CN113860437A - Water body in-situ remediation method for reinforced composite biological material - Google Patents

Water body in-situ remediation method for reinforced composite biological material Download PDF

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Publication number
CN113860437A
CN113860437A CN202111235212.4A CN202111235212A CN113860437A CN 113860437 A CN113860437 A CN 113860437A CN 202111235212 A CN202111235212 A CN 202111235212A CN 113860437 A CN113860437 A CN 113860437A
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straw
biological material
modified
composite biological
nano
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莫建刚
齐传阁
赵印举
梁家成
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Suzhou Zhongsheng Environmental Remediation Co ltd
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Suzhou Zhongsheng Environmental Remediation Co ltd
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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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • 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
    • C02F1/46109—Electrodes
    • 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
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/166—Nitrites

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)

Abstract

The invention provides a preparation method of a reinforced composite biological material, which comprises the following steps: mixing the modified straw particles with the modified MXene material to obtain a mixed material; making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biological material water body in-situ restoration method. The water body in-situ remediation method of the reinforced composite biological material comprises the following steps: the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor; placing an anode in a water body to be restored, and placing a cathode on the liquid level; after the power is on, the water treatment effect of the composite biological material can be enhanced. The material and the method are applied to water body restoration, wherein the photoelectric conversion performance can be enhanced after the conductive nano silk fiber cloth is conductive, the nano level can improve the surface area and increase the contact rate, and the material has good removal effect on ammonia nitrogen, nitrate nitrogen and total phosphorus, especially the ammonia nitrogen can reach 96.54%.

Description

Water body in-situ remediation method for reinforced composite biological material
Technical Field
The invention belongs to the field of environmental remediation, and particularly relates to a water body in-situ remediation method for a reinforced composite biological material.
Background
With the rapid development of urbanization, surface water such as rivers, lakes and the like is seriously polluted, and water resources in China are polluted by a large amount of domestic sewage and industrial wastewater containing nitrogen and phosphorus. The discharge of a large amount of nitrogen and phosphorus wastewater can not only pollute the water environment and destroy the ecological balance, but also cause harm to human health through irrigating farmlands or food chains.
The nitrogen and the phosphorus in the water exist in the forms of free ammonia, ammonium salt and phosphate respectively, and the removal method of the nitrogen and the phosphorus in the wastewater mainly comprises a biological method, a chemical precipitation method, an air stripping method and an adsorption method. Wherein, the adsorption method has the advantages of high removal efficiency, simple operation, economy, applicability and the like, and the adsorbent can be reused through a desorption process after being used. The basic principle of the adsorption process is to use a solid material as an adsorbent to remove the contaminants. There are also many factors that affect the adsorption effect, including modification of the adsorbent material, electrochemical strengthening, etc.
Disclosure of Invention
The technical problem to be solved is as follows: the invention takes Mxene material and modified straw particles as fillers, Ti3C2TxThe material being one of Mxene materials, Ti3C2TxThe modified nano-composite material has larger specific surface area and unique layered nano-structure, and the modified functional group (-OH) becomes rich, so that the adsorption effect is better; the conductive nano silk fiber cloth is adopted for coating, the photoelectric conversion performance can be enhanced after the conductivity is realized, and meanwhile, the nano level can improve the surface area and increase the contact rate.
The technical scheme is as follows: a composite biological material is prepared by coating modified straw particles and a modified MXene material on a conductive nano silk fiber cloth.
Further, the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning.
Further, the straw includes rice straw, corn straw and wheat straw.
Further, the preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 10-60 min, adding phytic acid and urea into the system, heating to 50-90 ℃, carrying out heat preservation reaction for 3-6 h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain the modified straw particles.
Further, the modified MXene material is prepared by the following steps of:
(1) taking 1-2 parts of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, keeping the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx；
(3) Taking 50 parts of Ti as the upper layer3C2TxAdding 0.1-0.15 part of magnesium nitrate hexahydrate, 0.05-0.1 part of aluminum nitrate nonahydrate and 0.1-0.12 part of dopamine into a beaker, stirring to obtain a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
Further, said Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen.
Further, said Ti3A1C2The particle size is 0.01-0.05 mm.
The preparation method of the composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 2-5 parts of modified MXene material to obtain a mixed material;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The in-situ water body restoration method for the reinforced composite biological material comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
Has the advantages that:
1. the invention adopts the conductive nano silk fiber cloth, can enhance the photoelectric conversion performance after being conductive, and simultaneously can improve the surface area and increase the contact rate by nano level.
2. The invention adopts Mxene material, is a novel graphene-like two-dimensional (2D) functional material, and has a chemical formula of Mn+lAXnWherein (n ═ 1-3), M represents an early transition metal such as Sc, Ti, Zr, V, Nb, Cr or Mo; a typically represents a third and fourth main group chemical element; x represents a C or N element. Ti3C2TxOne of the materials, Ti3C2TxHas larger specific surface area and unique layered nano structure, and the modified functional group (-OH) becomes rich and has better adsorption effect.
3. The invention also adopts modified straw particles, and the adsorption effect of the active carbon on compounds such as nitrogen, phosphorus and the like in the aqueous solution can be effectively improved after the straw particles are modified by urea.
4. The material and the method are applied to water body restoration, have good removal effect on ammonia nitrogen, nitrate nitrogen and total phosphorus, and particularly can reach 96.54 percent of ammonia nitrogen.
Detailed Description
Example 1
A preparation method of a composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 2 parts of modified MXene material to obtain a mixed material; wherein the straw comprises rice straw, corn straw and wheat straw;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 10min, adding phytic acid and urea into the system, heating to 50 ℃, carrying out heat preservation reaction for 3h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain modified straw particles.
The modified MXene material is prepared by the following steps of:
(1) taking 1 part of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, maintaining the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral, wherein Ti is3A1C2The particle size is 0.01-0.05 mm;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx(ii) a Wherein, Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen;
(3) taking 50 parts of Ti as the upper layer3C2TxAdding 0.1 part of magnesium nitrate hexahydrate, 0.05 part of aluminum nitrate nonahydrate and 0.1 part of dopamine into a beaker, stirring to obtain a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, and stirring1h, transferring the mixture into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
The water body in-situ remediation method of the reinforced composite biological material comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
Example 2
A preparation method of a composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 3 parts of modified MXene material to obtain a mixed material; wherein the straw comprises rice straw, corn straw and wheat straw;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 10min, adding phytic acid and urea into the system, heating to 50 ℃, carrying out heat preservation reaction for 3h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain modified straw particles.
The modified MXene material is prepared by the following steps of:
(1) taking 1 part of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, maintaining the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral, wherein Ti is3A1C2The particle size is 0.01-0.05 mm;
(2) at 6Vacuum drying at 0 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx(ii) a Wherein, Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen;
(3) taking 50 parts of Ti as the upper layer3C2TxAdding 0.1 part of magnesium nitrate hexahydrate, 0.05 part of aluminum nitrate nonahydrate and 0.1 part of dopamine into a beaker, stirring to form a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
The water body in-situ remediation method of the reinforced composite biological material comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
Example 3
A preparation method of a composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 4 parts of modified MXene material to obtain a mixed material; wherein the straw comprises rice straw, corn straw and wheat straw;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 10min, adding phytic acid and urea into the system, heating to 50 ℃, carrying out heat preservation reaction for 3h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain modified straw particles.
The modified MXene material is prepared by the following steps of:
(1) taking 1 part of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, maintaining the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral, wherein Ti is3A1C2The particle size is 0.01-0.05 mm;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx(ii) a Wherein, Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen;
(3) taking 50 parts of Ti as the upper layer3C2TxAdding 0.1 part of magnesium nitrate hexahydrate, 0.05 part of aluminum nitrate nonahydrate and 0.1 part of dopamine into a beaker, stirring to form a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
The water body in-situ remediation method of the reinforced composite biological material comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
Example 4
A preparation method of a composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 5 parts of modified MXene material to obtain a mixed material; wherein the straw comprises rice straw, corn straw and wheat straw;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 10min, adding phytic acid and urea into the system, heating to 50 ℃, carrying out heat preservation reaction for 3h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain modified straw particles.
The modified MXene material is prepared by the following steps of:
(1) taking 1 part of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, maintaining the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral, wherein Ti is3A1C2The particle size is 0.01-0.05 mm;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx(ii) a Wherein, Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen;
(3) taking 50 parts of Ti as the upper layer3C2TxAdding 0.1 part of magnesium nitrate hexahydrate and 0.05 part of nitric acid nonahydrate into a beakerStirring aluminum and 0.1 part of dopamine to form a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
The water body in-situ remediation method of the reinforced composite biological material comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
Example 5
A preparation method of a composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 4 parts of modified MXene material to obtain a mixed material; wherein the straw comprises rice straw, corn straw and wheat straw;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 20min, adding phytic acid and urea into the system, heating to 60 ℃, carrying out heat preservation reaction for 4h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain modified straw particles.
The modified MXene material is prepared by the following steps of:
(1) taking 1.5 parts of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, maintaining the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral, wherein Ti is3A1C2The particle size is 0.01-0.05 mm;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx(ii) a Wherein, Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen;
(3) taking 50 parts of Ti as the upper layer3C2TxAdding 0.12 part of magnesium nitrate hexahydrate, 0.06 part of aluminum nitrate nonahydrate and 0.11 part of dopamine into a beaker, stirring to obtain a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
The water body in-situ remediation method of the reinforced composite biological material comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
Example 6
A preparation method of a composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 4 parts of modified MXene material to obtain a mixed material; wherein the straw comprises rice straw, corn straw and wheat straw;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 30min, adding phytic acid and urea into the system, heating to 70 ℃, carrying out heat preservation reaction for 4h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain modified straw particles.
The modified MXene material is prepared by the following steps of:
(1) taking 1.5 parts of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, maintaining the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral, wherein Ti is3A1C2The particle size is 0.01-0.05 mm;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx(ii) a Wherein, Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen;
(3) taking 50 parts of Ti as the upper layer3C2TxAdding 0.13 part of magnesium nitrate hexahydrate, 0.07 part of aluminum nitrate nonahydrate and 0.11 part of dopamine into a beaker, stirring to form a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
The water body in-situ remediation method of the reinforced composite biological material comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
Example 7
A preparation method of a composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 4 parts of modified MXene material to obtain a mixed material; wherein the straw comprises rice straw, corn straw and wheat straw;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 40min, adding phytic acid and urea into the system, heating to 80 ℃, carrying out heat preservation reaction for 5h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain modified straw particles.
The modified MXene material is prepared by the following steps of:
(1) taking 1.5 parts of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, maintaining the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral, wherein Ti is3A1C2The particle size is 0.01-0.05 mm;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx(ii) a Wherein, Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen;
(3) taking 50 parts of Ti as the upper layer3C2TxAdding 0.14 part of magnesium nitrate hexahydrate, 0.08 part of aluminum nitrate nonahydrate and 0.11 part of dopamine into a beaker, stirring to obtain a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
The water body in-situ remediation method of the reinforced composite biological material comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
Example 8
A preparation method of a composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 4 parts of modified MXene material to obtain a mixed material; wherein the straw comprises rice straw, corn straw and wheat straw;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 60min, adding phytic acid and urea into the system, heating to 90 ℃, carrying out heat preservation reaction for 6h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain modified straw particles.
The modified MXene material is prepared by the following steps of:
(1) taking 2 parts of Ti3A1C2Soaking in 20 parts of 40% HF water solutionKeeping the temperature in the solution at 40 ℃, magnetically stirring the solution for 24 hours, centrifuging the solution, and washing the solution to be neutral by deionized water, wherein Ti is contained in the solution3A1C2The particle size is 0.01-0.05 mm;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx(ii) a Wherein, Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen;
(3) taking 50 parts of Ti as the upper layer3C2TxAdding 0.15 part of magnesium nitrate hexahydrate, 0.1 part of aluminum nitrate nonahydrate and 0.12 part of dopamine into a beaker, stirring to form a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
The water body in-situ remediation method of the reinforced composite biological material comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
Comparative example 1
A preparation method of a composite biological material comprises the following steps:
(1) mixing 1 part of modified straw particles and 4 parts of modified MXene material to obtain a mixed material; wherein the straw comprises rice straw, corn straw and wheat straw;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material; the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
The preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 60min, adding phytic acid and urea into the system, heating to 90 ℃, carrying out heat preservation reaction for 6h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain modified straw particles.
The modified MXene material is prepared by the following steps of:
(1) taking 2 parts of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, maintaining the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral, wherein Ti is3A1C2The particle size is 0.01-0.05 mm;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx(ii) a Wherein, Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen;
(3) taking 50 parts of Ti as the upper layer3C2TxAdding 0.15 part of magnesium nitrate hexahydrate, 0.1 part of aluminum nitrate nonahydrate and 0.12 part of dopamine into a beaker, stirring to form a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
The water body in-situ remediation method of the composite biological material comprises the following steps: and (3) placing the composite biological material in a water body to be restored for adsorption, and measuring the adsorption effect.
The water body remediation effect is realized by ammoniaThe removal effect of nitrogen, nitrate nitrogen and total phosphorus is taken as the basis, the concentration of initial ammonia nitrogen in the water body is 4.0 +/-0.2 mg/L, the concentration of nitrate nitrogen is 2.0 +/-0.1 mg/L and the concentration of total phosphorus is 3.5 +/-0.5 mg/L, the mass-volume ratio of the addition amount of the composite biological material to the water body is 1:2000, and the power density of the system is 1.3W/m3The current density was 4.50A/m3, indicating that the system had a repair time of 4h, and the repair results are shown in Table 1.
TABLE 1
Figure BDA0003317274260000101
Figure BDA0003317274260000111

Claims (9)

1. A composite biomaterial, characterized by: the modified straw particle and modified MXene material are coated by conductive nano silk fiber cloth.
2. A composite biomaterial according to claim 1, characterized in that: the conductive nano-silk fiber cloth is prepared from conductive monofilament nano-silk, and the conductive monofilament nano-silk is prepared through electrostatic spinning.
3. A composite biomaterial according to claim 1, characterized in that: the straw comprises rice straw, corn straw and wheat straw.
4. A composite biomaterial according to claim 1, characterized in that: the preparation method of the modified straw particles comprises the following steps:
mixing straw powder and N, N-dimethylene formamide, placing the mixture into an ultrasonic instrument for ultrasonic pretreatment for 10-60 min, adding phytic acid and urea into the system, heating to 50-90 ℃, carrying out heat preservation reaction for 3-6 h, cooling the product to room temperature, filtering, and drying in a 50 ℃ oven to obtain the modified straw particles.
5. A composite biomaterial according to claim 1, characterized in that: the preparation method of the modified MXene material comprises the following steps of:
(1) taking 1-2 parts of Ti3A1C2Soaking in 20 parts of 40% HF aqueous solution, keeping the temperature at 40 ℃, magnetically stirring for 24 hours, centrifuging, and washing with deionized water to be neutral;
(2) vacuum drying at 60 deg.C to obtain multilayer Ti3C2T, under the protection of inert gas, the obtained Ti3C2T is dispersed in 20ml of tetramethylammonium hydroxide aqueous solution, stirred for 2 hours, ultrasonically treated for 1 hour, then centrifuged for 0.5 hour at the centrifugal speed of 2000rpm, and the obtained supernatant is Ti-less layer3C2Tx；
(3) Taking 50 parts of Ti as the upper layer3C2TxAdding 0.1-0.15 part of magnesium nitrate hexahydrate, 0.05-0.1 part of aluminum nitrate nonahydrate and 0.1-0.12 part of dopamine into a beaker, stirring to obtain a uniform solution, dropwise adding a NaOH solution to adjust the pH value to 9, stirring for 1h, transferring into a stainless steel autoclave, heating to 1100 ℃, and keeping for 12 h;
(4) and alternately cleaning the product with ethanol and deionized water for 2 times respectively, and drying in a vacuum drying oven to obtain the final product.
6. A composite biomaterial according to claim 5, characterized in that: the Ti3C2T in T represents a surface terminal group, and is-O, -OH or-F; the Ti3C2TxWherein X is carbon, nitrogen or carbon nitrogen.
7. A composite biomaterial according to claim 5, characterized in that: the Ti3A1C2The particle size is 0.01-0.05 mm.
8. The method for preparing a composite biomaterial according to claim 1, wherein: the method comprises the following steps:
(1) mixing 1 part of modified straw particles and 2-5 parts of modified MXene material to obtain a mixed material;
(2) making a bag with the conductive nano-silk fiber cloth, reserving a mouth, and filling the mixed material;
(3) and (3) sealing the conductive nano silk fiber bag to obtain the reinforced composite biomaterial.
9. The in-situ water body restoration method for the reinforced composite biological material as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) the composite biological material is used as an anode, the carbon cloth is used as a cathode, and the cathode and the anode are connected through a lead and a resistor;
(2) placing an anode in a water body to be restored, and placing a cathode on the liquid level;
(3) after the power is on, the water treatment effect of the composite biological material can be enhanced.
CN202111235212.4A 2021-10-22 2021-10-22 Water body in-situ remediation method for reinforced composite biological material Withdrawn CN113860437A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114606652A (en) * 2022-02-17 2022-06-10 苏州美森无纺科技有限公司 Photo-thermal regulation and control type efficient oil adsorption wiping cloth and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114606652A (en) * 2022-02-17 2022-06-10 苏州美森无纺科技有限公司 Photo-thermal regulation and control type efficient oil adsorption wiping cloth and preparation method thereof
CN114606652B (en) * 2022-02-17 2023-07-21 苏州美森无纺科技有限公司 Photo-thermal regulation type efficient oil adsorption wiping cloth and preparation method thereof

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