A and b, c and d in fig. 1 indicate that the ball milling process can significantly reduce the particle size of the single material of tourmaline and biochar, and sodium stearate is irregularly loaded on the surface of tourmaline. Fig. 1, e and f, show that the tourmaline and the biochar in the unground composite material are more physically doped, and the two still maintain their own shapes, while SEM images of the ball-milled sodium stearate modified tourmaline-biochar composite material show that although part of the sodium stearate modified tourmaline still maintains its original structure, most of the surface of the sodium stearate modified tourmaline is loaded with the biochar, and the particle size of the ball-milled composite material is significantly lower than that of the unground composite material.
(IV) screening the performance of tourmaline-charcoal composite material
Prepared by the present example1g/L of Cd with the concentration of 50mg/L and the pH value of 6 is added into the composite material2+And uniformly mixing the solution, oscillating at the constant temperature of 25 ℃ for adsorption for 48h, filtering, and determining the concentration of heavy metal in the filtrate. According to different composite materials, Cd in aqueous solution2+The adsorption rate of (2) is used for evaluating the modification effect of the composite material, and the higher the adsorption rate of the material to heavy metals, the better the performance of the material.
A in figure 2 shows NBM-UTBC obtained when the mass ratio of the fine tourmaline to the biochar is 1:3 and the synthesis time of the fine tourmaline and the biochar is 1h by magnetic stirring1/3-1hFor Cd2+The highest adsorption rate of (2) was 75.78%. B in figure 2 shows BM-TBC obtained when the tourmaline and the biochar are in a mass ratio of 1:3, a ball-material ratio of 10 and a ball milling time of 12h10-1/3-12hFor Cd2+The highest adsorption rate of (2) was 97.10%. In figure 2, c shows NBM-SUTBC obtained when the mass ratio of the sodium stearate modified fine tourmaline to the biochar is 1:3 and the synthesis time of the magnetic stirring is 1h1/3-1hFor Cd2+The highest adsorption rate of (2) was 66.01%. D in figure 2 shows BM-STBC obtained when the sodium stearate modified tourmaline and the biochar are in the mass ratio of 1:3, the ball-material ratio of 10 and the ball milling time of 6h10-1/3-6hFor Cd2+The highest adsorption rate of 97.26% was obtained, compared with that of the unground material (NBM-STBC) under the same conditions1/3-6h) For Cd2+The adsorption rate of the composite material is higher by more than 2 times and is approximately 4 times higher than that of a ball-milled tourmaline single material, and the composite material can realize optimal adsorption in a shorter time and at a lower ball-material ratio compared with a ball-milled tourmaline-biochar composite material, and is a material with optimal performance.
Example 2 effects example-Water remediation
The ball-milled sodium stearate modified tourmaline-biochar composite material used in the embodiment is a BM-STBC composite material obtained under the conditions that the mass ratio of the sodium stearate modified tourmaline to the biochar is 1:3, the ball-to-material ratio is 10 and the ball milling time is 6 hours10-1/3-6h. The performance of the ball-milling sodium stearate modified tourmaline-biochar composite material for absorbing heavy metals in a water body is detected, and cadmium (Cd) is selected as a representative.
Ball-milling sodium stearate modified tourmaline-biochar composite materialAdsorbing heavy metals in a water body by using the material:
(1) adsorption time: the dosage of the ball-milled sodium stearate modified tourmaline-biochar composite material is 1g/L, and Cd2+The initial concentration was 50mg/L, pH was 6, the adsorption temperature was 25 ℃, the adsorption was oscillated at 180rpm, and samples were taken when the adsorption proceeded to 5, 15, 30, 60, 120, 240, 360, 480, 720, 960, 1200, 1440, and 2880min, respectively. The content of the target contaminant in the sample was measured by using a continuous light source atomic absorption spectrometer, and the result is shown in fig. 3 (a).
(2) The dosage of the ball-milled sodium stearate modified tourmaline-biochar composite material is as follows: the dosages of the ball-milled sodium stearate modified tourmaline-biochar composite material are respectively 0.5, 1, 2, 4 and 8g/L, and Cd2+The initial concentration was 50mg/L, pH was 6, the adsorption temperature was 25 ℃, and the sample was taken after adsorbing for 24 hours with shaking at 180rpm, and the results are shown in (b) of FIG. 3.
(3) Adsorption temperature: the dosage of the ball-milled sodium stearate modified tourmaline-biochar composite material is 1g/L, and Cd2+The initial concentration was 50mg/L, pH was 6, and the adsorption was carried out at 15, 25 and 35 ℃ respectively with shaking at 180rpm for 24 hours, followed by sampling and examination, and the results are shown in (c) of FIG. 3.
(4) pH of the reaction system: adding 1g/L of ball-milled sodium stearate modified tourmaline-biochar composite material into 50mg/L of Cd with initial concentration of pH 2, 3, 4,5, 6, 7 and 8 respectively2+In the solution, samples were taken and examined after shaking at a rotation speed of 180rpm at 25 ℃ for 24 hours, and the results are shown in (d) of FIG. 3.
(5) Concentration of the contaminant: setting the dosage of the ball-milled sodium stearate modified tourmaline-biochar composite material to be 1g/L, and Cd at the pH of 62+The initial concentrations were 25, 50, 100, 150, 200, 250, 300, 350 and 400mg/L, respectively, and the samples were taken after shaking at a rotation speed of 180rpm at 25 ℃ for 24 hours for examination, and the results are shown in (e) of FIG. 3.
Fig. 3 shows the influence of various technical parameters on the adsorption effect of the ball-milled sodium stearate modified tourmaline-biochar composite material on heavy metals in a water body. Finally determining the adsorption equilibrium timeThe optimal dose of the ball-milled sodium stearate modified tourmaline-biochar composite material is 1g/L for 24h, the optimal adsorption temperature is 25 ℃, the pH is 4-8, and Cd2+The concentration of (A) can be in the range of 25-400mg/L to achieve high removal efficiency. When the dosage of the ball-milled sodium stearate modified tourmaline-biochar composite material is 1g/L, the adsorption time is 24h, the adsorption temperature is 25 ℃, the pH is 6, and Cd2+When the initial concentration of the sodium stearate is 50mg/L, the sodium stearate modified tourmaline-biochar composite material is ball-milled for Cd2+The adsorption rate of the adsorbent can reach 98.08 percent, and the equilibrium adsorption capacity can reach 49.04 mg/L.
(II) the way of heavy metal adsorption of the ball-milling sodium stearate modified tourmaline-biochar composite material is as follows:
in the embodiment, the concentration and the pH of cations in the solution before and after adsorption and the ball-milling sodium stearate modified tourmaline-biochar composite material BM-STBC are measured10-1/3-6hThe surface functional group change and the Zeta potential thereof are used for exploring the heavy metal adsorption mechanism of the water body.
(1) Cation exchange: ball-milled sodium stearate modified tourmaline-biochar composite material for adsorbing Cd2+In the process of (2), a large amount of Na is released+(429.40mg/L) with a small amount of K+(0.19Mg/L) and Mg2+(0.24mg/L), which shows that heavy metal cations in the water body can be removed by exchanging with the metal cations on the surface of the ball-milled sodium stearate modified tourmaline-biochar composite material.
(2) Complexing functional groups: ball-milled sodium stearate modified tourmaline-biochar composite material for adsorbing Cd under different pH conditions2+After that, the-OH of the surface thereof (3425 cm)-1)、C＝O(1635cm-1)、-CH2(711cm-1) Characteristic peak of (2) and characteristic peak of sodium stearate (2920 cm)-1) All of which are significantly changed while also being partially offset (see fig. 4). In addition, the surface functional group of the ball-milled sodium stearate modified tourmaline-biochar composite material is 1442-783cm-1The abundance of Cd is obviously changed, which indicates that Cd is adsorbed in the process of adsorption2+Enters the structure of the ball-milled sodium stearate modified tourmaline-biochar composite material and is combined with functional groups。
(3) Hydroxide precipitation: adsorption of Cd in comparison to SEM image of original ball-milled sodium stearate modified tourmaline-biochar composite, see (a) in FIG. 52+More newly formed small round particles appear on the surface of the ball-milled sodium stearate modified tourmaline-biochar composite material, and as shown in (b) in fig. 5, the heavy metal probably forms a precipitate on the surface of the ball-milled sodium stearate modified tourmaline-biochar composite material. According to Cd2+K ofspCalculate at the initial Cd2+At a concentration of 50mg/L, Cd is adjusted2+The maximum pH at which a precipitate formed was 8.8. FIG. 5 (c) shows the adsorption of Cd by the ball-milled sodium stearate modified tourmaline-biochar composite in different initial pH solutions2+Measurement of the pH after equilibrium has been reached. When the initial pH of the solution is more than or equal to 6, the pH after the reaction is more than 8.8, which shows that when the initial pH of the solution is more than or equal to 6, Cd can appear in the adsorption process2+Precipitating the hydroxide of (2). The product can adjust the pH of the solution to convert the acidic solution into neutral or alkalescent solution, and the adjusted pH is beneficial to the conversion of the heavy metal to a stable form, such as a precipitate 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 equivalent charge point iszpc3.38 (see fig. 6). Thus, when the initial pH of the solution is>3.38, the surface of the ball-milled 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-heavy metal adsorption in groundwater of Industrial park
(1) And (3) measuring the background value of heavy metal in underground water of the industrial park: in this example, groundwater used for the experiment was collected from an industrial park of Ningxia Hui autonomous region, and the background value of heavy metals was measured by ICP-MS, and the result is shown in FIG. 7 (a).
(2) Heavy metal adsorption of underground water in industrial parks: adding ball-milled sodium stearate modified tourmaline-biochar composite BM-STBC into underground water of the industrial park at a dose of 1g/L10-1/3-6hAfter that, the air conditioner is started to work,after 24h of adsorption at 25 ℃ with shaking at 180rpm, the suspension was filtered and the concentration of heavy metals in the filtrate was determined by ICP-MS.
Background values of heavy metals Cd, Cu, and Pb contained in groundwater of Ningxia Industrial park are shown in (a) of FIG. 7. According to GB/T14848-2017, the content of Cd exceeds the standard of class II water. Fig. 7 (b) shows the effect of the ball-milled sodium stearate modified tourmaline-biochar composite on adsorption of heavy metals to groundwater in Ningxia Industrial park. After adsorption, the removal rate of Cd and Pb in the groundwater is high (both are more than 93%), and then Cu is added. Meanwhile, the pH value of the underground water after adsorption is increased by 0.46 unit and is 7.90, which indicates that the composite material BM-STBC is added10-1/3-6hThe method is favorable for the stability of the form of the heavy metal, and prevents the reduction of the pH value of the environment so as to prevent partial heavy metal which generates the precipitate from recovering the dissolved state.
Example 4 application example-establishment of heavy metal contaminated site soil remediation System
(1) Measuring the background value of the heavy metal in the field soil: the soil used in the experiment of this example was collected from an industrial park (field soil 1 and field soil 2) in a national autonomous region of Ningxia Hui and a production field (field soil 3 and field soil 4) in a chemical industry in Nanjing City of Jiangsu province, and according to the investigation results, the field pollution was mainly heavy metal pollution. Naturally drying the soil, sieving by a 2mm sieve, removing impurities, and placing in a shade place for later use. The method for measuring the concentration of heavy metal in the soil comprises the following steps: sieving the air-dried soil sample with a 100-mesh sieve, accurately weighing 0.10g of sample in a polytetrafluoroethylene digestion tank, and adding 6mL of HNO3And 2mL of HF, uniformly mixing, standing for 10min to finish the initial reaction, uniformly mixing, covering and sealing, digesting, and measuring the concentration of heavy metal in the digested soil by using ICP-MS. The results are shown in fig. 8 (a).
(2) Ball-milled sodium stearate modified tourmaline-biochar composite BM-STBC10-1/3-6hRepairing heavy metal contaminated site soil: applying ball-milled sodium stearate modified tourmaline-biochar composite material to field soil at dosages of 0, 2% and 10% of field soil mass, namely 0g/kg, 20g/kg and 100g/kg for repairing for 30 days (d), and weighingAnd (3) periodically irrigating distilled water to keep the water content of the soil in the field to be 60% of the maximum water holding capacity in the field. Meanwhile, the pH values of the soil in the four fields before and after the restoration are measured.
(3) Ball-milled sodium stearate modified tourmaline-biochar composite BM-STBC10-1/3-6hThe physical and chemical properties of the heavy metal contaminated site soil are influenced: and measuring the metal cation concentration, the cation exchange amount and the organic matter concentration in Ningxia field soil 1 and field soil 2 before and after restoration.
As shown in (a) of fig. 8, according to GB 15618-. According to GB36600-2018, the Cd content in Nanjing site soil 3 and site soil 4 exceeds the risk screening value of the first-class land.
As shown in fig. 8 (b), when the ball-milled sodium stearate-modified tourmaline-biochar composite was applied at a dose of 20g/kg, it was found that the content of Cd in the field soil in the active state could be reduced by 6.73% at the maximum, and the content of Cd in the residue state could be increased by 5.95-9.35%. When the ball-milled sodium stearate modified tourmaline-biochar composite material is applied at a dosage of 100g/kg, the effective state content of Cd in field soil is reduced to 13.1%, and the residue state content can be increased by 13.5-21.5%. In addition, the pH of the field soil after remediation is increased by 0.05-0.35 units (see c in FIG. 8).
The ball-milled sodium stearate modified tourmaline-biochar composite can increase the metal cation concentration in Ningxia field soil 1 (see (a) in figure 9) and field soil 2 (see (b) in figure 9), and the metal cation concentration is in positive correlation with the field soil. Dosage of sodium stearate modified tourmaline-biochar composite material and K in ground soil 1 through ball milling+、Na+The correlation coefficient r with the concentration of the total cations is 0.958, 0.771 and 0.924 respectively, the dosage of the sodium stearate modified tourmaline-biochar composite material in the ball mill in the field soil 2 and the K+、Na+、Mg2+And the total cation concentration, r, were 0.710, 0.974, 0.989, and 0.903, respectively. After the material is added, the concentration of metal cations is increased, which shows that the cations in the material are exchanged with heavy metal cations in the soil and released into the soil, and is favorable forAnd (5) repairing.
The ball-milled sodium stearate modified tourmaline-biochar composite material can increase the cation exchange capacity in Ningxia field soil 1 and field soil 2, wherein the cation exchange capacity in the field soil 1 is increased by 0.18-0.59 cmol/kg, see (c) in figure 9, the cation exchange capacity in the field soil 2 is increased by 0.82-0.91 cmol/kg, see (d) in figure 9, and the increase of the cation exchange capacity can promote the material to remove heavy metal cations in the soil through cation exchange.
The ball-milled 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 remarkably increased by 1.24-8.35 g/kg, as shown in (e) in fig. 9, the organic matter content in the field soil 2 is remarkably increased by 1.93-8.51 g/kg, as shown in (f) in fig. 9, and the increase in organic matter concentration can promote heavy metals to be converted into a stable form through organic complexation.
Finally, it should also be noted that, in the present 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 an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
While the application has been disclosed by the description of specific embodiments thereof, it should be understood that various modifications, adaptations, and equivalents may occur to one skilled in the art and are within the spirit and scope of the appended claims. Such modifications, improvements and equivalents are intended to be included within the scope of the claims.

Claims (10)

1. A preparation method of an environmental heavy metal pollution remediation agent is characterized by comprising the following steps:
mixing tourmaline or modified tourmaline and biochar and carrying out first ball milling treatment to obtain a ball milling product; the first ball milling treatment is wet ball milling treatment, and the mass ratio of the tourmaline or the modified tourmaline to the biochar is 1: 1-3;
and step two, drying the product obtained by the first ball milling treatment to obtain the environmental heavy metal pollution remediation agent.
2. The preparation method according to claim 1, wherein in the first step, the ball-to-material ratio of the first ball-milling treatment is 10-20:1, the ball-milling time is 5-24h, the rotation speed is 1000-;
preferably, the ball milling medium of the first ball milling treatment is ultrapure water, and the material water ratio is 1g:2mL-1g:5 mL.
3. 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 1-24 h.
4. The method of preparing of claim 1, wherein the particle size of the tourmaline or modified tourmaline at the first step is 50 μm or less and the particle size of the biochar is 75 μm or less.
5. The method according to any one of claims 2 to 4, wherein the drying treatment is carried out at a temperature of 50 to 60 ℃ for 8 to 12 hours in the second step.
6. The preparation method according to claim 1, wherein in the first step, the modified tourmaline is a sodium stearate modified tourmaline prepared by subjecting sodium stearate and tourmaline to a second ball milling treatment, and the mass ratio of the tourmaline to the sodium stearate is 80:1-120: 1;
preferably, 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-;
more preferably, the second ball milling treatment is wet ball milling treatment, the ball milling medium is water, and the water ratio of the material is preferably 1g:2mL-1g:4 mL.
7. The preparation method according to claim 6, wherein in the first step, the ball milling medium of the first ball milling treatment is ultrapure water, and the water ratio of the material is 1g:2mL-1g:5 mL; 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-; preferably, the ball milling time of the first ball milling treatment is 6-12 h.
8. The preparation method of claim 6, wherein in the first step, the mass ratio of the modified tourmaline to the biochar is 1:3, the ball-to-material ratio of the first ball-milling treatment is 10-20:1, and the ball-milling time is 1-24 h; preferably, the ball milling time of the first ball milling treatment is 3-6 h.
9. An environmental heavy metal pollution remediation agent prepared by the method of any one of claims 1 to 8.
10. An application of an environmental heavy metal pollution remediation agent in the aspect of water/soil heavy metal pollution treatment comprises the following steps: carrying out in-situ chemical treatment on the heavy metal polluted water body or soil by using the environmental heavy metal pollution remediation agent as defined in claim 9;
preferably, the heavy metal polluted water body is treated, the pH of the heavy metal polluted water body is 4-8, 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, the treatment time is 480-2880min, and the treatment temperature is 15-35 ℃; preferably, the treatment time is 700-;
preferably, 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 using amount ratio of the repairing agent to the soil is 20-100g/kg, the water is poured in the treatment process to keep the water content of the soil at 60% of the maximum field water holding capacity, and the treatment time is 30 days.
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5601909A (en) * 1993-12-07 1997-02-11 Kubo; Tetsujiro Permanent electrode carrier using tourmaline
WO2001010251A1 (en) * 1999-08-04 2001-02-15 Dorikamu Kabushiki Kaisha Composition containing bamboo charcoal and carrier having the same
JP2007261906A (en) * 2006-03-29 2007-10-11 Eco Life Kk Porous granule
JP2009082559A (en) * 2007-10-01 2009-04-23 Jen-Taut Yeh Composite powdery body which emits negative ion at high efficiency, composite powdery body deposit, and its manufacturing method
CN101844072A (en) * 2010-06-03 2010-09-29 浙江碧岩环保材料有限公司 Adsorption decomposition agent and preparation method thereof
CN103588202A (en) * 2013-11-18 2014-02-19 曹南萍 Manufacturing method for active carbon/tourmaline composite material and product manufactured according to manufacturing method
CN103608104A (en) * 2011-02-03 2014-02-26 萨里大学 Composite adsorbent material containing a porous carbon matrix
CN103894403A (en) * 2012-12-27 2014-07-02 南开大学 Method for restoring heavy metal polluted farmland soil with tourmaline as modifying agent
CN103896356A (en) * 2012-12-27 2014-07-02 南开大学 Adsorption of novel tourmaline material on cadmium in acid solution
CN108325509A (en) * 2018-04-17 2018-07-27 钦州学院 A kind of environment-friendly type water pollution sorbing material and preparation method thereof
CN110423621A (en) * 2019-07-25 2019-11-08 中国林业科学研究院亚热带林业研究所 A kind of biomass composite, preparation method and its application
CN112694677A (en) * 2021-01-08 2021-04-23 会通新材料股份有限公司 Bamboo charcoal and tourmaline composite Ag-loaded antibacterial agent, antibacterial polypropylene composition and preparation method

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5601909A (en) * 1993-12-07 1997-02-11 Kubo; Tetsujiro Permanent electrode carrier using tourmaline
WO2001010251A1 (en) * 1999-08-04 2001-02-15 Dorikamu Kabushiki Kaisha Composition containing bamboo charcoal and carrier having the same
JP2007261906A (en) * 2006-03-29 2007-10-11 Eco Life Kk Porous granule
JP2009082559A (en) * 2007-10-01 2009-04-23 Jen-Taut Yeh Composite powdery body which emits negative ion at high efficiency, composite powdery body deposit, and its manufacturing method
CN101844072A (en) * 2010-06-03 2010-09-29 浙江碧岩环保材料有限公司 Adsorption decomposition agent and preparation method thereof
CN103608104A (en) * 2011-02-03 2014-02-26 萨里大学 Composite adsorbent material containing a porous carbon matrix
CN103894403A (en) * 2012-12-27 2014-07-02 南开大学 Method for restoring heavy metal polluted farmland soil with tourmaline as modifying agent
CN103896356A (en) * 2012-12-27 2014-07-02 南开大学 Adsorption of novel tourmaline material on cadmium in acid solution
CN103588202A (en) * 2013-11-18 2014-02-19 曹南萍 Manufacturing method for active carbon/tourmaline composite material and product manufactured according to manufacturing method
CN108325509A (en) * 2018-04-17 2018-07-27 钦州学院 A kind of environment-friendly type water pollution sorbing material and preparation method thereof
CN110423621A (en) * 2019-07-25 2019-11-08 中国林业科学研究院亚热带林业研究所 A kind of biomass composite, preparation method and its application
CN112694677A (en) * 2021-01-08 2021-04-23 会通新材料股份有限公司 Bamboo charcoal and tourmaline composite Ag-loaded antibacterial agent, antibacterial polypropylene composition and preparation method

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
JIA WEILI 等: "Tourmaline and biochar for the remediation of acid soil polluted with heavy metals", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 *
LI WENXUAN 等: "STUDY ON THE REMEDIATION EFFECT OF A NEW TYPE OF IMPROVER ON HEAVY METAL CONTAMINATED SOILS: BASED ON RESPONSE SURFACE METHOD" *
LIANG YAFENG 等: "A review: Application of tourmaline in environmental fields", 《CHEMOSPHERE》 *
王宝琳 等: "电气石和沸石对土壤-小麦幼苗系统中重金属行为的影响", 《环境化学》 *
王翠苹 等: "新型材料电气石对酸性溶液中镉离子的吸附", 《科学通报》 *
胡应模 等: "硬脂酸钠对电气石的表面改性及其结构表征", 《中国非金属矿工业导刊》 *

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