CN113979508A - Filling material for permeable reactive barrier, preparation method and application - Google Patents
Filling material for permeable reactive barrier, preparation method and application Download PDFInfo
- Publication number
- CN113979508A CN113979508A CN202111401863.6A CN202111401863A CN113979508A CN 113979508 A CN113979508 A CN 113979508A CN 202111401863 A CN202111401863 A CN 202111401863A CN 113979508 A CN113979508 A CN 113979508A
- Authority
- CN
- China
- Prior art keywords
- filling material
- parts
- tourmaline
- activated carbon
- zero
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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, in particular 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 oil are increased, and the inevitable oil leakage in the extraction, storage and refining is estimated to be about 1 х 10 annually all over the world9The 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 the important part in the technology lies in the selection of filling materials, 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, volcanic cinders, turfy soil, zeolite and the like, the redox type mainly uses zero-valent iron and a bimetallic system thereof, and the microbial degradation filling materials mainly comprise some oxygen releasing agents and provide oxygen for microorganisms; 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 this, the 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 by the following steps:
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 not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment of the invention provides a filling material of a permeable reactive barrier, a preparation method and application, the filling material is solid spherical porous small particles, the main components of the filling material are zero-valent iron, activated carbon and tourmaline, an auxiliary forming material comprises a bonding agent and a pore-forming agent, the main active reactive materials of the filling material are the zero-valent iron and the activated carbon, the 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.
Fe produced by the reaction3+Has strong oxidability, 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 can be increased and OH can be generated after the reaction-Will react with Fe3+Generating ferric hydroxide precipitate, wherein the ferric hydroxide precipitate has a flocculation effect, 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 pH can increase the biodegradability of underground water; 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 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 barrier, 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 bioactivity, 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 barrier, 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 of the zero-valent iron and the activated carbon can form an iron-carbon primary battery in a groundwater environment and has 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, cathode reaction 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 reaction2+Has strong reducing power and can make some organic mattersThe reduction can also open the double bonds of some unsaturated groups (such as carboxyl-COOH, azo-N ═ N-), so that part of cyclic and long-chain organic matters which are difficult to degrade can be decomposed into small molecular organic matters which are easy to biodegrade, thereby improving the biodegradability.
In an aerobic environment, Fe produced by cathodic reaction3+Has strong oxidability, 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 can be increased and OH can be generated after the reaction-Will react with Fe3+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, Fe2+And Fe3+Is a good flocculant, especially nascent Fe2+Has higher adsorption-flocculation activity, can change iron ions into flocculent precipitates of hydroxides by adjusting the pH value of the wastewater, adsorbs suspended or colloid-state micro particles and organic macromolecules in the wastewater, can further reduce the chromaticity of the wastewater, and simultaneously removes partial organic pollutants to purify the wastewater.
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.
Moreover, the filling material can also be used by loading microorganisms, and the biodegradability of the underground water can be increased by the increase 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 preparation method of a filling material for a permeable reactive barrier, including the following steps:
(1) weighing a proper amount of 200-mesh zero-valent iron powder with the granularity of 100-; (2) weighing a proper amount of active carbon powder with the granularity of 100-200 meshes in a beaker; (3) putting enough granular tourmaline into a grinder, grinding the granular tourmaline into powder, and screening out 100-200-mesh tourmaline powder by using a screen; (4) weighing a proper amount of 100-200-mesh 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 the temperature of 400-700 ℃, naturally cooling, and sieving to obtain spherical particles with the particle size 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 calcination temperature is 400-700 ℃, if the calcination temperature is too low, the pressure bearing performance of the finished product filler is poor, and if the calcination temperature is too high, the loss of the activated carbon 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, placing the 200-mesh iron powder into a 2L beaker, weighing 414.6g of 200-mesh activated carbon (coconut shell) into a 2L beaker, weighing 414.6g of the 200-mesh tourmaline powder ground into powder, placing the 3 materials into a 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 the fine sand after naturally cooling to room temperature, roasting in a muffle furnace at 400 ℃ for 1 hour, naturally cooling, removing fine sand on the surface, and sieving to obtain spherical particles of 2-3mm, wherein the spherical particles are used as the filling material 1.
Example 2
Weighing 138.2g of 200-mesh iron powder, placing the 200-mesh iron powder into a 2L beaker, weighing 414.6g of 200-mesh activated carbon (coconut shell) into a 2L beaker, weighing 414.6g of the 200-mesh tourmaline powder ground into powder, placing the 3 materials 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 226.1g of bentonite, adding the bentonite into the beaker, weighing 62.8g of ammonium bicarbonate, adding 50mL of distilled water into the beaker, uniformly stirring the slurry in the beaker, preparing the slurry into spherical particles of 2-3mm 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, roasting in a muffle furnace at 400 ℃ for 1 hour, naturally cooling, removing fine sand on the surface, and sieving to obtain spherical particles of 2-3mm, wherein the spherical particles are used as the filling material 2.
Example 3
Weighing 138.2g of 200-mesh iron powder, placing the 200-mesh iron powder into a 2L beaker, weighing 414.6g of 200-mesh activated carbon (coconut shell) into a 2L beaker, weighing 414.6g of the 200-mesh tourmaline powder ground into powder, placing the 3 materials into a 2L beaker, mechanically and uniformly mixing the 3 materials in the beaker, 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 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, roasting in a muffle furnace at 400 ℃ for 1 hour, naturally cooling, removing fine sand on the surface, and sieving to obtain spherical particles of 2-3mm, wherein the spherical particles are used as the filling material 3.
Example 4
Weighing 138.2g of 200-mesh iron powder, placing the 200-mesh iron powder into a 2L beaker, weighing 414.6g of 200-mesh activated carbon (coconut shell) into a 2L beaker, weighing 414.6g of the 200-mesh tourmaline powder ground into powder, placing the 3 materials into a 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, uniformly stirring the slurry in the beaker, preparing the slurry into spherical particles of 2-3mm 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, roasting in a muffle furnace for 1 hour at 500 ℃, naturally cooling, removing fine sand on the surface, and sieving to obtain spherical particles of 2-3mm, wherein the spherical particles are used as the filling material 4.
Example 5
Weighing 138.2g of 200-mesh iron powder, placing the 200-mesh iron powder into a 2L beaker, weighing 414.6g of 200-mesh activated carbon (coconut shell) into a 2L beaker, weighing 414.6g of the 200-mesh tourmaline powder ground into powder, placing the 3 materials 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 226.1g of bentonite, adding the bentonite into the beaker, weighing 62.8g of ammonium bicarbonate, adding 50mL of distilled water into the beaker, uniformly stirring the slurry in the beaker, preparing the slurry into spherical particles of 2-3mm 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, roasting in a muffle furnace for 1 hour at 500 ℃, naturally cooling, removing fine sand on the surface, and sieving to obtain spherical particles of 2-3mm, wherein the spherical particles are used as the filling material 5.
The macro and micro morphologies of the filling material of the permeable reactive barrier 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 barrier, and it can be seen from fig. 1 that the filling material is compact spheres with uniform particle size.
Fig. 2 is a photograph of the filling material of the permeable reactive barrier at 40 times magnification, and it can be seen from fig. 2 that it is a mixture of iron, activated carbon and tourmaline coated 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 pollutant removal effect of the filling material under the set condition and the permeability coefficient of the filling material are evaluated, and the petroleum pollutant removal effect 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 100:1, standing for 2 h, taking a lower-layer solution after layering to obtain the simulated petroleum polluted underground water, and measuring the concentration range of petroleum in the simulated petroleum polluted underground water by using an infrared oil measuring instrument to be 10-20 mg/L; 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 Effect on removing 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 cell number in the stuffing, low petroleum hydrocarbon eliminating 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 (10)
1. The filling material for 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.
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 of claim 1, wherein the filling material is spherical porous particles;
preferably, the volume ratio of spherical particles with the particle diameter of 2-3mm in the filling material is more than 90%, and more preferably, the volume ratio is more than 95%;
preferably, the porosity of the filler material is above 50%, more preferably above 55%.
6. The filling material according to claim 1, wherein the compressive strength of the filling material is above 0.5MPa, more preferably above 0.7 MPa.
7. A method for preparing a filling material according to any of claims 1-6, 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.
8. The preparation method as claimed in claim 7, wherein the particle sizes of the zero-valent iron, the activated carbon and the tourmaline are all 100-200 mesh.
9. The method according to claim 7, wherein the granulated material is dried before calcination;
preferably, the surface of the granulated substance obtained by granulation is covered with fine sand, and then dried at 40-90 ℃;
preferably, the dried particles are naturally cooled to room temperature, the surface is covered with fine sand again, the particles are calcined at the temperature of 400-700 ℃ for 1-2 hours, the particles are naturally cooled, the fine sand on the surface is removed, and the particles are sieved to obtain spherical porous particles, so that the filling material is obtained.
10. Use of the filling material according to claim 1 or the filling material prepared by the preparation method according to any one of claims 7 to 9 as a filling medium of a permeable reactive barrier in-situ remediation of polluted groundwater in a petrochemical site.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111401863.6A CN113979508B (en) | 2021-11-19 | 2021-11-19 | Filling material of permeable reactive barrier, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111401863.6A CN113979508B (en) | 2021-11-19 | 2021-11-19 | Filling material of permeable reactive barrier, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113979508A true CN113979508A (en) | 2022-01-28 |
| CN113979508B CN113979508B (en) | 2023-03-17 |
Family
ID=79750198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111401863.6A Active CN113979508B (en) | 2021-11-19 | 2021-11-19 | Filling material of permeable reactive barrier, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113979508B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973610A (en) * | 2010-04-22 | 2011-02-16 | 吉林大学 | Method for in-situ remediation of petroleum hydrocarbon polluted underground water by taking tourmaline as additive medium |
| 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 |
| GB201219329D0 (en) * | 2012-03-01 | 2012-12-12 | Chinese Res Academy Of Enviromental Sciences | Double-layer permeable reactive barrier remediation system and its constructive method and application |
| CN107235561A (en) * | 2017-08-04 | 2017-10-10 | 南京大学 | It is a kind of for permeable reaction wall composite of PAHs in groundwater pollution amelioration 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 |
| 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 |
| CN113185194A (en) * | 2021-04-27 | 2021-07-30 | 山东大学 | Porous permeable geopolymer material and preparation method and application thereof |
| CN114054484A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Permeable reactive barrier and method for repairing polluted underground water by permeable reactive barrier |
-
2021
- 2021-11-19 CN CN202111401863.6A patent/CN113979508B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973610A (en) * | 2010-04-22 | 2011-02-16 | 吉林大学 | Method for in-situ remediation of petroleum hydrocarbon polluted underground water by taking tourmaline as additive medium |
| GB201219329D0 (en) * | 2012-03-01 | 2012-12-12 | Chinese Res Academy Of Enviromental Sciences | Double-layer permeable reactive barrier remediation system and its constructive 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 |
| CN107235561A (en) * | 2017-08-04 | 2017-10-10 | 南京大学 | It is a kind of for permeable reaction wall composite of PAHs in groundwater pollution amelioration 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 |
| CN114054484A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Permeable reactive barrier and method for repairing polluted underground water by permeable reactive barrier |
| 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 |
| CN113185194A (en) * | 2021-04-27 | 2021-07-30 | 山东大学 | Porous permeable geopolymer material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| RUOLIN CAO ET AL: "Enhanced remediation of Cr(VI)-contaminated groundwater by coupling electrokinetics with ZVI/Fe 3 O 4 /AC-based permeable reactive barrier", 《JOURNAL OF ENVIRONMENTAL SCIENCES》 * |
| 刘子璐等: "Fe~0可渗透反应墙处理地下水污染的研究现状与展望", 《应用化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113979508B (en) | 2023-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Soltani et al. | Silica nanopowders/alginate composite for adsorption of lead (II) ions in aqueous solutions | |
| CN113979508B (en) | Filling material of permeable reactive barrier, preparation method and application | |
| CN111871389B (en) | Preparation method of lanthanum hydroxide modified aerogel dephosphorization adsorbent | |
| KR101409721B1 (en) | Biochar-Alginate bead for removal of heavy metal using biochar powder and the method of manufacturing the same | |
| Sanguanpak et al. | Porous metakaolin-based geopolymer granules for removal of ammonium in aqueous solution and anaerobically pretreated piggery wastewater | |
| Zhu et al. | High-efficiency and low-cost α-Fe2O3 nanoparticles-coated volcanic rock for Cd (II) removal from wastewater | |
| Du et al. | La-doped activated carbon as high-efficiency phosphorus adsorbent: DFT exploration of the adsorption mechanism | |
| Song et al. | Enhanced synergistic removal of Cr (VI) and Cd (II) with bi-functional biomass-based composites | |
| CN103464102A (en) | Porous composite adsorbing agent for removing stream substrate sludge contamination and preparation process of agent | |
| Beni et al. | Design and optimization of a new reactor based on biofilm-ceramic for industrial wastewater treatment | |
| Xu et al. | Adsorption of phosphorus from eutrophic seawater using microbial modified attapulgite-cleaner production, remove behavior, mechanism and cost-benefit analysis | |
| CN113634228B (en) | Sludge biochar loaded magnesium-iron oxide composite material for removing lead and cadmium in water and preparation method and application thereof | |
| Zhou et al. | A novel absorbent of nano-Fe loaded biomass char and its enhanced adsorption capacity for phosphate in water | |
| Feng et al. | In-situ formed Prussian blue nanoparticles supported by porous biochar as highly efficient removal of cesium ions | |
| CN111151226B (en) | Preparation method and application of copper-iron-carbon nanogel pellets | |
| CN110746045A (en) | River sewage treatment method capable of recycling | |
| Li et al. | Rapid and selective harvest of low-concentration phosphate by La (OH) 3 loaded magnetic cationic hydrogel from aqueous solution: Surface migration of phosphate from–N+ (CH3) 3 to La (OH) 3 | |
| CN112121770A (en) | Sludge ceramsite for heavy metal wastewater treatment and preparation method thereof | |
| CN114713837A (en) | Nano zero-valent iron-carbon ceramsite, preparation method thereof and application thereof in wastewater treatment | |
| Deng et al. | Arsenate removal from underground water by polystyrene-confined hydrated ferric oxide (HFO) nanoparticles: effect of humic acid | |
| Wang et al. | Phosphorus-rich biochar modified with Alcaligenes faecalis to promote U (VI) removal from wastewater: Interfacial adsorption behavior and mechanism | |
| Kulkarni et al. | Sustainable wastewater management via biochar derived from industrial sewage sludge | |
| CN114229947A (en) | Composite sustained-release material and preparation method and application thereof | |
| Ramteke et al. | Improved treatment approach for the removal of aromatic compounds using polymeric beads in Fenton pretreatment and biological oxidation | |
| Wang et al. | Synchronously construction of hierarchical porous channels and cationic surface charge on lanthanum-hydrogel for rapid phosphorus removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |