CN111533188A - Repairing agent for heavy metal polluted underground water, preparation method and application method - Google Patents

Repairing agent for heavy metal polluted underground water, preparation method and application method Download PDF

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CN111533188A
CN111533188A CN202010323962.6A CN202010323962A CN111533188A CN 111533188 A CN111533188 A CN 111533188A CN 202010323962 A CN202010323962 A CN 202010323962A CN 111533188 A CN111533188 A CN 111533188A
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heavy metal
agent
contaminated groundwater
metal contaminated
remediation agent
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CN111533188B (en
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李来庆
陶盈冰
郑明霞
牟永明
吴晶晶
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Beijing Longtech Environment Restoration Co ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06Contaminated groundwater or leachate

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
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  • Water Supply & Treatment (AREA)
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  • Inorganic Chemistry (AREA)
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  • Water Treatment By Sorption (AREA)

Abstract

The invention discloses a repairing agent for heavy metal polluted groundwater, a preparation method and an application method thereof, wherein the repairing agent comprises the following components in percentage by weight: hydroxyapatite, silicate minerals, alkali and a template agent; the mol ratio among the components is as follows: hydroxyapatite: silicate mineral: alkali: templating agent (300-: (50-100): (0-20): (5-15). According to one embodiment of the invention, the repairing agent has more remarkable cation exchange property, adsorbability and shape selectivity, and can effectively repair heavy metal pollution in underground water.

Description

Repairing agent for heavy metal polluted underground water, preparation method and application method
Technical Field
The invention relates to the technical field of groundwater remediation, and particularly relates to a remediation agent for heavy metal polluted groundwater, and a preparation method and an application method thereof.
Background
Groundwater is an important component of water resources, and in recent years, with increasingly serious water pollution and excessive development of groundwater resources, the current situation of groundwater in China is not optimistic. According to the '2018 Chinese ecological environment condition bulletin', the percentage of IV-class water and V-class water in 10168 national-level underground water quality monitoring points is more than 85%, and the standard exceeding indexes are manganese, iron, turbidity, total hardness, soluble total solids, iodide, chloride, "trinitrogen", sulfate and heavy (class) metal lead, zinc, arsenic, mercury, hexavalent chromium, cadmium and the like. Heavy metals can not only cause harm to human health, but also cause serious damage to surrounding soil environment, animals and vegetation, and the frequent occurrence of strange diseases in rural areas such as 'cancer village' and 'malformation village' exposed in various regions in recent years is mostly related to groundwater heavy metal pollution.
Because groundwater pollution is hidden, the migration speed is relatively slow, and the groundwater is deeply buried, if ex-situ remediation modes such as pumping treatment and the like are used, not only is the system required to be periodically overhauled and maintained, but also the remediation area and the surrounding water body are easily interfered in the process of repeated pumping and recharging, and the operation cost is huge.
Therefore, a new technical solution is needed to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a repairing agent for heavy metal polluted underground water, a preparation method and a new technical scheme of an application method.
According to a first aspect of the present invention, there is provided a remediation agent for heavy metal contaminated groundwater, the remediation agent comprising in admixture: hydroxyapatite, silicate minerals, alkali and a template agent;
the mol ratio among the components is as follows: hydroxyapatite: silicate mineral: alkali: templating agent (300-: (50-100): (0-20): (5-15).
Optionally, the paint also comprises distilled water, and the molar ratio of the distilled water is 2000-10000.
Optionally, the silicate mineral comprises at least one of kaolin, bentonite, illite, sepiolite, attapulgite, zeolite, and diatomaceous earth.
Optionally, the templating agent comprises at least one of n-butylamine, diethanolamine, tetrapropylammonium hydride, tetrapropylammonium bromide, tetrapropylammonium hydroxide, hexylamine, and hexamethylenediamine.
Alternatively, the base comprises: at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and calcium carbonate.
According to a second aspect of the present invention, there is provided a method for preparing a remediation agent for heavy metal contaminated groundwater, comprising:
preparing raw materials, and taking hydroxyapatite as a raw material according to a molar ratio: silicate mineral: alkali: template agent: distilled water (300-: (50-100): (0-20): (5-15): (2000-10000) to form a mixed solution;
heating the mixed solution to a preset temperature and stirring to age the mixed solution;
heating the aged mixed solution until hydrothermal crystallization reaction occurs to form a suspension;
carrying out solid-liquid separation on the suspension, and washing to be neutral;
and drying the washed material to prepare the repairing agent.
Optionally, the predetermined temperature is 40-90 ℃, the stirring speed is 100-500 r/min, and the aging time is 4-8 h.
Optionally, in the process of heating the aged mixed solution to generate hydrothermal crystallization reaction, the heating temperature is 100-200 ℃, and the reaction time is 1d-3 d.
Optionally, in the process of solid-liquid separation of the suspension, a suction filtration or centrifugation mode is adopted, optionally, in the process of drying the washed material, the drying temperature is 80-110 ℃, and the drying time is 8-16 h.
According to a third aspect of the present invention, there is provided an application method of a remediation agent for heavy metal contaminated groundwater, comprising:
preparing the remediation agent for heavy metal contaminated groundwater as described above;
mixing a repairing agent and a binder, and forming into a three-dimensional structure;
and placing the formed repairing agent at the downstream of the heavy metal polluted groundwater pollution feather.
According to one embodiment of the disclosure, the repairing agent disclosed by the disclosure has more remarkable cation exchange property, adsorption property and shape selectivity, and can effectively repair heavy metal pollution in underground water.
Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments thereof, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is a flow chart of a method of applying a remediation agent in one embodiment of the disclosure.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
According to one embodiment of the present disclosure, there is provided a remediation agent for heavy metal contaminated groundwater, wherein the remediation agent comprises, in admixture: hydroxyapatite, silicate minerals, alkali and a template agent; the mol ratio among the components is as follows: hydroxyapatite: silicate mineral: alkali: templating agent (300-: (50-100): (0-20): (5-15).
In the embodiment, compared with the existing repairing agent, the repairing agent has more remarkable cation exchange property, adsorbability and shape selectivity, and can effectively repair heavy metal pollution in underground water. Wherein, the hydroxyapatite has a special crystal chemical structure, and the silicate mineral has a large specific surface area and a pore channel structure. The repairing agent combines hydroxyapatite and silicate minerals together, so that cation exchange property, adsorptivity and shape selectivity of the repairing agent are remarkably improved, and heavy metals in a water body are removed through the actions of ion exchange, adsorption, fixation and the like, so that heavy metal pollution in underground water is effectively repaired. Heavy metal ions capable of being repaired include Pb2+、Cd2+、Cu2+、Zn2+、Cr6+、Ni2+And the like.
The components of the repairing agent in the disclosure also comprise distilled water, and the molar ratio of the distilled water is 2000-10000.
In one embodiment, the silicate mineral comprises at least one of kaolin, bentonite, illite, sepiolite, attapulgite, zeolite, and diatomaceous earth. The silicate mineral in the embodiment has the characteristic of large specific surface area and a pore structure, and the large specific surface area and the pore structure can improve the repair capability of the repair agent on heavy metals.
In one embodiment, the templating agent comprises at least one of n-butylamine, diethanolamine, tetrapropylammonium hydride, tetrapropylammonium bromide, tetrapropylammonium hydroxide, hexylamine, and hexamethylenediamine. The template agent in this embodiment can facilitate the formation of a pore structure in the repair agent, thereby improving the repair ability of the repair agent.
In one embodiment, the base comprises: at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and calcium carbonate. The alkali in the embodiment can provide an alkaline condition for the repairing agent, and can promote the combination of aluminosilicate gel generated by silicate mineral dissolution and hydroxyapatite.
According to another embodiment of the present disclosure, there is provided a method for preparing a remediation agent for heavy metal contaminated groundwater, including:
preparing raw materials, and taking hydroxyapatite as a raw material according to a molar ratio: silicate mineral: alkali: template agent: distilled water (300-: (50-100): (0-20): (5-15): (2000-10000) to form a mixed solution;
heating the mixed solution to a preset temperature and stirring to age the mixed solution;
heating the aged mixed solution until hydrothermal crystallization reaction occurs to form a suspension;
carrying out solid-liquid separation on the suspension, and washing to be neutral;
and drying the washed material to prepare the repairing agent.
The repairing agent prepared by the preparation method has more remarkable cation exchange property, adsorbability and shape selectivity, removes heavy metals in a water body through the actions of ion exchange, adsorption and fixation and the like, and can effectively repair heavy metal pollution in underground water.
In one embodiment, the hydroxyapatite is prepared from animal bones, and the main inorganic component in the animal bones is hydroxyapatite, and the content of the hydroxyapatite can reach 70%. Obtaining hydroxyapatite from animal bones can reduce the cost of hydroxyapatite.
In one embodiment, the predetermined temperature is 40 ℃ to 90 ℃, the stirring speed is 100r/min to 500r/min, and the aging time is 4h to 8 h. Under the conditions of this example, the material for preparing the repair agent can be effectively precipitated. The stirring process can be carried out by adopting a stirring kettle.
In one embodiment, in the process of heating the aged mixed solution to generate the hydrothermal crystallization reaction, the heating temperature is 100-200 ℃, and the reaction time is 1d-3 d.
In one embodiment, during the solid-liquid separation of the suspension, a suction filtration or a centrifugation mode is adopted. The solid-liquid separation of the suspension can be effectively realized by both suction filtration and centrifugal separation modes.
In one embodiment, in the process of drying the washed material, the drying temperature is 80-110 ℃, and the drying time is 8-16 h. Washing may be performed using distilled water. After washing, the repairing agent can be effectively dried under the drying condition and obtained. For example, a cake produced after solid-liquid separation can be washed with distilled water.
According to another embodiment of the present disclosure, there is provided an application method of a remediation agent for heavy metal contaminated groundwater, as shown in fig. 1, the application method including:
preparing a remediation agent for heavy metal contaminated groundwater as in the above example;
mixing a repairing agent and a binder, and forming into a three-dimensional structure;
and placing the formed repairing agent at the downstream of the heavy metal polluted groundwater pollution feather.
In this embodiment, the repair agent is mixed with a binder to form a three-dimensional structure, such as a cylinder, a honeycomb, or other three-dimensional structure. The three-dimensional structure is arranged at the downstream of the heavy metal polluted underground water pollution plume to realize the restoration effect, and the heavy metal polluted underground water passes through the restoration agent when flowing through the pollution plume in the restoration process. The repairing agent can play roles of ion exchange, adsorption and fixation and the like, thereby removing heavy metal pollution in water.
The repairing agent is formed into a three-dimensional structure, so that the range of the action of the repairing agent can be enlarged, and the problem that the repairing agent cannot be repaired when the repairing agent is too small in volume and washed away by water flow can be solved. The repairing agent with the three-dimensional structure can effectively repair underground water polluted by heavy metals in a placed in-situ manner. The repairing agent is environment-friendly, and the repairing process does not cause secondary pollution.
The process of repairing groundwater by the repairing agent is simulated in the following examples, so that the repairing effect of the repairing agent is tested through experiments.
The main experimental device required by the simulation process comprises a water distribution tank, a peristaltic pump, a reaction column and a water collecting tank. The reaction column is made of organic glass, the inner diameter is 15cm, the height is 70cm, 10cm of quartz sand is filled at the bottom and the top of the reaction column respectively, and the repairing agent in the disclosure is filled in the middle of the reaction column. The water in the water distribution tank is flushed by the peristaltic pump to enter the reaction column, and then flows out of the reaction column to enter the water collection tank. Wherein the flow direction of water from the reaction column is from bottom to top. Wherein the peristaltic pump controls the flow velocity of water flow to be 2.5 cm.h-1-3.0cm·h-1And a sampling port is arranged at the position where the reaction column flows out. The method comprises the following specific steps:
example 1
Preparing groundwater polluted by single heavy metal by adopting chromium chloride, wherein the initial concentration of Cr (II) is 1 mg.L-1. The contaminated groundwater after the configuration was allowed to flow through the experimental apparatus and sampled at the sampling ports on days 7, 15 and 30 respectively for detection, and the results are shown in the following table.
Reaction time (sky) 7 15 30
Heavy Metal concentration (mg/L) 0.42 0.11 0.025
Removal Rate (%) 58.00% 89.00% 97.50%
Example 2
The potassium dichromate is adopted to prepare the underground water polluted by single heavy metal, and the initial concentration of Cr (VI) is 10 mg.L-1. The contaminated groundwater after the configuration was allowed to flow through the experimental apparatus and sampled at the sampling ports on days 7, 15 and 30 respectively for detection, and the results are shown in the following table.
Reaction time (sky) 7 15 30
Heavy Metal concentration (mg/L) 5.94 2.36 0.18
Removal Rate (%) 40.60% 76.40% 92.00%
Example 3
Preparing underground water polluted by single heavy metal by adopting nickel chloride, wherein the initial concentration of Ni (II) is 10 mg.L-1. The polluted underground water after being configured flows through the experimental device,and samples were taken at the sampling ports on day 7, day 15 and day 30, respectively, and the results of the measurements are shown in the following table.
Reaction time (sky) 7 15 30
Heavy Metal concentration (mg/L) 4.22 1.29 0.070
Removal Rate (%) 57.80% 87.10% 99.30%
Example 4
Preparing groundwater polluted by single heavy metal by adopting copper sulfate, wherein the initial concentration of Cu (II) is 50 mg.L-1. The contaminated groundwater after the configuration was allowed to flow through the experimental apparatus and sampled at the sampling ports on days 7, 15 and 30 respectively for detection, and the results are shown in the following table.
Reaction time (sky) 7 15 30
Heavy Metal concentration (mg/L) 21.40 9.53 0.80
Removal Rate (%) 57.20% 80.94% 98.40%
Example 5
Cadmium chloride, potassium dichromate, nickel chloride and copper sulfate are adopted to prepare underground water polluted by single heavy metal, and the initial concentrations of Cd (II), Cr (VI), Ni (II) and Cu (II) are respectively 0.5 mg.L-1、5mg·L-1、10mg·L-1And 20 mg. L-1. The contaminated groundwater after the configuration was allowed to flow through the experimental apparatus and sampled at the sampling ports on days 7, 15 and 30 respectively for detection, and the results are shown in the following table.
Figure BDA0002462493380000071
According to the test results of the embodiment, the repairing agent disclosed by the invention can effectively remove heavy metal pollutants in underground water, the removal rate is obviously improved along with the increment of time, and the repairing agent can more effectively remove the heavy metal pollutants in the underground water.
Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.

Claims (11)

1. A remediation agent for heavy metal contaminated groundwater, wherein the remediation agent comprises, in admixture: hydroxyapatite, silicate minerals, alkali and a template agent;
the mol ratio among the components is as follows: hydroxyapatite: silicate mineral: alkali: templating agent (300-: (50-100): (0-20): (5-15).
2. The remediation agent for heavy metal contaminated groundwater according to claim 1, further comprising distilled water, wherein the molar ratio of the distilled water is 2000-10000.
3. The remediation agent for heavy metal contaminated groundwater of claim 1, wherein the silicate mineral comprises at least one of kaolin, bentonite, illite, sepiolite, attapulgite, zeolite, and diatomaceous earth.
4. The remediation agent for heavy metal contaminated groundwater of claim 1, wherein the templating agent comprises at least one of n-butylamine, diethanolamine, tetrapropylammonium hydride, tetrapropylammonium bromide, tetrapropylammonium hydroxide, hexylamine, and hexamethylenediamine.
5. The remediation agent for heavy metal contaminated groundwater according to claim 1, wherein the base comprises: at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and calcium carbonate.
6. A preparation method of a remediation agent for heavy metal contaminated groundwater comprises the following steps:
preparing raw materials, and taking hydroxyapatite as a raw material according to a molar ratio: silicate mineral: alkali: template agent: distilled water (300-: (50-100): (0-20): (5-15): (2000-10000) to form a mixed solution;
heating the mixed solution to a preset temperature and stirring to age the mixed solution;
heating the aged mixed solution until hydrothermal crystallization reaction occurs to form a suspension;
carrying out solid-liquid separation on the suspension, and washing to be neutral;
and drying the washed material to prepare the repairing agent.
7. A method for preparing a remediation agent for heavy metal contaminated groundwater according to claim 6, wherein the predetermined temperature is 40 ℃ to 90 ℃, the stirring speed is 100r/min to 500r/min, and the aging time is 4h to 8 h.
8. The method for preparing a remediation agent for heavy metal contaminated groundwater of claim 6, wherein in the process of heating the aged mixed solution to hydrothermal crystallization reaction, the heating temperature is 100 ℃ to 200 ℃ and the reaction time is 1d to 3 d.
9. The preparation method of the remediation agent for heavy metal contaminated groundwater according to claim 6, wherein a suction filtration or centrifugation manner is adopted in the solid-liquid separation process of the suspension.
10. The method for preparing a remediation agent for heavy metal contaminated groundwater of claim 6, wherein in the drying of the washed material, the drying temperature is 80 ℃ to 110 ℃ and the drying time is 8h to 16 h.
11. An application method of a remediation agent for heavy metal contaminated groundwater, wherein the remediation agent comprises the following steps:
preparing a remediation agent for heavy metal contaminated groundwater as claimed in any one of claims 1 to 5;
mixing a repairing agent and a binder, and forming into a three-dimensional structure;
and placing the formed repairing agent at the downstream of the heavy metal polluted groundwater pollution feather.
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