CN113979508B - Filling material of permeable reactive barrier, preparation method and application - Google Patents
Filling material of permeable reactive barrier, preparation method and application Download PDFInfo
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- CN113979508B CN113979508B CN202111401863.6A CN202111401863A CN113979508B CN 113979508 B CN113979508 B CN 113979508B CN 202111401863 A CN202111401863 A CN 202111401863A CN 113979508 B CN113979508 B CN 113979508B
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- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention discloses a filling material for a permeable reactive barrier, a preparation method and application, belonging to the technical field of underground water environmental pollution prevention and control, and the filling material for the permeable reactive barrier is mainly prepared from the following raw materials, by weight, 5-20 parts of zero-valent iron, 30-50 parts of activated carbon, 30-50 parts of tourmaline, 10-20 parts of a binder and 3-10 parts of a pore-forming agent. The provided filling material is solid spherical porous small particles, the main components of the filling material are zero-valent iron, activated carbon and tourmaline, the auxiliary forming material comprises a bonding agent and a pore-forming agent, the zero-valent iron and the activated carbon can form an iron-carbon primary battery in an underground water environment and have an iron-carbon micro-electrolysis effect, the tourmaline in the filling material has an infrared emission characteristic, the emitted infrared rays can enable water molecules to vibrate, and partial hydrogen bonds are broken, so that a water molecule cluster mechanism is reduced, the permeability is increased, the blockage of a reaction wall is relieved, the service life of the filling material is prolonged, and the removal effect of petroleum pollutants is improved.
Description
Technical Field
The invention relates to the technical field of underground water environmental pollution prevention and treatment, and particularly relates to a filling material for a permeable reactive barrier, a preparation method and application.
Background
With the continuous development of petrochemical industry, the extraction and refining of petroleum are increased, petroleum leakage is inevitable during the extraction, storage and refining, and the petroleum leakage is estimated to be about 1 \ 1093 every year around the world 9 The method is characterized in that ton of petroleum and products thereof enter the environment through various ways, leaked petroleum and products thereof enter underground water through permeation to cause pollution of the underground water, petroleum substances have 'three-cause effect', not only have serious influence on the environment, but also cause great harm to human beings, and have great significance in repairing the underground water polluted by the petroleum hydrocarbons.
The permeable reactive barrier technology is used as an underground water in-situ remediation technology, has the characteristics of good treatment effect, long-term treatment and the like in remediation of petroleum-polluted underground water, and has the important one that the selection of filling materials is selected, aiming at petroleum-polluted substances, the widely used filling materials mainly comprise 3 types, namely, adsorption type, redox type and microbial degradation type, the adsorption type comprises activated carbon, scoria, turfy soil, zeolite and the like, the redox type mainly comprises zero-valent iron and a bimetallic system thereof, and the microbial degradation filling materials mainly comprise some oxygen-releasing agents and provide oxygen for microbes; the filling materials are single in use and are often single in use in practical experimental research, the treatment effect on single target pollutants is good, but the effect is not ideal when the petroleum type mixed pollutants with complex components are treated, the multiple filling materials are compounded for use, the types of pollutants treated by the permeable reactive barrier can be increased by utilizing the synergistic effect among the filling materials, so that the removal effect of the composite filling materials on the petroleum type pollutants is improved, therefore, the mutual matching use among different filling materials is an effective way for improving the treatment effect of the petroleum type pollutants in underground water, and the key point is the selection of the matching materials and the corresponding proportion.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a filling material of a permeable reactive barrier, a preparation method and application.
The invention is realized in the following way:
the invention provides a filling material for a permeable reactive barrier, which is prepared by mixing 5-20 parts of zero-valent iron, 30-50 parts of activated carbon, 30-50 parts of tourmaline, 10-20 parts of a binder and 3-10 parts of a pore-forming agent.
In a second aspect, the present invention further provides a method for preparing the above filling material, which comprises: the raw materials are uniformly mixed according to a proportion, then the mixture is mixed with water to form slurry, and the slurry is granulated and calcined to obtain the filling material.
In a third aspect, the invention also provides an application of the filling material as a filling medium of the permeable reactive barrier in the aspect of in-situ treatment of the polluted underground water of the petrochemical site.
The invention has the following beneficial effects:
the invention provides a filling material for a permeable reactive barrier, a preparation method and application thereof, wherein the filling material for the permeable reactive barrier is mainly prepared from the following raw materials, by weight, 5-20 parts of zero-valent iron, 30-50 parts of activated carbon, 30-50 parts of tourmaline, 10-20 parts of a binder and 3-10 parts of a pore-forming agent. The main components of the filling material are zero-valent iron, activated carbon and tourmaline, the auxiliary forming material comprises a bonding agent and a pore-forming agent, the zero-valent iron and the activated carbon can form an iron-carbon galvanic cell in an underground water environment and have the iron-carbon micro-electrolysis effect, the tourmaline in the filling material has the infrared emission characteristic, the emitted infrared rays can enable water molecules to vibrate, and partial hydrogen bonds are broken, so that the water molecule cluster mechanism is reduced, the permeability is increased, the blockage of a reaction wall is relieved, the service life of the filling material is prolonged, and the removal effect of petroleum pollutants is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a photograph showing the appearance of a filling material for a permeable reactive barrier according to an embodiment of the present invention;
fig. 2 is a photograph of the filling material of the permeable reactive barrier provided by the embodiment of the present invention at a magnification of 40 times.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The embodiment of the invention provides a filling material of a permeable reactive wall, a preparation method and application, the filling material is solid spherical porous small particles, the main components are zero-valent iron, active carbon and tourmaline, an auxiliary forming material comprises a binder and a pore-forming agent, the main active reactive materials of the filling material are the zero-valent iron and the active carbon, and the zero-valent iron and the active carbon can form an iron-carbon primary battery in a groundwater environment and have an iron-carbon micro-electrolysis effect.
Reaction of produced Fe 3+ Has strong oxidizability, can effectively oxidize long-chain petroleum hydrocarbon to decompose the long-chain petroleum hydrocarbon into small molecules, is beneficial to removing petroleum pollutants, and the pH value of underground water rises after reaction, OH - Will react with Fe 3+ Generating ferric hydroxide precipitate which has flocculation effect and can enhance the adsorption capacity of the filling material and improve the removal effect of the filling material on petroleum pollutants, and in addition, the filling material can also be used by loading microorganisms, and the increase of the pH can increase the biodegradability of underground water; the tourmaline in the filling material has infrared emission characteristic, and the emitted infrared rays can make water molecules vibrate and part of hydrogen bonds break, therebyThe water molecule cluster mechanism is reduced, the permeability is increased, the blockage of the reaction wall is relieved, the service life of the filling material is prolonged, and the removal effect of petroleum pollutants is improved.
In order to achieve the use effect, the technical scheme adopted by the invention is as follows:
in a first aspect, the embodiment of the invention provides a filling material for a permeable reactive wall, which is mainly prepared from the following raw materials, by weight, 5-20 parts of zero-valent iron, 30-50 parts of activated carbon, 30-50 parts of tourmaline, 10-20 parts of a binder and 3-10 parts of a pore-forming agent, wherein the raw materials are in proportion related to the accessibility, the biological activity, the pressure bearing capacity and the pore structure of a molded primary battery filled with the filling material. When the ratio is changed, the removal effect of the filling material on the contaminants is not good.
The embodiment of the invention provides a filling material of a permeable reactive wall, which mainly comprises zero-valent iron, activated carbon and tourmaline, wherein an auxiliary forming material comprises a bonding agent and a pore-forming agent, and the main active reactive material zero-valent iron and the activated carbon can form an iron-carbon primary battery in a groundwater environment and have an iron-carbon micro-electrolysis effect.
The working principle of the iron-carbon micro-electrolysis is as follows:
iron-carbon microelectrolysis is based on galvanic reactions in electrochemistry. When iron and carbon are immersed in the electrolyte solution, a potential difference of 1.2V exists between Fe and C, so that countless micro-battery systems are formed, and an electric field is formed in the action space of the micro-battery systems.
And (3) iron-carbon primary battery reaction:
anode:
cathode:
the aerobic environment, the cathode reaction is as follows:
anaerobic environment, the cathode reaction is as follows:
the cathode reaction generates a large amount of nascent H and O, and under the condition of subacidity, the active ingredients can generate oxidation-reduction reaction with a plurality of components in the wastewater, so that the organic macromolecules are subjected to chain scission degradation, thereby eliminating the chromaticity of the organic wastewater and improving the biodegradability of the wastewater.
Nascent state Fe produced by anodic reaction 2+ Has stronger reducing capability, can reduce certain organic matters, can open double bonds of certain unsaturated groups (such as carboxyl-COOH, azo-N = N-), and can decompose partial cyclic and long-chain organic matters which are difficult to degrade into micromolecular organic matters which are easy to biodegrade, thereby improving the biodegradability.
Aerobic environment, cathode reaction of produced Fe 3+ Has strong oxidizability, can effectively oxidize long-chain petroleum hydrocarbon to decompose the long-chain petroleum hydrocarbon into small molecules, is beneficial to removing petroleum pollutants, and the pH value of underground water rises after reaction, OH - Will react with Fe 3+ And generating ferric hydroxide precipitate which has flocculation effect and can enhance the adsorption capacity of the filling material and improve the removal effect of the filling material on petroleum pollutants.
Further, fe 2+ And Fe 3+ Is a good flocculant, especially nascent Fe 2+ Has higher adsorption-flocculation activity, can change iron ions into flocculent precipitates of hydroxides by adjusting the pH value of the wastewater, can adsorb suspended or colloidal micro-particles and organic macromolecules in the wastewater, and can be used forThe chroma of the waste water is reduced in one step, and simultaneously, part of organic pollutants are removed to purify the waste water.
Meanwhile, the filling material provided by the embodiment of the invention further comprises a binder and a pore-forming agent, wherein carbon and iron are wrapped in the porous spherical small particles, iron atoms and carbon atoms are mutually contained to form a framework to form a galvanic cell reaction, the proportion of the binder influences the pressure-bearing property of the filling material, and the proportion of the pore-forming agent influences the biological accessibility of the galvanic cell in the filling material. The iron-carbon contact does not have the layering problem of iron and carbon, so that the method is more favorable for transferring electrons, the charge efficiency is higher, and the removal efficiency of organic matters in the wastewater is higher.
In addition, the filling material can also be used by loading microorganisms, and the biodegradability of the underground water can be increased by the rising of the pH value; tourmaline in the filling material has the infrared emission characteristic, and the emitted infrared rays can enable water molecules to vibrate and part of hydrogen bonds to break, so that a water molecule cluster mechanism is reduced, the permeability is increased, the blockage of a reaction wall is relieved, the service life of the filling material is prolonged, and the removal effect on petroleum pollutants is improved.
In an optional embodiment, the filling material is mainly prepared from the following raw materials, by weight, 10-15 parts of zero-valent iron, 35-45 parts of activated carbon, 35-45 parts of tourmaline, 10-15 parts of a binder and 5-8 parts of a pore-forming agent.
In an alternative embodiment, the binder includes at least one of bentonite, clay, and the like having high temperature sintering properties.
In an alternative embodiment, the pore former comprises at least one of ammonium bicarbonate, ammonium chloride, and paraffin wax microspheres.
In an alternative embodiment, the filler material is spherical in shape and the solid spherical particles are porous spherical particles.
In an alternative embodiment, the filler material particle size distribution is: the 2-3mm particles are greater than 90% (by volume), preferably greater than 95% (by volume).
In an alternative embodiment, the filler material has a porosity of more than 50%, preferably more than 55%.
In an alternative embodiment, the compressive strength of the filler material is above 0.5MPa, preferably above 0.7 MPa.
In a second aspect, an embodiment of the present invention further provides a method for preparing a filling material for a permeable reactive barrier, including the following steps:
(1) Weighing a proper amount of zero-valent iron powder with the granularity of 100-200 meshes and putting the zero-valent iron powder into a beaker; (2) Weighing a proper amount of activated carbon powder with the granularity of 100-200 meshes in a beaker; (3) Putting enough granular tourmaline into a grinder, grinding into powder, and sieving with a sieve to obtain 100-200 mesh tourmaline powder; (4) Weighing a proper amount of 100-200 meshes of tourmaline powder and putting the tourmaline powder into the beaker; (5) weighing a proper amount of bentonite and putting the bentonite into a beaker; (6) weighing a proper amount of ammonium bicarbonate and putting the ammonium bicarbonate into a beaker; (7) Mechanically mixing the components in the beaker uniformly, adding a proper amount of water, stirring uniformly, and putting into a granulator to form spherical particles; (8) Covering the surface of the spherical particles with fine sand, and primarily drying for 1 hour in a vacuum drying oven at 50 ℃; (9) Covering the surface of the spherical particles with fine sand, roasting for 1-2 hours in a muffle furnace at 400-700 ℃, naturally cooling, and sieving to obtain spherical particles with the diameter of 2-3mm, wherein the spherical particles are used as the filling material of the invention. In the preparation process of the filling material, the fine sand is covered to avoid the adhesion among the small balls, the subsequent calcining temperature is 400-700 ℃, if the calcining temperature is too low, the pressure bearing performance of the finished filling material is poor, and if the calcining temperature is too high, the active carbon loss is serious, and the pore structure is influenced.
In a third aspect, the invention also provides an application of the filling material as a filling medium of the permeable reactive barrier in the aspect of in-situ treatment of the polluted underground water of the petrochemical site.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Weighing 138.2g of 200-mesh iron powder, putting the 200-mesh iron powder into a 2L beaker, weighing 414.6g of 200-mesh activated carbon (coconut shell) in the 2L beaker, weighing 414.6g of the 200-mesh tourmaline powder ground into powder, putting the 200-mesh activated carbon into the 2L beaker, mechanically and uniformly mixing the 3 materials in the beaker, gradually adding 100mL of distilled water into the beaker, continuously stirring, weighing 188.4g of bentonite, adding the bentonite into the beaker, weighing 100.5g of ammonium bicarbonate, adding 50mL of distilled water into the beaker, finally uniformly stirring the slurry in the beaker, preparing the slurry into 2-3mm spherical particles in a granulator, covering the surfaces of the spherical particles with fine sand after molding, primarily drying for 1 hour in a 50 ℃ vacuum drying oven, covering the surfaces of the spherical particles with fine sand after naturally cooling to room temperature, naturally cooling for 1 hour at 400 ℃, naturally cooling in the oven, removing the fine sand on the surfaces, and roasting to obtain 2-3mm spherical particles which are used as the spherical filling material of the invention with 1 mm.
Example 2
138.2g of 200-mesh iron powder is weighed and placed in a 2L beaker, 414.6g of 200-mesh activated carbon (coconut shell) is weighed and placed in a 2L beaker, 414.6g of the 200-mesh tourmaline powder ground into powder is weighed and placed in a 2L beaker, the 3 materials are mechanically and uniformly mixed in the beaker, 100mL of distilled water is gradually added into the beaker, stirring is continuously carried out, 226.1g of bentonite is weighed and added into the beaker, 62.8g of ammonium bicarbonate is weighed and added into the beaker, 50mL of distilled water is added into the beaker, finally the slurry in the beaker is uniformly stirred, the slurry is made into 2-3mm spherical particles in a granulator, the surfaces of the spherical particles are covered with fine sand after molding, the spherical particles are preliminarily dried in a 50 ℃ vacuum drying oven for 1 hour, the fine sand is also covered with the surfaces of the spherical particles after naturally cooling to room temperature, the spherical particles are naturally cooled for 1 hour in a muffle furnace, the fine sand on the surfaces are removed, and the spherical particles with the size of 2-3mm are screened out and used as the filling material of the invention, which is 2-3 mm.
Example 3
Weighing 138.2g of 200-mesh iron powder, putting the 200-mesh iron powder into a 2L beaker, weighing 414.6g of 200-mesh activated carbon (coconut shell) in the 2L beaker, weighing 414.6g of the 200-mesh tourmaline powder ground into powder, putting the 3 materials in the beaker, mechanically and uniformly mixing the 3 materials, gradually adding 100mL of distilled water into the beaker, continuously stirring, weighing 251.2g of bentonite, adding the bentonite into the beaker, weighing 37.7g of ammonium bicarbonate, adding 50mL of distilled water into the beaker, finally uniformly stirring the slurry in the beaker, preparing the slurry into 2-3mm spherical particles in a granulator, covering the surfaces of the spherical particles with fine sand after molding, primarily drying the spherical particles in a 50 ℃ vacuum drying oven for 1 hour, covering the surfaces of the spherical particles with the fine sand after naturally cooling to room temperature, covering the surfaces of the spherical particles with the fine sand at 400 ℃ for 1 hour, naturally cooling the spherical particles, roasting the fine sand on the surfaces to obtain 2-3mm spherical particles, and taking the spherical particles as the invention filling material.
Example 4
Weighing 138.2g of 200-mesh iron powder, putting the 200-mesh iron powder into a 2L beaker, weighing 414.6g of 200-mesh activated carbon (coconut shell) in the 2L beaker, weighing 414.6g of the 200-mesh tourmaline powder ground into powder, putting the 200-mesh activated carbon into the 2L beaker, mechanically and uniformly mixing the 3 materials in the beaker, gradually adding 100mL of distilled water into the beaker, continuously stirring, weighing 188.4g of bentonite, adding the bentonite into the beaker, weighing 100.5g of ammonium bicarbonate, adding 50mL of distilled water into the beaker, finally uniformly stirring the slurry in the beaker, preparing the slurry into 2-3mm spherical particles in a granulator, covering the surfaces of the spherical particles with fine sand after molding, primarily drying in a 50 ℃ vacuum drying oven for 1 hour, covering the surfaces of the spherical particles with fine sand after naturally cooling to room temperature, covering the surfaces of the spherical particles with fine sand at the temperature of 500 ℃ for 1 hour, naturally cooling, roasting to obtain 2-3mm fine sand on the surfaces, and taking the spherical particles as the 4-mesh filling material of the invention.
Example 5
Weighing 138.2g of 200-mesh iron powder, putting the 200-mesh iron powder into a 2L beaker, weighing 414.6g of 200-mesh activated carbon (coconut shell) in the 2L beaker, weighing 414.6g of the 200-mesh tourmaline powder ground into powder, putting the 3 materials in the beaker, mechanically and uniformly mixing, gradually adding 100mL of distilled water into the beaker, continuously stirring, weighing 226.1g of bentonite, adding the bentonite into the beaker, weighing 62.8g of ammonium bicarbonate, adding 50mL of distilled water into the beaker, finally uniformly stirring the slurry in the beaker, preparing the slurry into 2-3mm spherical particles in a granulator, covering the surfaces of the spherical particles with fine sand after molding, primarily drying in a 50 ℃ vacuum drying oven for 1 hour, covering the surfaces of the spherical particles with the fine sand after naturally cooling to room temperature, naturally cooling for 1 hour in a muffle furnace for 1 hour, naturally cooling, removing the fine sand on the surfaces to obtain 2-3mm spherical particles, and taking the spherical particles as the 5-mm spherical filling material.
The macro and micro morphologies of the filling material of the permeable reactive wall provided by the above embodiment are shown in fig. 1 and fig. 2, fig. 1 is a photograph of the appearance of the filling material of the permeable reactive wall, and it can be seen from fig. 1 that the filling material is compact pellets with uniform particle size.
Fig. 2 is a photograph of the filling material for the permeable reactive barrier, magnified 40 times, and it can be seen from fig. 2 that it is a mixture of iron, activated carbon and tourmaline, which are wrapped with a binder, and the formed pellet does not contain a pore-forming agent because the pore-forming agent is decomposed during calcination.
Examples 6 to 10
The evaluation results of the removal effect of the filling material on the petroleum pollutants in the underground water are as follows:
the petroleum-polluted underground water removal experiment is simulated in the permeable reactive wall column reactor, the petroleum-polluted underground water removal effect of the filling material and the permeability coefficient of the filling material under the set conditions are evaluated, and the petroleum-polluted underground water removal experiment is compared with that of a single filling material. The simulated petroleum polluted underground water is prepared by stirring distilled water and diesel oil at a high speed for 1h under a stirrer according to a volume ratio of 100; the permeable reactive wall column reactor is cylindrical, the diameter of the bottom surface of the permeable reactive wall column reactor is 50mm, the length of the permeable reactive wall column reactor is 500mm, quartz sand with the length of 50mm is filled at a simulated water inlet in an experiment, then a filling material with the length of 400mm is filled, finally the quartz sand with the length of 50mm is filled, the filling materials are respectively 1-5 filling materials of the permeable reactive wall column reactor, zero-valent iron (200 meshes) and active carbon (200 meshes), and the permeability coefficient of the permeable reactive wall column reactor is measured after the filling; injecting the simulated petroleum polluted water into the inlet of the column reactor at the speed of 50mL/min by using a peristaltic pump, operating for 30d, taking inlet and outlet water samples, measuring the concentration of petroleum in the water by using an infrared oil measuring instrument, and calculating the removal rate.
TABLE 1 permeation coefficient of filler and removal effect on petroleum
As can be seen from the table above, the filling material provided by the embodiment of the invention can effectively remove petroleum pollutants in underground water, and has the effects of good treatment effect, long service life and the like.
Comparative example 1
Similar to the procedure of example 1, except that: no pore-forming agent is added, so that the contact between the primary cell and the petroleum hydrocarbon in the filler is poor, and the removal rate of the petroleum hydrocarbon is 38.6 percent.
Comparative example 2
Similar to the procedure of example 1, except that: the addition of less Fe results in less total cells in the filler, low petroleum hydrocarbon removal rate of 51.2%.
Comparative example 3
Similar to the procedure of example 1, except that: no adhesive is added, so that the pressure bearing performance of the finished filler is poor, and the finished filler cannot be used as a filler.
To sum up, the embodiment of the invention provides a filling material of a permeable reactive barrier, a preparation method and application, wherein the filling material of the permeable reactive barrier is mainly prepared from the following raw materials, by weight, 5-20% of zero-valent iron, 30-50% of activated carbon, 30-50% of tourmaline, 10-20% of a binder and 3-10% of a pore-forming agent. The main components of the filling material are zero-valent iron, activated carbon and tourmaline, the auxiliary forming material comprises a bonding agent and a pore-forming agent, the zero-valent iron and the activated carbon can form an iron-carbon primary battery in an underground water environment, the iron-carbon micro-electrolysis effect is achieved, the tourmaline in the filling material has an infrared emission characteristic, the emitted infrared rays can enable water molecules to vibrate, and partial hydrogen bonds are broken, so that a water molecule cluster mechanism is reduced, the permeability is increased, the blockage of a reaction wall is relieved, the service life of the filling material is prolonged, and the removal effect of petroleum pollutants is improved.
Compared with the prior art, the scheme provided by the embodiment of the invention has the following beneficial effects.
The filling material provided by the embodiment of the invention comprises zero-valent iron, activated carbon and tourmaline as main components, the auxiliary forming material comprises a bonding agent and a pore-forming agent, the zero-valent iron and the activated carbon as the main active components can form an iron-carbon galvanic cell in a groundwater environment and have an iron-carbon micro-electrolysis effect, the tourmaline has an infrared emission characteristic, and the bonding agent and the pore-forming agent of the auxiliary forming material can wrap the main components in spherical porous small particles, so that the carbon-iron galvanic cell is not layered, and the removal efficiency of organic matters in wastewater is improved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The filling material of the permeable reactive barrier is characterized by being mainly prepared from the following raw materials, by weight, 5-20 parts of zero-valent iron, 30-50 parts of activated carbon, 30-50 parts of tourmaline, 10-20 parts of a binder and 3-10 parts of a pore-forming agent, wherein the filling material is spherical porous particles, and the volume ratio of the spherical particles with the particle size of 2-3mm in the filling material is more than 90%; the porosity of the filling material is more than 50%; the compression strength of the filling material is more than 0.5 MPa.
2. The filling material of claim 1, which is prepared from (by weight parts) zero-valent iron 10-15, activated carbon 35-45, tourmaline 35-45, binder 10-15, and pore-forming agent 5-8.
3. The filling material of claim 1, wherein the binder comprises at least one of bentonite and clay.
4. The filler material of claim 1, wherein the pore former comprises at least one of ammonium bicarbonate, ammonium chloride, paraffin wax microspheres.
5. The filling material according to claim 1, wherein the filling material has a volume ratio of spherical particles with a particle size of 2-3mm of more than 95%.
6. The filling material of claim 1, wherein the filling material has a porosity greater than 55%.
7. The filling material according to claim 1, wherein the compressive strength of the filling material is 0.7MPa or more.
8. A method for preparing a filling material according to any of claims 1-7, characterized in that it comprises: the raw materials are uniformly mixed according to a proportion, then the mixture is mixed with water to form slurry, and the slurry is granulated and calcined to obtain the filling material.
9. The method as set forth in claim 8, wherein the zero-valent iron, the activated carbon and the tourmaline each have a particle size of 100-200 meshes.
10. The method according to claim 8, wherein the granulated particles are dried before the calcination.
11. The method according to claim 10, wherein the granulated material obtained by granulation is coated with fine sand and then dried at 40 to 90 ℃.
12. The preparation method of claim 10, wherein the dried granules are naturally cooled to room temperature, covered with fine sand again on the surface, calcined at 400-700 ℃ for 1-2 hours, naturally cooled, and sieved after removing the fine sand on the surface to obtain spherical porous granules, thus obtaining the filling material.
13. Use of the filling material according to claim 1 or the filling material prepared by the preparation method according to any one of claims 8 to 12 as a filling medium of a permeable reactive barrier for in-situ remediation of polluted groundwater in petrochemical sites.
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| CN114713837A (en) * | 2022-04-20 | 2022-07-08 | 桂林电子科技大学 | Nano zero-valent iron-carbon ceramsite, preparation method thereof and application thereof in wastewater treatment |
| CN115636460A (en) * | 2022-09-28 | 2023-01-24 | 昆明理工大学 | Method for in-situ remediation of heavy metal-organic composite polluted groundwater by using electrochemically-enhanced permeable reactive barrier |
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| CN101973610B (en) * | 2010-04-22 | 2013-08-07 | 吉林大学 | Method for in-situ remediation of petroleum hydrocarbon polluted underground water by taking tourmaline as additive medium |
| CN102583827B (en) * | 2012-03-01 | 2013-07-24 | 中国环境科学研究院 | Repairing system for double-layer permeable reaction wall, preparation method and application |
| CN102744041A (en) * | 2012-07-30 | 2012-10-24 | 山东省水利科学研究院 | Filling material used for removing permeable reactive barrier of nitrate and preparation method thereof |
| CN107235561B (en) * | 2017-08-04 | 2020-01-07 | 南京大学 | Permeable reaction wall composite material for groundwater polycyclic aromatic hydrocarbon pollution remediation and preparation method thereof |
| CN109179677A (en) * | 2018-10-24 | 2019-01-11 | 湖南新九方科技有限公司 | A kind of complex media PRB restorative procedure of chlorohydrocarbon polluted underground water |
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| CN112850891A (en) * | 2021-04-08 | 2021-05-28 | 广东开源环境科技有限公司 | Permeable reactive barrier system for biologically removing nitrite in underground water |
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