CN105668689A - Multifunctional slow-release restoration agent applied to underground water in-situ restoration - Google Patents
Multifunctional slow-release restoration agent applied to underground water in-situ restoration Download PDFInfo
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- CN105668689A CN105668689A CN201610220717.6A CN201610220717A CN105668689A CN 105668689 A CN105668689 A CN 105668689A CN 201610220717 A CN201610220717 A CN 201610220717A CN 105668689 A CN105668689 A CN 105668689A
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- renovation agent
- release
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Treatment Of Biological Wastes In General (AREA)
Abstract
The invention discloses a multifunctional slow-release restoration agent applied to in-situ restoration of an underground water body polluted by organic matter and applied to a permeable reactive wall (PCR) underground water restoration technology, and belongs to the technical field of underground water restoration.The restoration agent is mainly prepared from calcium peroxide, clay, molysite, cyclodextrin and an adhesive, and a slow-release ball which is with a structure of an inner layer and an outer layer is obtained according to a certain proportion.The inner layer is used for providing oxygen needed by growth and propagation of microorganisms in a natural water body, and the outer layer is used for degrading organic pollutants in the underground water.The multifunctional slow-release restoration agent has the advantages that the organic pollutants and heavy metal in the underground water body are adsorbed, and diffusion of pollution and concentration of the pollutants in the water body are reduced; oxidation of the organic pollutants is promoted, the toxicity of the organic pollutants is reduced, and the biodegradability is improved; oxygen is provided for the microorganisms, indigenous microorganisms are promoted to grow rapidly, and the pollutants in the water body are thoroughly degraded.
Description
Technical field
The present invention relates to body of groundwater based technique for in-situ remediation polluted by organic matter, particularly relate to one and there is absorption, oxidation subsoil water Organic substance, and the multifunctional slow-release renovation agent improving Dissolved Oxygen in Water and preparation method thereof.
Background technology
Subsoil water is as the freshwater resources of mankind's preciousness, along with the development of modern society's process of industrialization, occurring in that pollution problem in various degree, each pollutant of generation first passes through surface water, the surrounding mediums such as soil, by osmosis and recharge of ground water polluted underground water environment. From eighties of last century sixties, underground water pollution aggravates gradually, and then the recovery technique of subsoil water also grows up consequent therewith.
At present the groundwater remediation technology polluted is broadly divided into showering technology and based technique for in-situ remediation. Showering technology is that contaminated underground water is drawn to the technology that earth's surface carries out processing again. This technology treating capacity in a short time is big, treatment effeciency is higher, but prolonged application ubiquity the phenomenons such as pollutant levels hangover, bounce-back, eventually reduces treatment effeciency, increases processing cost. Based technique for in-situ remediation is just repaired thoroughly with it, the advantages such as pollutant kind is many, the time is relatively short, relative inexpensiveness that process are repaired field at underground water pollution and shown up prominently, and is widely applied to today. The mainstream technology being applied to Organic Contamination of Groundwater thing reparation at present is permeable reaction wall technology, this technology have easy and simple to handle, run and the low advantage of maintenance cost, reaction medium long lasting for in-situ treatment, mankind's activity and ecological environment disturbance is less, can have broad application prospects.
The features such as calper calcium peroxide is high owing to having environmental friendliness oxygen release efficiency, low price and be widely used in soil as the oxygen release renovation agent commonly used, surface water, in sediment remediation process. Calper calcium peroxide is also the compound with oxygen release function and oxidative function. Both functions of calper calcium peroxide are concurrently presented in a kind of product by slow release method and nucleocapsid structure by inventor, and there is the cyclodextrin of adsorption fouling thing function and catalyst iron salt optimizes the process of oxidation stain thing by adding, it is achieved that collection absorption, oxidation, oxygen release three zones slow release renovation agent. This materials application serves as center-filled thing in permeable reaction wall. When subsurface flow is through permeable reaction wall, organic pollution therein is repaired rapidly the absorption of agent cyclodextrin or is promoted the oxidation of organic pollution by co-oxidation, reduces its toxicity, improves biodegradability; While removing pollutant, this material, also at slow releasing oxygen, improves the environment of low dissolved oxygen in subsoil water, provides oxygen for microorganism, promotes that indigenous microorganism quickly increases, thoroughly pollutant in degraded water body.
Summary of the invention
The invention aims to solve the deficiencies in the prior art, in the process repairing subsoil water polluted by organic matter, it is provided that one can remove organic pollution simultaneously, improves the Multifunction slow-release material of the low dissolved oxygen environment of subsoil water.
Technical scheme: a kind of multifunctional slow-release renovation agent being applied to subsoil water in-situ immobilization polluted by organic matter of the present invention, it is made up of inside and outside two-layer: internal layer is slow release oxygen layer, it is mainly composed of calper calcium peroxide, adhesive, clay, its each constituent mass percentage ratio is followed successively by 40%-50%, 2%-5%, 45%-58%; Outer layer is oxide layer, is mainly composed of calper calcium peroxide, iron salt, adhesive, cyclodextrin, and its each constituent mass percentage ratio is followed successively by 60%-80%, 0.5%-1%, 2%-5%, 14%-37.5%. Described adhesive refer to ethyl cellulose, hydroxyethyl cellulose, cellulose acetate, chitosan one or more, described iron salt refer to ferrous sulfate, iron sulfate, ferrous chloride, iron chloride one or more; The mass percent of renovation agent internal layer and outer two-layer respectively 60%-80%, 20%-40%.
The preparation method of a kind of multifunctional slow-release renovation agent being applied to body of groundwater in-situ immobilization polluted by organic matter of the present invention, comprise the steps: that (1) is by calper calcium peroxide, clay, adhesive mixing and stirring, at being used in 55-65 DEG C, dehydrated alcohol is dropwise instilled, and be stirred continuously, until solid is all wetted, the mixture obtained is passed through granulator granulation, obtains the spherical particle that diameter is 5-60mm and be the internal layer of renovation agent; (2) calper calcium peroxide, iron salt, adhesive, cyclodextrin are added in dehydrated alcohol with certain mass ratio; making mass fraction is 50%(w/w) mixture; sprayed on the internal layer surface of the renovation agent prepared with spray thrower; after internal layer is completely capped and during mass percent respectively 60%-80% and the 20%-40% of internal layer and outer layer; take out prepared solid renovation agent at 60-85 DEG C; dry under the protection of nitrogen, and reclaim ethanol.
The application process of described multifunctional slow-release renovation agent, it is characterized in that, kind according to the degree of underground water pollution, water volume flow rate and pollutant, adjust each component ratio in multifunctional slow-release renovation agent, overall dimensions and dosage, make calper calcium peroxide in renovation agent, iron salt, cyclodextrin combine and have an effect, and adsorbs and aoxidizes pollutant in water body, and control oxygen release so as to other indigenous microorganism is utilized to greatest extent, promote microbial growth under stimulation.
Below in conjunction with specific embodiment, the present invention done further description, but protection scope of the present invention is not limited to that.
Embodiment 1
(1) calper calcium peroxide, adhesive, clay being pressed mass percent 50%, 48%, 2% mixing and stirring, be used at 60 DEG C, dehydrated alcohol dropwise instills, and is stirred continuously, until solid is all wetted. The mixture obtained is passed through granulator granulation, obtains the spherical particle that diameter is 10mm and be the internal layer of renovation agent. (2) calper calcium peroxide, iron salt, adhesive, cyclodextrin are pressed mass percent 80%, 1%, 2%, 17% in dehydrated alcohol, making mass fraction is 50%(w/w) mixture, sprayed on the internal layer surface of renovation agent prepared with spray thrower, obtain the mass percent of internal layer and outer layer respectively 60% and 40% renovation agent. By prepared solid renovation agent at 60 DEG C, dry under the protection of nitrogen, and reclaim ethanol.
The renovation agent 1g obtained is placed in the 20mg/L bisphenol-A anaerobic solution of 1L, it is placed in the light protected environment that room temperature is 15 DEG C and is stirred continuously, period sampling measuring bisphenol A concentration and dissolved oxygen concentration, intraday bisphenol-A clearance is 92.2%, and dissolved oxygen concentration is increased to 8mg/L from 0mg/L.
Embodiment 2
(1) calper calcium peroxide, adhesive, clay being pressed mass percent 40%, 55%, 5% mixing and stirring, be used at 60 DEG C, dehydrated alcohol dropwise instills, and is stirred continuously, until solid is all wetted. The mixture obtained is passed through granulator granulation, obtains the spherical particle that diameter is 10mm and be the internal layer of renovation agent. (2) calper calcium peroxide, iron salt, adhesive, cyclodextrin are pressed mass percent 60%, 1%, 5%, 34% in dehydrated alcohol, making mass fraction is 50%(w/w) mixture, sprayed on the internal layer surface of renovation agent prepared with spray thrower, obtain the mass percent of internal layer and outer layer respectively 60% and 40% renovation agent. Finally by prepared solid renovation agent at 60 DEG C, dry under the protection of nitrogen, and reclaim ethanol.
The renovation agent 1g obtained is placed in the 20mg/L bisphenol-A anaerobic solution of 1L, it is placed in the light protected environment that room temperature is 15 DEG C and is stirred continuously, period sampling measuring bisphenol A concentration and dissolved oxygen concentration, intraday bisphenol-A clearance is 90.2%, and dissolved oxygen concentration is increased to 3mg/L from 0mg/L.
Embodiment 3
(1) calper calcium peroxide, adhesive, clay being pressed mass percent 45%, 52%, 3% mixing and stirring, be used at 60 DEG C, dehydrated alcohol dropwise instills, and is stirred continuously, until solid is all wetted. The mixture obtained is passed through granulator granulation, obtains the spherical particle that diameter is 10mm and be the internal layer of renovation agent. (2) calper calcium peroxide, iron salt, adhesive, cyclodextrin are pressed mass percent 70%, 1%, 3%, 26% in dehydrated alcohol, making mass fraction is 50%(w/w) mixture, sprayed on the internal layer surface of renovation agent prepared with spray thrower, obtain the mass percent of internal layer and outer layer respectively 60% and 40% renovation agent. Finally by prepared solid renovation agent at 60 DEG C, dry under the protection of nitrogen, and reclaim ethanol.
The renovation agent 1g obtained is placed in the 20mg/L Nitrobenzol anaerobic solution of 1L, it is placed in the light protected environment that room temperature is 15 DEG C and is stirred continuously, period sampling measuring bisphenol A concentration and dissolved oxygen concentration, intraday bisphenol-A clearance is 89.2%, and dissolved oxygen concentration is increased to 5mg/L from 0mg/L.
Embodiment 4
(1) calper calcium peroxide, adhesive, clay being pressed mass percent 45%, 52%, 3% mixing and stirring, be used at 60 DEG C, dehydrated alcohol dropwise instills, and is stirred continuously, until solid is all wetted. The mixture obtained is passed through granulator granulation, obtains the spherical particle that diameter is 10mm and be the internal layer of renovation agent. (2) calper calcium peroxide, iron salt, adhesive, cyclodextrin are pressed mass percent 70%, 1%, 3%, 26% in dehydrated alcohol, making mass fraction is 50%(w/w) mixture, sprayed on the internal layer surface of renovation agent prepared with spray thrower, obtain the mass percent of internal layer and outer layer respectively 60% and 40% renovation agent. Finally by prepared solid renovation agent at 60 DEG C, dry under the protection of nitrogen, and reclaim ethanol.
Taking the lower 2 meters of bisphenol-A pollutant effluents in Shanghai City plastic molding and processing plant sewage draining exit waste water earth's surface, its bisphenol A concentration is 0.5mg/L. Making content of oxygen dissolved in water lower than 0.5mg/L to the subsoil water nitrogen blowing (3ml/L) in container, hermetic container prevents the oxygen in air from reentering water body afterwards.
The experimental facilities of simulation permeable reactive barrier is a lucite reaction column, and length is 20cm, and internal diameter is 10cm, and the quartz sand of 3mm is filled at the bottom of pillar and top, and mid-section body is partially filled with prepared renovation agent, and fills up space with sand.Bottom and top are respectively provided with a water inlet and outlet, arrange sample tap at water inlet and outlet.
Pumping into pillar in the flow velocity of 15ml/h from water inlet by the subsoil water of acquirement with peristaltic pump, the concentration of water inlet place bisphenol-A is 0.5mg/L, and solution oxygen concentration is 0.3mg/L. Under the effect of peristaltic pump, water body flows upward to capital water outlet from the low water inlet of post, and this process needs 1 day, and every day from each sample tap sampling of pillar, detects the concentration of the bisphenol-A of water sample and the concentration of dissolved oxygen in different time points.
Experimental result: the 1st day, the bisphenol A concentration of water outlet is 0.015, and clearance is 97%, and dissolved oxygen concentration is 6.2mg/L.
2nd day, the bisphenol A concentration of water outlet was 0.007, and clearance is 98.6%, and dissolved oxygen concentration is 5.8mg/L.
4th day, the bisphenol A concentration of water outlet was 0.009, and clearance is 98.2%, and dissolved oxygen concentration is 4.9mg/L.
6th day, the bisphenol A concentration of water outlet was 0.012, and clearance is 97.6%, and dissolved oxygen concentration is 5.3mg/L.
10th day, the bisphenol A concentration of water outlet was 0.007, and clearance is 98.6%, and dissolved oxygen concentration is 5.8mg/L.
15th day, the bisphenol A concentration of water outlet was 0.017, and clearance is 96.6%, and dissolved oxygen concentration is 6.1mg/L.
30th day, the bisphenol A concentration of water outlet was 0.010, and clearance is 98.0%, and dissolved oxygen concentration is 5.5mg/L.
Claims (6)
1. the multifunctional slow-release renovation agent being applied to subsoil water in-situ immobilization polluted by organic matter, it is made up of inside and outside two-layer: internal layer is slow release oxygen layer, is mainly composed of calper calcium peroxide, adhesive, clay, its each constituent mass percentage ratio is followed successively by 40%-50%, 2%-5%, 45%-58%; Outer layer is oxide layer, is mainly composed of calper calcium peroxide, iron salt, adhesive, cyclodextrin, and its each constituent mass percentage ratio is followed successively by 60%-80%, 0.5%-1%, 2%-5%, 14%-37.5%; Described adhesive refer to ethyl cellulose, hydroxyethyl cellulose, cellulose acetate, chitosan one or more, described iron salt refer to ferrous sulfate, iron sulfate, ferrous chloride, iron chloride one or more; The mass percent of renovation agent internal layer and outer two-layer respectively 60%-80% and 20%-40%.
2. the preparation method of multifunctional slow-release renovation agent according to claim 1, it is characterized in that, it carries out as follows: (1) is by calper calcium peroxide, clay, adhesive mixing and stirring, at being used in 55-65 DEG C, dehydrated alcohol is dropwise instilled, and is stirred continuously, until solid is all wetted, the mixture obtained is passed through granulator granulation, obtains the spherical particle that diameter is 5-60mm and be the internal layer of renovation agent; (2) calper calcium peroxide, iron salt, adhesive, cyclodextrin are added in dehydrated alcohol with certain mass ratio; making mass fraction is 50%(w/w) mixture; sprayed on the internal layer surface of the renovation agent prepared with spray thrower; after internal layer is completely capped and during mass percent respectively 60%-80% and the 20%-40% of internal layer and outer layer; take out; the solid renovation agent prepared is at 60-85 DEG C, dry under the protection of nitrogen, and reclaims ethanol.
3. multifunctional slow-release renovation agent according to claim 1, it is characterized in that, the structure of this renovation agent is divided into inside and outside two-layer, and internal layer is slow release oxygen layer, being mainly composed of calper calcium peroxide, adhesive, clay, its each constituent mass percentage ratio is followed successively by 50%, 5%, 45%;Outer layer is oxide layer, is mainly composed of calper calcium peroxide, iron salt, adhesive, cyclodextrin, and its each constituent mass percentage ratio is followed successively by 80%, 1%, 5%, 14%.
4. multifunctional slow-release renovation agent according to claim 1, it is characterised in that this renovation agent has slow-releasing under the effect of adhesive.
5. multifunctional slow-release renovation agent according to claim 1, it is characterised in that for the subsoil water in-situ immobilization of Organic Pollution.
6. multifunctional slow-release renovation agent according to claim 1, it is characterised in that in use this renovation agent is filled in permeable reactive barrier, and the stage of replacement be limited to 60 days～280 days.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610220717.6A CN105668689A (en) | 2016-04-11 | 2016-04-11 | Multifunctional slow-release restoration agent applied to underground water in-situ restoration |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409080A (en) * | 2018-04-09 | 2018-08-17 | 四川众淼环保科技有限公司 | A kind of in-situ sediment remediation particle and preparation method thereof, application method, application |
| CN110407266A (en) * | 2019-08-01 | 2019-11-05 | 山东省地质矿产勘查开发局八〇一水文地质工程地质大队 | Slow-release medicament for in-situ remediation of underground water polluted by hydrochloric ether in deep mine |
| CN110451590A (en) * | 2019-08-01 | 2019-11-15 | 山东省地质矿产勘查开发局八〇一水文地质工程地质大队 | Preparation method of in-situ remediation slow-release agent for underground water polluted by hydrochloric ether in deep mine |
| CN110871056A (en) * | 2019-12-03 | 2020-03-10 | 江西夏氏春秋环境股份有限公司 | Underground water repairing agent, preparation method and use method |
| CN111892155A (en) * | 2020-08-20 | 2020-11-06 | 江苏苏美达成套设备工程有限公司 | Slow-release oxidizing agent for removing underground water polluted organic matter and process thereof |
| CN114054484A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Permeable reactive barrier and method for repairing polluted underground water by permeable reactive barrier |
| CN115433584A (en) * | 2022-08-17 | 2022-12-06 | 吉林建筑大学 | Calcium peroxide-sodium persulfate synergistic in-situ remediation method for organic composite polluted site |
| CN115722529A (en) * | 2022-11-17 | 2023-03-03 | 南开大学 | Method for promoting Fenton reaction to repair organic contaminated soil by microwave slow-release material |
| CN115845625A (en) * | 2022-11-24 | 2023-03-28 | 哈尔滨工业大学 | Solid hydrogen peroxide effervescent tablet, preparation method thereof and method for cleaning ultrafiltration membrane in situ by using solid hydrogen peroxide effervescent tablet |
| CN115893679A (en) * | 2022-11-15 | 2023-04-04 | 吉林大学 | Nutrient matrix sustained-release medicament for stimulating bioremediation of VCHs polluted underground water |
| CN114054484B (en) * | 2020-07-31 | 2024-06-07 | 中国石油化工股份有限公司 | Permeable reactive barrier and method for repairing polluted underground water by same |
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- 2016-04-11 CN CN201610220717.6A patent/CN105668689A/en active Pending
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| CN108409080B (en) * | 2018-04-09 | 2021-10-22 | 四川众淼环保科技有限公司 | Sediment in-situ remediation particles and preparation method, use method and application thereof |
| CN108409080A (en) * | 2018-04-09 | 2018-08-17 | 四川众淼环保科技有限公司 | A kind of in-situ sediment remediation particle and preparation method thereof, application method, application |
| CN110407266A (en) * | 2019-08-01 | 2019-11-05 | 山东省地质矿产勘查开发局八〇一水文地质工程地质大队 | Slow-release medicament for in-situ remediation of underground water polluted by hydrochloric ether in deep mine |
| CN110451590A (en) * | 2019-08-01 | 2019-11-15 | 山东省地质矿产勘查开发局八〇一水文地质工程地质大队 | Preparation method of in-situ remediation slow-release agent for underground water polluted by hydrochloric ether in deep mine |
| CN110871056A (en) * | 2019-12-03 | 2020-03-10 | 江西夏氏春秋环境股份有限公司 | Underground water repairing agent, preparation method and use method |
| CN114054484A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Permeable reactive barrier and method for repairing polluted underground water by permeable reactive barrier |
| CN114054484B (en) * | 2020-07-31 | 2024-06-07 | 中国石油化工股份有限公司 | Permeable reactive barrier and method for repairing polluted underground water by same |
| CN111892155A (en) * | 2020-08-20 | 2020-11-06 | 江苏苏美达成套设备工程有限公司 | Slow-release oxidizing agent for removing underground water polluted organic matter and process thereof |
| CN115433584A (en) * | 2022-08-17 | 2022-12-06 | 吉林建筑大学 | Calcium peroxide-sodium persulfate synergistic in-situ remediation method for organic composite polluted site |
| CN115433584B (en) * | 2022-08-17 | 2024-04-19 | 吉林建筑大学 | Synergistic in-situ repair method for calcium peroxide-sodium persulfate in organic composite polluted site |
| CN115893679A (en) * | 2022-11-15 | 2023-04-04 | 吉林大学 | Nutrient matrix sustained-release medicament for stimulating bioremediation of VCHs polluted underground water |
| CN115722529A (en) * | 2022-11-17 | 2023-03-03 | 南开大学 | Method for promoting Fenton reaction to repair organic contaminated soil by microwave slow-release material |
| CN115845625A (en) * | 2022-11-24 | 2023-03-28 | 哈尔滨工业大学 | Solid hydrogen peroxide effervescent tablet, preparation method thereof and method for cleaning ultrafiltration membrane in situ by using solid hydrogen peroxide effervescent tablet |
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Application publication date: 20160615 |