CN114906945A - Slow-release oxygen material and preparation method and application thereof - Google Patents

Slow-release oxygen material and preparation method and application thereof Download PDF

Info

Publication number
CN114906945A
CN114906945A CN202110184406.XA CN202110184406A CN114906945A CN 114906945 A CN114906945 A CN 114906945A CN 202110184406 A CN202110184406 A CN 202110184406A CN 114906945 A CN114906945 A CN 114906945A
Authority
CN
China
Prior art keywords
oxygen
release
agent
slow
stirring
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.)
Pending
Application number
CN202110184406.XA
Other languages
Chinese (zh)
Inventor
姚猛
林笑雨
房师平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
Original Assignee
China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Qingdao Safety Engineering Institute filed Critical China Petroleum and Chemical Corp
Priority to CN202110184406.XA priority Critical patent/CN114906945A/en
Publication of CN114906945A publication Critical patent/CN114906945A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F7/00—Aeration of stretches of water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • C02F2101/30—Organic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of microorganisms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

The invention discloses a slow-release oxygen material and a preparation method and application thereof. The slow release material comprises the following components in percentage by mass: 40-75% of oxygen release agent, 10-30% of embedding agent, 3-16% of binder, 3-7% of dispersing agent and 3-7% of pH buffering agent. The slow-release oxygen material uses peroxide and persulfate as oxygen release agents, and utilizes the mechanism that sulfuric acid generated by the reaction of persulfate and water can react with peroxide and water to generate hydroxide to generate neutralization reaction, thereby effectively solving the problem of environmental pH value increase caused by using metal peroxide as the oxygen release agents. Meanwhile, the pH buffering agent is added into the slow release material, so that the condition that the pH value of the environment fluctuates greatly in the working process of the slow release material is avoided, and a stable environment is provided for the growth and metabolism of microorganisms.

Description

Slow-release oxygen material and preparation method and application thereof
Technical Field
The invention relates to the field of soil and underground water pollution treatment, in particular to a slow-release oxygen material and a preparation method thereof.
Background
Common soil and underground water remediation technologies include in-situ remediation and ex-situ remediation, and the in-situ remediation technology is more and more prone to be adopted for organic matter polluted sites which are large in pollution depth and difficult to excavate. The in-situ repair technology mainly comprises biological repair and chemical repair. The chemical remediation technology is easy to damage the soil structure, so that the secondary pollution of the soil is caused; the in-situ bioremediation technology is regarded as an ideal technical means for treating the large-area polluted soil due to the advantages of high efficiency, economy, no secondary pollution and the like. The in-situ bioremediation technology mainly comprises a biological adding method, a biological stimulation method, a biological ventilation method, a microbial fuel cell and the like. The biological adding method is used for improving the biological repair efficiency by improving the number of microorganisms, and comprises the steps of adding efficient degrading bacteria, immobilized bacteria, microorganism-plant cooperative repair and the like; the biological stimulation method is to improve the biological repair rate by improving the living environment of microorganisms, and comprises the steps of adding nutrient substances, surfactants and co-metabolism substrates, improving the oxygen condition and the like.
In the process of removing organic pollutants in soil and underground water, the aerobic microbial metabolism has more technical advantages because the mineralization degree of the organic pollutants is far higher than that of the organic pollutants due to anaerobic metabolism. In the process of aerobic metabolism of organic matters by microorganisms, the organic matters are used as a carbon source and an electron donor, sufficient oxygen is needed to be used as an electron acceptor for realizing the complete oxidation of the organic matters, and the organic matters are oxidized into inorganic matters to realize the mineralization of organic pollutants.
At present, a limiting bottleneck exists in the process of repairing soil and underground water by adopting a biological method, namely, enough electron acceptors are lacked, so that the degradation speed of pollutants is limited, measures such as air or oxygen injection, ozone injection, micro-bubble injection, hydrogen peroxide injection, solid oxygen release agent feeding and the like are required to be adopted to increase the oxygen content in the soil and the underground water, improve the environmental conditions for the growth and degradation of microorganisms, and improve the metabolism and degradation activity level of the microorganisms so as to promote the degradation speed of the pollutants. However, the above method has a fast oxygen release rate, and cannot release oxygen stably for a long time, and the operation cost is also high.
The slow-release oxygen material (ORC) is a composite material which is relatively common abroad in recent years and is used for biologically enhanced restoration of underground water, and the main oxygen-release component is generally peroxide, such as calcium peroxide (CaO) 2 ) Magnesium peroxide (MgO) 2 ) And persulfate (Na) 2 S 2 O 8 ) Etc. based on the principle of using calcium peroxide (CaO) 2 ) Magnesium peroxide (MgO) 2 ) And persulfates (Na) 2 S 2 O 8 ) Etc. with H 2 O reaction releases O 2 Increasing DO concentration of the water body, further increasing oxidation-reduction potential of the water body and promoting aerobic biodegradation of organic pollutants (2 CaO) 2 +2H 2 O＝2Ca(OH) 2 +O 2 ↑，2Na 2 S 2 O 8 +2H 2 O＝2Na 2 SO 4 +2H 2 SO 4 +O 2 ×) in the table. Sustained release oxygen compounds (ORC) are of interest because of their simplicity of operation, low cost, significant effectiveness, and ability to be used in conjunction with permeable barriers and other technologies. Relevant researches prove that the DO concentration of the water body can be obviously improved by slowly releasing the oxygen compound.
The application modes of the slow-release oxygen material in the actual polluted site restoration project are as follows:
(1) arranging a plurality of oxygen release wells at the downstream of a polluted site, filling oxygen release materials into porous filter bags, and putting the porous filter bags into the oxygen release wells, and taking out the filter bags to replace new oxygen release materials after the oxygen release materials fail;
(2) injecting ORC into the contaminated aquifer by a high pressure pump in powder or slurry form;
(3) the activated carbon is used as a Permeable Reactive Barrier (PRB) filler, is added into PRB and is combined with other physical, chemical, biological and other underground water remediation means for use, so that the purpose of degrading and removing pollutants is achieved.
Research has shown that ORC can be used to remediate most aerobiodegradable contaminants such as benzene-based materials (BTEX) and other light oil components, MTBE, chlorinated alkenes, chlorinated alkanes, various herbicides (e.g., atrazine, acetochlor), and the like.
Patent CN102491502A discloses a sustained oxygen release material for groundwater remediation and a preparation method thereof, the method uses calcium peroxide as an oxygen release agent, cement and the like are used as a binder in the preparation process, the loss of the oxygen release agent can be caused because the calcium peroxide reacts with water in the preparation process, and the sustained release material can cause the rise of the environmental pH value in the oxygen release process, destroy the growth environment of microorganisms, be not beneficial to the degradation of pollutants by the microorganisms, and be not suitable for being used in certain polluted saline and alkaline land.
Patent CN110184072A discloses a method for preparing a calcium peroxide slow-release oxygen material, which uses polylactic acid as embedding agent, and avoids the loss of oxygen-releasing agent caused by the contact of calcium peroxide and water during the preparation process, but still cannot solve the problem of the increase of environmental pH value caused by the use of slow-release material.
Patent CN206382324U discloses an organic pollution site strengthening repair system, and the system adopts sodium persulfate as an oxygen release agent, which can cause the problem of environmental pH value reduction in the system operation process and is not beneficial to the degradation of the pollutants by microorganisms.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a slow-release oxygen material and a preparation method thereof. So as to solve the problem of the rise of the pH value of the environment caused in the using process of the prior oxygen release agent. The invention also aims to solve the problem of great fluctuation of the pH value of the environment caused in the working process of the oxygen release material and provide a stable environment for the growth and metabolism of microorganisms. Still another object of the present invention is to solve the problem of premature loss of oxygen-releasing agent during the preparation process.
The invention aims to provide a slow-release oxygen material which can continuously and stably provide an electron acceptor for the process of biologically and intensively repairing the underground water of the polluted soil and improve the effect of removing pollutants by microorganisms.
In order to achieve the above object, a first aspect of the present invention provides a slow-release oxygen material, which comprises the following components by mass:
40 to 75 percent of oxygen release agent, preferably 45 to 70 percent;
10-30% of embedding agent, preferably 15-30%;
3% -16% of binder, preferably 5% -15%;
3 to 7 percent of dispersant, preferably 3 to 5 percent; and
pH buffer 3% -7%, preferably 3% -5%.
In the technical scheme, the oxygen release agent is a mixture of metal peroxide and persulfate, and the mass ratio of the peroxide to the persulfate is (1: 1) - (1): 4 (pure substance), preferably in a mass ratio of 1: 3. Wherein the peroxide can adopt one or a combination of more of calcium peroxide, magnesium peroxide and sodium peroxide; the persulfate can adopt one or a combination of sodium persulfate, potassium persulfate or ammonium persulfate; the oxygen releasing agent is powder oxygen releasing agent, the mesh number is 90-200 meshes, and preferably 100-150 meshes.
In the above technical scheme, the embedding agent may be composed of one or more of chitosan, polybutylene succinate, polyhydroxyalkanoate, polycaprolactone, polylactic acid, ethylcellulose, hydroxypropylcellulose, and cellulose acetate.
In the above technical scheme, the binder may be composed of one or more of sodium alginate, polyethylene glycol and polyvinyl alcohol.
In the above technical scheme, the dispersant may be composed of one or more of polyethylene oxide, dextrin, starch, and polyacrylic acid.
In the above technical solution, the pH buffer may be composed of one or more of ammonium acetate, sodium dihydrogen phosphate and potassium dihydrogen phosphate.
The second aspect of the invention provides a preparation method of a slow-release oxygen material, which comprises the following steps:
(1) adding an embedding agent into a first organic solvent, heating and stirring under the protection of nitrogen until the embedding agent is completely dissolved to obtain a first solution;
(2) adding the binder and the dispersant into a second organic solvent, heating and stirring the mixture under the protection of nitrogen until the binder and the dispersant are completely dissolved to obtain a second solution;
(3) mixing the first solution and the second solution prepared in the steps (1) and (2), heating under the protection of nitrogen and fully stirring to obtain a mixed solution;
(4) respectively adding the oxygen-releasing agent and the pH buffering agent into the mixed solution obtained in the step (3), and continuously heating and stirring until the oxygen-releasing agent and the pH buffering agent are completely and uniformly dispersed in the mixed solution to obtain a mixture solution;
(5) and (4) removing the organic solvent from the mixture solution prepared in the step (4), drying by a dryer, and granulating to obtain the slow-release material.
In the foregoing technical solution, the first organic solvent in step (1) is one or more of dichloromethane, chloroform, and carbon tetrachloride. The second organic solvent in the step (2) is one or more of methanol, isopropanol, acetone and propylene glycol. The organic solvent removed in the step (5) can be removed by heating and evaporating under reduced pressure. The drying in the step (5) can be one or more of freeze drying, spray drying, reduced pressure distillation drying, microwave drying and the like.
The third aspect of the invention is to provide an application of the oxygen-releasing-retarding material in a composite material for biologically and intensively repairing underground water.
The invention has the following effects:
the slow-release oxygen material uses peroxide and persulfate as oxygen release agents, and utilizes the mechanism that sulfuric acid generated by the reaction of persulfate and water can react with peroxide and water to generate hydroxide to generate neutralization reaction, thereby effectively solving the problem of environmental pH value increase caused by using metal peroxide as the oxygen release agent. Meanwhile, persulfate is decomposed to generate sulfate radicals, so that an electron acceptor can be provided for microorganisms, and the decomposition of the microorganisms on organic pollutants is promoted. Meanwhile, the pH buffering agent is added into the slow release material, so that the condition that the pH value of the environment fluctuates greatly in the working process of the slow release material is avoided, and a stable environment is provided for the growth and metabolism of microorganisms. The slow release material does not contact with water in the preparation process, so that the advanced loss of the oxygen release agent is not caused, and the embedding material adopts environment-friendly degradable organic matters, so that a co-metabolism carbon source can be provided for microorganisms, and the secondary pollution is not caused.
Detailed Description
Example 1
Dissolving 2g of polycaprolactone into 250ml of dichloromethane, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at the constant temperature of 65 ℃, and stirring at the rotating speed of 400 r/min; dissolving 1g of sodium alginate and 0.5g of polyacrylic acid in 250ml of propylene glycol, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 65 ℃, and stirring at a rotating speed of 400 r/min; after the embedding agent in the step 1 and the binder and the dispersing agent in the step 2 are completely dissolved, mixing the liquids in the steps 1 and 2, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 60 ℃, and stirring at a rotating speed of 300 r/min; when the mixed liquor in the step 3 is uniformly mixed to be in a uniform and clear state, respectively adding 2g of powdery calcium peroxide, 100-mesh powdery sodium persulfate, 4g of powdery sodium persulfate, 100-mesh powdery potassium dihydrogen phosphate and 0.5g of powdery potassium dihydrogen phosphate, continuously heating and stirring under the protection of nitrogen until the three substances are uniformly dispersed in the mixed liquor, heating at the constant temperature of 60 ℃, and stirring at the rotating speed of 250 r/min; and after the dichloromethane is evaporated until the mixed solution is in a gel semi-solid state, carrying out freeze drying treatment and granulation on the mixture to obtain the slow-release oxygen granular material with the grain diameter of 3-4 mm.
Boiling deionized water for 3 minutes, placing 1L of deionized water and 1g of slow-release oxygen granular material in a three-opening reaction bottle, cooling, arranging pH and DO probes, blowing off with nitrogen for 30min, sealing the bottle opening, and continuously monitoring dissolved oxygen and pH in water; the dissolved oxygen in water tends to be stable after 120 days, the concentration of the dissolved oxygen is 9.3mg/L, and the pH value is stable at 6.5.
Example 2
Dissolving 3g of polylactic acid in 250ml of carbon tetrachloride, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 65 ℃, and stirring at a rotation speed of 400 r/min; dissolving 0.5g of polyethylene glycol and 0.5g of dextrin in 250ml of methanol, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at the constant temperature of 65 ℃, and stirring at the rotating speed of 400 r/min; after the embedding medium in the step 1 and the binder and the dispersing agent in the step 2 are completely dissolved, mixing the liquids in the step 1 and the step 2, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 60 ℃, and stirring at a rotating speed of 300 r/min; when the mixed solution in the step 3 is uniformly mixed to be in a uniform and clear state, respectively adding 1.1g of calcium peroxide, 4.4g of sodium persulfate and 0.5g of potassium dihydrogen phosphate, continuously heating and stirring under the protection of nitrogen until the three substances are uniformly dispersed in the mixed solution, heating at a constant temperature of 60 ℃ and stirring at a rotating speed of 250 r/min; and after the dichloromethane is evaporated until the mixed solution is in a gel semi-solid state, carrying out freeze drying treatment and granulation on the mixture to obtain the slow-release oxygen granular material with the grain diameter of 3-4 mm.
Boiling deionized water for 3 minutes, placing 1L of deionized water and 1g of slow-release oxygen granular material in a three-mouth reaction bottle, cooling, placing a pH probe and a DO probe, blowing off with nitrogen for 30min, sealing the bottle mouth, and monitoring dissolved oxygen and pH in water; the dissolved oxygen in water tends to be stable after 109 days, the concentration of the dissolved oxygen is 9.8mg/L, and the pH value is stable at 6.7.
Example 3
Dissolving 1.5g of chitosan in 250ml of dichloromethane, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 65 ℃, and stirring at a rotating speed of 400 r/min; dissolving 0.5g of polyvinyl alcohol and 0.7g of starch in 250ml of isopropanol, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 65 ℃, and stirring at a rotating speed of 400 r/min; after the embedding medium in the step 1 and the binder and the dispersing agent in the step 2 are completely dissolved, mixing the liquids in the step 1 and the step 2, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 60 ℃, and stirring at a rotating speed of 300 r/min; when the mixed solution in the step 3 is uniformly mixed to be in a uniform and clear state, respectively adding 2g of powdery magnesium peroxide, 150-mesh powdery potassium persulfate, 5g of powdery potassium persulfate, 150-mesh powdery potassium dihydrogen phosphate and 0.3g of powdery potassium dihydrogen phosphate, continuously heating and stirring under the protection of nitrogen until the three substances are uniformly dispersed in the mixed solution, heating at the constant temperature of 60 ℃, and stirring at the rotating speed of 250 r/min; and after the dichloromethane is evaporated until the mixed solution is in a gel semi-solid state, carrying out freeze drying treatment and granulation on the mixture to obtain the slow-release oxygen granular material with the grain diameter of 3-4 mm.
Boiling deionized water for 3 minutes, placing 1L of deionized water and 1g of slow-release oxygen granular material in a three-mouth reaction bottle, cooling, placing a pH probe and a DO probe, blowing off with nitrogen for 30min, sealing the bottle mouth, and monitoring dissolved oxygen and pH in water; the dissolved oxygen in water tends to be stable after 116 days, the concentration of the dissolved oxygen is 10.2mg/L, and the pH value is stable at 7.2.
Example 4
Dissolving 3g of polybutylene succinate in 250ml of dichloromethane, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at the constant temperature of 65 ℃, and stirring at the rotating speed of 400 r/min; dissolving 1.5g of polyvinyl alcohol and 0.3g of starch in 250ml of isopropanol, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 65 ℃, and stirring at a rotating speed of 400 r/min; after the embedding agent in the step 1 and the binder and the dispersing agent in the step 2 are completely dissolved, mixing the liquids in the steps 1 and 2, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 60 ℃, and stirring at a rotating speed of 300 r/min; when the mixed liquid in the step 3 is uniformly mixed to be in a uniform and clear state, respectively adding 1.5g of powdered sodium peroxide, 200 meshes of powdered ammonium persulfate, 3g of powdered ammonium persulfate, 100 meshes of powdered potassium dihydrogen phosphate and 0.7g of potassium dihydrogen phosphate, continuously heating and stirring under the protection of nitrogen until the three substances are uniformly dispersed in the mixed liquid, heating at the constant temperature of 60 ℃, and stirring at the rotating speed of 250 r/min; and after the dichloromethane is evaporated until the mixed solution is in a gel semi-solid state, carrying out freeze drying treatment and granulation on the mixture to obtain the slow-release oxygen granular material with the grain diameter of 3-4 mm.
Boiling deionized water for 3 minutes, placing 1L of deionized water and 1g of slow-release oxygen granular material in a three-mouth reaction bottle, cooling, placing a pH probe and a DO probe, blowing off with nitrogen for 30min, sealing the bottle mouth, and monitoring dissolved oxygen and pH in water; the dissolved oxygen in water tends to be stable after 121 days, the concentration of the dissolved oxygen is 9.8mg/L, and the pH value is stable at 6.8.
Example 5
Dissolving 2g of hydroxypropyl cellulose in 250ml of dichloromethane, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at the constant temperature of 65 ℃, and stirring at the rotating speed of 400 r/min; dissolving 1g of sodium alginate and 0.5g of starch in 250ml of isopropanol, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 65 ℃, and stirring at a rotating speed of 400 r/min; after the embedding medium in the step 1 and the binder and the dispersing agent in the step 2 are completely dissolved, mixing the liquids in the step 1 and the step 2, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 60 ℃, and stirring at a rotating speed of 300 r/min; when the mixed solution in the step 3 is uniformly mixed to be in a uniform and clear state, respectively adding 2g of powdered calcium peroxide, 100 meshes of powdered sodium persulfate, 4g of powdered sodium persulfate, 100 meshes of powdered potassium dihydrogen phosphate and 0.5g of powdered potassium dihydrogen phosphate, continuously heating and stirring under the protection of nitrogen until the three substances are uniformly dispersed in the mixed solution, heating at the constant temperature of 60 ℃, and stirring at the rotating speed of 250 r/min; and after the dichloromethane is evaporated until the mixed solution is in a gel semi-solid state, carrying out freeze drying treatment and granulation on the mixture to obtain the slow-release oxygen granular material with the grain diameter of 3-4 mm.
Boiling deionized water for 3 minutes, placing 1L of deionized water and 1g of slow-release oxygen granular material in a three-mouth reaction bottle, cooling, placing a pH probe and a DO probe, blowing off with nitrogen for 30min, sealing the bottle mouth, and monitoring dissolved oxygen and pH in water; the dissolved oxygen in water tends to be stable after 115 days, the concentration of the dissolved oxygen is 10.5mg/L, and the pH value is stable at 6.5.
Example 6
Dissolving 2g of ethyl cellulose in 250ml of dichloromethane, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 65 ℃, and stirring at a rotating speed of 400 r/min; dissolving 1g of polyethylene glycol and 0.5g of starch in 250ml of isopropanol, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at the constant temperature of 65 ℃, and stirring at the rotating speed of 400 r/min; after the embedding agent in the step 1 and the binder and the dispersing agent in the step 2 are completely dissolved, mixing the liquids in the steps 1 and 2, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 60 ℃, and stirring at a rotating speed of 300 r/min; when the mixed liquor in the step 3 is uniformly mixed to be in a uniform and clear state, respectively adding 2g of powdery calcium peroxide, 100 meshes of powdery sodium persulfate, 4g of powdery sodium persulfate, 100 meshes of powdery potassium dihydrogen phosphate and 0.5g of powdery potassium dihydrogen phosphate, continuously heating and stirring under the protection of nitrogen until the three substances are uniformly dispersed in the mixed liquor, heating at the constant temperature of 60 ℃, and stirring at the rotating speed of 250 r/min; and after the dichloromethane is evaporated until the mixed solution is in a gel semi-solid state, carrying out freeze drying treatment and granulation on the mixture to obtain the slow-release oxygen granular material with the grain diameter of 3-4 mm.
Boiling deionized water for 3 minutes, placing 1L of deionized water and 1g of slow-release oxygen granular material in a three-mouth reaction bottle, cooling, placing a pH probe and a DO probe, blowing off with nitrogen for 30min, sealing the bottle mouth, and monitoring dissolved oxygen and pH in water; the dissolved oxygen in water tends to be stable after 115 days, the concentration of the dissolved oxygen is 10.2mg/L, and the pH value is stable at 6.6.
Comparative example 1
Dissolving 2g of polycaprolactone into 250ml of dichloromethane, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at the constant temperature of 65 ℃, and stirring at the rotating speed of 400 r/min; dissolving 1g of sodium alginate and 0.5g of polyacrylic acid in 250ml of propylene glycol, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 65 ℃, and stirring at a rotating speed of 400 r/min; after the embedding agent in the step 1 and the binder and the dispersing agent in the step 2 are completely dissolved, mixing the liquids in the steps 1 and 2, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 60 ℃, and stirring at a rotating speed of 300 r/min; when the mixed solution in the step 3 is uniformly mixed to be in a uniform and clear state, adding 6g of powdery calcium peroxide with the mesh number of 100, continuously heating and stirring under the protection of nitrogen until the three substances are uniformly dispersed in the mixed solution, heating at the constant temperature of 60 ℃, and stirring at the rotating speed of 250 r/min; and after the dichloromethane is evaporated until the mixed solution is in a gel semi-solid state, carrying out freeze drying treatment and granulation on the mixture to obtain the slow-release oxygen granular material with the grain diameter of 3-4 mm.
Boiling deionized water for 3 minutes, placing 1L of deionized water and 1g of slow-release oxygen granular material in a three-mouth reaction bottle, cooling, placing a pH probe and a DO probe, blowing off with nitrogen for 30min, sealing the bottle mouth, and monitoring dissolved oxygen and pH in water; the dissolved oxygen in water tends to be stable after 122 days, the concentration of the dissolved oxygen is 9.9mg/L, and the pH value is stable at 14.1.
Comparative example 2
Dissolving 2g of polycaprolactone into 250ml of dichloromethane, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at the constant temperature of 65 ℃, and stirring at the rotating speed of 400 r/min; dissolving 1g of polyvinyl alcohol and 0.5g of polyacrylic acid in 250ml of isopropanol, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at the constant temperature of 65 ℃, and stirring at the rotating speed of 400 r/min; after the embedding agent in the step 1 and the binder and the dispersing agent in the step 2 are completely dissolved, mixing the liquids in the steps 1 and 2, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at a constant temperature of 60 ℃, and stirring at a rotating speed of 300 r/min; when the mixed solution in the step 3 is uniformly mixed to be in a uniform and clear state, adding 6g of powdery sodium persulfate with the mesh number of 100, continuously heating and stirring under the protection of nitrogen until the three substances are uniformly dispersed in the mixed solution, heating at the constant temperature of 60 ℃, and stirring at the rotating speed of 250 r/min; and after the dichloromethane is evaporated until the mixed solution is in a gel semi-solid state, carrying out freeze drying treatment and granulation on the mixture to obtain the slow-release oxygen granular material with the grain diameter of 3-4 mm.
Boiling deionized water for 3 minutes, placing 1L of deionized water and 1g of slow-release oxygen granular material in a three-mouth reaction bottle, cooling, placing a pH probe and a DO probe, blowing off with nitrogen for 30min, sealing the bottle mouth, and monitoring dissolved oxygen and pH in water; the dissolved oxygen in water tends to be stable after 128 days, the concentration of the dissolved oxygen is 9.8mg/L, and the pH value is stable at 1.5.
Comparative example 3
Dissolving 2g of polycaprolactone into 250ml of dichloromethane, stirring by using a heating magnetic stirrer under the protection of nitrogen, heating at the constant temperature of 65 ℃, and stirring at the rotating speed of 400 r/min; when the mixed solution is uniformly mixed to be in a uniform and clear state, respectively adding 2g of powdery calcium peroxide, 100-mesh powdery sodium persulfate, 4g of powdery sodium persulfate, 100-mesh powdery potassium dihydrogen phosphate and 0.5g of powdery potassium dihydrogen phosphate, continuously heating and stirring under the protection of nitrogen until the three substances are uniformly dispersed in the mixed solution, heating at the constant temperature of 60 ℃, and stirring at the rotating speed of 250 r/min; and after the dichloromethane is evaporated until the mixed solution is in a gel semi-solid state, carrying out freeze drying treatment and granulation on the mixture to obtain the slow-release oxygen granular material with the grain diameter of 3-4 mm.
Boiling deionized water for 3 minutes, placing 1L of deionized water and 1g of slow-release oxygen granular material in a three-mouth reaction bottle, cooling, placing a pH probe and a DO probe, blowing off with nitrogen for 30min, sealing the bottle mouth, and continuously monitoring dissolved oxygen and pH in water; the dissolved oxygen in water tends to be stable after 60 days, the concentration of the dissolved oxygen is 6.9mg/L, and the pH value is stable at 6.2.
Comparative example 4
0.5g of powdery calcium peroxide, 100 meshes of powdery sodium persulfate, 1.5g of powdery sodium persulfate, 100 meshes of powdery sodium persulfate and 7.5g of activated carbon powder are fully stirred and mixed uniformly, deionized water is boiled for 3 minutes, 1L of deionized water and 1g of mixed material are placed in a three-port reaction bottle, a pH probe and a DO probe are arranged after cooling, a bottle opening is sealed after blowing off for 30 minutes by using nitrogen, and the dissolved oxygen and the pH in water are monitored; the oxygen dissolved in water tends to be stable after 6 days.
Comparative example 5
0.5g of powdery calcium peroxide, 100 meshes of powdery sodium persulfate, 1.5g of powdery sodium persulfate, 100 meshes of powdery bentonite and 7.5g of powdery bentonite are fully stirred and mixed uniformly, 1L of deionized water and 1g of mixed material are placed in a three-port reaction bottle after the deionized water is boiled for 3 minutes, a pH probe and a DO probe are arranged after cooling, the bottle opening is sealed after blowing off for 30 minutes by using nitrogen, and the dissolved oxygen and the pH in the water are monitored; the dissolved oxygen in water tends to be stable after 8 days.

Claims (13)

1. The slow-release oxygen material is characterized by comprising the following components in percentage by mass:
40 to 75 percent of oxygen release agent;
10 to 30 percent of embedding agent;
3% -16% of a binder;
3% -7% of a dispersant; and
3 to 7 percent of pH buffering agent.
2. The oxygen-release-retarding material as claimed in claim 1, which comprises the following components by mass:
45 to 70 percent of oxygen release agent;
15 to 30 percent of embedding agent;
5% -15% of a binder;
3% -5% of a dispersant; and
3 to 5 percent of pH buffering agent.
3. The slow-release oxygen material according to claim 1, wherein the oxygen release agent is a mixture of metal peroxide and persulfate, and the mass ratio of the peroxide to the persulfate is (1: 1) - (1): 4, preferably in a mass ratio of 1: 3.
4. The oxygen slow-release material as claimed in claim 1, wherein the peroxide is one or more of calcium peroxide, magnesium peroxide and sodium peroxide; the persulfate is one or a combination of sodium persulfate, potassium persulfate or ammonium persulfate.
5. The oxygen-release material according to claim 1, wherein the oxygen-releasing agent is a powdered oxygen-releasing agent, and the mesh number of the powdered oxygen-releasing agent is 90-200 meshes, preferably 100-150 meshes.
6. The slow-release oxygen material of claim 1, wherein the embedding agent is one or more of chitosan, polybutylene succinate, polyhydroxyalkanoate, polycaprolactone, polylactic acid, ethyl cellulose, hydroxypropyl cellulose and cellulose acetate.
7. The oxygen-release material as claimed in claim 1, wherein the binder is one or more of sodium alginate, polyethylene glycol and polyvinyl alcohol.
8. The slow-release oxygen material as claimed in claim 1, wherein the dispersing agent is one or more of polyethylene oxide, dextrin, starch and polyacrylic acid.
9. The oxygen-release material as claimed in claim 1, wherein the pH buffer is one or more of ammonium acetate, sodium dihydrogen phosphate and potassium dihydrogen phosphate.
10. A method for preparing the oxygen-release-retarding material as claimed in any one of claims 1 to 9, comprising the steps of:
(1) adding an embedding agent into a first organic solvent, heating and stirring under the protection of nitrogen until the embedding agent is completely dissolved to obtain a first solution;
(2) adding the binder and the dispersant into a second organic solvent, heating and stirring the mixture under the protection of nitrogen until the binder and the dispersant are completely dissolved to obtain a second solution;
(3) mixing the first solution and the second solution prepared in the steps (1) and (2), heating under the protection of nitrogen and fully stirring to obtain a mixed solution;
(4) respectively adding the oxygen-releasing agent and the pH buffering agent into the mixed solution obtained in the step (3), and continuously heating and stirring until the oxygen-releasing agent and the pH buffering agent are completely and uniformly dispersed in the mixed solution to obtain a mixture solution;
(5) and (5) removing the organic solvent from the mixture solution prepared in the step (4), drying by a dryer, and granulating to obtain the slow release material.
11. The method according to claim 10, wherein the first organic solvent in step (1) is one or more of dichloromethane, chloroform and carbon tetrachloride.
12. The method according to claim 10, wherein the second organic solvent in step (2) is one or more selected from methanol, isopropanol, acetone and propylene glycol.
13. The use of the oxygen-release material according to any one of claims 1 to 9 or the oxygen-release material prepared by the preparation method according to any one of claims 10 to 12 in a composite material for biologically enhanced remediation of groundwater.
CN202110184406.XA 2021-02-08 2021-02-08 Slow-release oxygen material and preparation method and application thereof Pending CN114906945A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110184406.XA CN114906945A (en) 2021-02-08 2021-02-08 Slow-release oxygen material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110184406.XA CN114906945A (en) 2021-02-08 2021-02-08 Slow-release oxygen material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114906945A true CN114906945A (en) 2022-08-16

Family

ID=82761497

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110184406.XA Pending CN114906945A (en) 2021-02-08 2021-02-08 Slow-release oxygen material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114906945A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114455704A (en) * 2022-03-01 2022-05-10 南京大学 Method for deep biological denitrification enhancement and endocrine disrupting toxicity reduction

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008515881A (en) * 2004-10-07 2008-05-15 エヌジーイーエヌ・ファーマソーティカルズ・エヌ．ブイ． Stabilized oxygen release composition
CN102441566A (en) * 2011-12-07 2012-05-09 浙江省环境保护科学设计研究院 Advanced oxidization repair method for agricultural chemically contaminated soil
CN102583694A (en) * 2012-03-01 2012-07-18 中国环境科学研究院 Persulfate slow-release material used for permeable reactive barrier and preparation method thereof
CN107555607A (en) * 2017-08-21 2018-01-09 吴杨 A kind of compound oxygenation agent of biology and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008515881A (en) * 2004-10-07 2008-05-15 エヌジーイーエヌ・ファーマソーティカルズ・エヌ．ブイ． Stabilized oxygen release composition
US20080274206A1 (en) * 2004-10-07 2008-11-06 Ngen Pharmaceuticals N.V. Stabilised Oxygen Releasing Composition
CN102441566A (en) * 2011-12-07 2012-05-09 浙江省环境保护科学设计研究院 Advanced oxidization repair method for agricultural chemically contaminated soil
CN102583694A (en) * 2012-03-01 2012-07-18 中国环境科学研究院 Persulfate slow-release material used for permeable reactive barrier and preparation method thereof
CN107555607A (en) * 2017-08-21 2018-01-09 吴杨 A kind of compound oxygenation agent of biology and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114455704A (en) * 2022-03-01 2022-05-10 南京大学 Method for deep biological denitrification enhancement and endocrine disrupting toxicity reduction
CN114455704B (en) * 2022-03-01 2022-12-27 南京大学 Method for deep biological denitrification enhancement and endocrine disrupting toxicity reduction

Similar Documents

Publication Publication Date Title
Lu et al. Application of calcium peroxide in water and soil treatment: a review
O'Connor et al. Sustainable in situ remediation of recalcitrant organic pollutants in groundwater with controlled release materials: A review
CN105772499A (en) In-situ combined remediation method for petroleum contaminated site soil
US6258589B1 (en) Methods for providing a chemical to a microorganism
CN105855289A (en) In-situ combination remediation method of high-concentration petroleum hydrocarbon contaminated soil
CN105457996A (en) Method for remediating organic-contaminated place soil by using microwave in collaboration with sodium percarbonate
ES2926175T3 (en) Composition with a prolonged release material for the elimination of halogenated hydrocarbons from contaminated environments and in situ soil remediation procedure using said composition
CN112480935A (en) Calcium peroxide slow-release composite material and preparation method and application thereof
CN104445570A (en) Method for removing polycyclic aromatic hydrocarbon methylnaphthalene substance by adopting double oxidants including persulfate and calcium peroxide
KR100258781B1 (en) Use of metalic peroxides in bioremediation
CN112960765A (en) Biological permeable reactive barrier slow-release filler capable of removing trichloroethylene in underground water in situ and having core-shell structure and preparation method thereof
CN114433161B (en) Composite material for efficiently activating monopersulfate, and preparation method and application thereof
CN106623382A (en) Method for repairing organochlorine pesticide-polluted soil through microwave-enhanced sodium percarbonate
CN103709694B (en) The technique of perchlorate and degradable composite material used in a kind of degradation water
CN106583441A (en) Method for recovery of organic chloride-polluted soil through ultrasonic intensified potassium ferrate/hydrogen peroxide
Gao et al. Bioaugmented removal of 17β-estradiol, nitrate and Mn (II) by polypyrrole@ corn cob immobilized bioreactor: Performance optimization, mechanism, and microbial community response
CN114906945A (en) Slow-release oxygen material and preparation method and application thereof
CN110964536B (en) Iron-based soil remediation agent and preparation method thereof
CN113121290A (en) Method for synchronously promoting ammonia nitrogen removal and lead-cadmium passivation in soil
CN115231680A (en) Preparation method and application of biochar loaded nano zero-valent iron material
CN114177845A (en) Preparation method of multifunctional water ecological restoration polyvinyl alcohol hydrogel material
CN110540283A (en) Method for enhanced removal of sulfamethoxazole in water
Miao et al. Norfloxacin degradation in synthetic human urine using nickel converter slag-laterite heterogeneous Electro-Fenton process
Beolchini et al. Bioremediation of sediments contaminated with polycyclic aromatic hydrocarbons: the technological innovation patented review
CN108480394A (en) A kind of efficient chemical for organic polluted soil aoxidizes restorative procedure

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