CN110407266A - Slow-release medicament for in-situ remediation of underground water polluted by hydrochloric ether in deep mine - Google Patents
Slow-release medicament for in-situ remediation of underground water polluted by hydrochloric ether in deep mine Download PDFInfo
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- CN110407266A CN110407266A CN201910724355.8A CN201910724355A CN110407266A CN 110407266 A CN110407266 A CN 110407266A CN 201910724355 A CN201910724355 A CN 201910724355A CN 110407266 A CN110407266 A CN 110407266A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
-
- 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
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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
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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
- C02F1/722—Oxidation by peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/22—O2
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/29—Chlorine compounds
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
- C02F2305/04—Surfactants, used as part of a formulation or alone
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The slow released medicine for in-situ remediation of underground water polluted by hydrochloric ether in deep mine includes peroxide 10-40 wt%, iron tourmaline 5-30 wt%, persulfate 20-50 wt%, surfactant 1-5 wt% and adhesive 5-20 wt%. The slow-release medicament for in-situ remediation of underground water polluted by hydrochloric ether in a deep mine has higher solid particle density, can enter the bottom layer of underground polluted water by utilizing the gravity settling effect of the slow-release medicament in the process of injecting the slow-release medicament into the underground water in the deep mine, forms a double oxidation system after being dissolved in the water, degrades and treats the hydrochloric ether pollutants settled at the bottom of the water, obviously improves the degradation efficiency, and can adjust the pH value of an aqueous solution to lead the aqueous solution to tend to be neutral.
Description
Technical field
The invention belongs to groundwater remediation fields, are related to a kind of for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization
Slow-releasing agent.
Background technique
In recent years, with China's economization and the continuous quickening of process of industrialization, " moving back two into three ", " garden Tui Chengjin " policy
Further implement, large quantities of contaminating enterprises are forced resettlement, transformation is even switched off halts production, and city and its surrounding area is caused to occur greatly
Abandonment contaminated site is left in the industry of amount, causes seriously to pollute to underground water and soil, especially more tight with chlorinated hydrocarbon contaminants
Weight, and such organic pollutant has " three cause " effect, i.e. mutagenesis, carcinogenic and teratogenic effect, constitutes to human health tight
It threatens again, there is an urgent need to take measure rapidly and efficiently to be administered.
Chlorohydrocarbon exists in underground water in the form of DNAPL (dense non-aqueous phase liquid), molten
Xie Du is smaller, and density ratio water is big, is sunken to the bottom, and viscosity is low.The chlorohydrocarbon dissolved in underground water has good migration, can shape
It at elongated Pollution Plume, causes to pollute on a large scale, and Ecotoxicology effect is very big, is not easy to be dropped by the microorganism of nature
Solution, Natural Attenuation may need the century-old time.
Currently, the recovery technique of shallow-layer chlorohydrocarbon polluted underground water mainly has showering and two kinds of in-situ immobilization.Dystopy
The main method of reparation is extraction-water treatment technology, and in-situ immobilization mainly includes in situ chemical oxidation technology, underground water aeration skill
Art, electro reclamation and hydrodynamic seepage pressure technology etc. in situ.Wherein, it is directed to get dirty using more in situ chemical oxidation technology
The strong oxidizers such as hydrogen peroxide, persulfate, potassium permanganate, ozone are injected in the underground water of dye, and oxidation occurs also with pollutant
Contaminant degradation is the smaller molecule of harmless or toxicity by original reaction.
Rarely have in the prior art for the repairing research of deep layer mine chlorohydrocarbon polluted underground water and is related to.The invention relates to
And deep layer mine refer to depth be greater than 70 meters of underground mine.Utilize existing in situ chemical oxidation technical treatment deep layer mine
During polluted underground water, liquid hydrogen peroxide is repaired in deep phreatic water due to its resolution characteristic and is easy hair in injection process
Raw disproportionated reaction etc., does not reach deep layer mine bottom, is just decomposed to form oxygen and water, so as to the repairing effect pole of deep layer mine
Difference, or even do not work.Therefore the disproportionation decomposition in liquid hydrogen peroxide transmission process is that it is applied to deep layer polluted underground water
The problem of reparation.
Calper calcium peroxide has both the environmentally friendly material of oxygen release and oxidisability as one kind, is used for underground water in recent years
Reparation field.Calper calcium peroxide, which is dissolved in water, can be generated hydrogen peroxide and oxygen, and the yield maximum of hydrogen peroxide is reachable
0.47gH2O2/gCaO2, so calper calcium peroxide is also referred to as " solid hydrogen peroxide ".Compared with liquid hydrogen peroxide, calper calcium peroxide
Property is more stable, and the amount for generating hydrogen peroxide can control rate of dissolution to regulate and control, so calper calcium peroxide by regulating system pH
It is more fully utilized in actual repair compared to hydrogen peroxide.Moreover, it is micro- can also to generate oxygen promotion original inhabitants for it
The growth of biology, and then improve biological prosthetic efficiency.Patent No.: 201110426869.9, invention and created name is " a kind ofly
Reparation is lauched with slow-release oxygen material and preparation method thereof " Chinese patent disclose a kind of groundwater remediation slow-release oxygen material,
Including inner nuclear material and sheathing material, the inner nuclear material is made of following component according to weight percent: 50-80% is released
Oxygen agent, 10-40% plasticity bond mineral, 1-30%pH buffer, 1-30% high osmosis material.This slow-release oxygen material is main
Increase the dissolved oxygen content of sewage using the oxygen release of peroxide.Deep layer mine middle and high concentration, the biggish chlorine of bio-toxicity
For hydrocarbon polluted underground water, it is difficult to degrade high-solubility oxygen content is provided, therefore patent of invention offer is this slow
Oxygen-release material Biodegradation Times are long, or are difficult that biodegrade occurs, and chlorohydrocarbon polluted underground water cannot be effectively treated.Moreover,
The slow-release oxygen material outer layer has sheathing material, is impregnated in water without broken, after so that pharmacy particle is entered the bottom effective agent from
Disperse to spread with subsurface flow direction, is unfavorable for increasing repairing effect.
Foregoing invention patent additionally provides the preparation method of the groundwater remediation slow-release oxygen material, including walks as follows
Rapid: (1) to be all crushed to 200 mesh according to the raw material in the constituent of aforementioned slow-release oxygen material in addition to high osmosis material standby
With；(2) standby according to all 50 mesh are crushed in addition to quartz sand in the constituent middle and high infiltration transpirant material of aforementioned slow-release oxygen material
With；(3) constituent of various slow-release oxygen materials is sufficiently mixed uniformly, in pelletizer plus water is rolled to ball-type, until reaching
To expected partial size 0.5-3cm；(4) it rolls to expected partial size, sheathing material is added, with a thickness of 0.05cm；(5) by sphere material
It is placed in confined space and conserves 2-3 days, until the granule strength of slow-release oxygen material reaches 20-50N/ testing level, and
Its hardness can reach impregnates without broken degree for a long time in water.The preparation method for the slow-release oxygen material that the patent of invention provides
In have plus water step, raw material adds persulfate and calper calcium peroxide after water to meet water and react, and medicament is caused to waste.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization
Slow-releasing agent.
A kind of slow-releasing agent for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization, according to weight percent, packet
Include peroxide 10%~40%, iron tourmaline 5%~30%, persulfate 20%~50%, surfactant 1%~5%,
Adhesive 5%~20%.
Preferably, the peroxide is peromag or calper calcium peroxide or both mixture.
Preferably, the persulfate is sodium peroxydisulfate or potassium peroxydisulfate or both mixture.
Preferably, surfactant is cyclodextrin.
Preferably, the binder is ordinary portland cement or chitosan.
Provided by the present invention for the slow-releasing agent of deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization, solid particle
Density is larger, can enter the bottom of underground pollution water using the effect of its gravitational settling during injecting deep layer mine groundwater
Layer carries out degradation treatment to demersal chlorinated hydrocarbon contaminants.
Mistake provided by the present invention for the slow-releasing agent of deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization, in ingredient
Oxide, which is dissolved in water, can be generated hydrogen peroxide and oxygen.The iron tourmaline reaction reacted in the hydrogen peroxide and ingredient generated can
To generate hydroxyl radical free radical, hydroxyl radical free radical can degrade to the chlorohydrocarbon in sewage；Persulfate in ingredient is by ferroelectricity
(dissolution generates Fe to gas stone2+) activation, it can produce hydroxyl radical free radical and potentiometric titrations, degrade to chlorohydrocarbon.Over cure
Hydrochlorate and calper calcium peroxide mutually cooperate with, and form dual oxide system, hence it is evident that improve degradation efficiency.
Moreover, the iron tourmaline in ingredient influences the oxidation-reduction potential of aqueous solution since there are permanent electrodes for itself,
The pH value for adjusting aqueous solution is allowed to tend to neutral.
Surfactant in the invention ingredient has the function of to adsorb pollutant；Iron tourmaline and peroxide in ingredient
Compound and persulfate form hydroxyl radical free radical and potentiometric titrations, it is made to have oxidative function, improve biodegradability；Ingredient
In peroxide meet water discharge oxygen, be conducive to biodegrade；Therefore, what the invention provided is used for deep layer mine chloro
The slow-releasing agent of hydrocarbon polluted underground water in-situ immobilization has absorption, oxidation, oxygen release three zones, and makes during environment pH maintains
Under the conditions of property.
The preparation method of slow-releasing agent for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization, including walk as follows
It is rapid:
(1) raw material is ground, 200 meshes are crossed, by weight percentage, according to following ratio mixed raw material: 10%~40%
Peroxide, 20%~50% persulfate, 5%~30% iron tourmaline, 5%~20% adhesive, 1%~
5% surfactant, obtains mixture of powders；
(2) under the conditions of 25-65 DEG C of temperature, dehydrated alcohol is instilled to the mixture of powders dropwise, and be stirred continuously, directly
It is all soaked to the mixture of powders, obtains muddy mixture；Wherein, the weight ratio of dehydrated alcohol and the mixture of powders
It is 1~3: 10；
(3) the muddy mixture is granulated by pelletizer, obtains the spherical particle that diameter is 10-50mm；
(4) dry under the protection of nitrogen by spherical particle obtained at a temperature of 60-85 DEG C, and ethyl alcohol is recycled, it obtains into
Product.
Preferably, the peroxide is peromag or calper calcium peroxide or both mixture.
Preferably, the persulfate is sodium peroxydisulfate or potassium peroxydisulfate or both mixture.
Preferably, surfactant is cyclodextrin.
Preferably, the binder is ordinary portland cement or chitosan.
Provided by the present invention for the preparation method of the slow-releasing agent of deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization,
Without adding water step in raw material mixed process, persulfate and calper calcium peroxide will not meet water and react, and avoid medicament waste.
The preparation method carries out recycling and reusing to ethyl alcohol, economizes on resources, and reduces production cost.Preparation method preparation is used for deep layer
The slow-releasing agent density of mine chlorohydrocarbon polluted underground water in-situ immobilization is big, can effectively fall to deep layer mine underground pollution water
Bottom, and effective agent is made to disperse to spread with subsurface flow direction, increase repairing effect, to the chlorohydrocarbon for being sunken to underground water bottom
Polluted underground water carries out in-situ immobilization.
Specific embodiment
Embodiment 1:
Raw material is ground, 200 meshes are crossed, by weight percentage, according to following ratio mixed raw material: 20% peroxidating
Calcium, 40% sodium peroxydisulfate, 15% portland cement, 2% cyclodextrin, 23% iron tourmaline are mixed evenly, In
At 25 DEG C, dehydrated alcohol is instilled dropwise, and be stirred continuously, until solid mixture is all wetted, obtain muddy mixture,
In, obtained muddy mixture is granulated by the weight ratio of dehydrated alcohol and the mixture of powders for 1: 5 by pelletizer, is obtained
The spherical particle for being 10mm to diameter；Spherical particle obtained is dry at 60 DEG C, under the protection of nitrogen, and ethyl alcohol is recycled,
It must be used for the slow-releasing agent finished product of deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization.
The slow-releasing agent injection deeper subsurface obtained for being used for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization is dirty
It contaminates in water, period sampling measuring trichloro ethylene concentration and dissolved oxygen concentration, the trichloro ethylene removal rate in 18h is 92.2%, molten
It solves oxygen concentration and is increased to 4mg/L from 0mg/L.
Embodiment 2:
Raw material is ground, 200 meshes are crossed, by weight percentage, according to following ratio mixed raw material: 30% peroxidating
Calcium, 30% sodium peroxydisulfate, 20% chitosan, 4% cyclodextrin, 16% iron tourmaline are mixed evenly, at 30 DEG C
Under, dehydrated alcohol is instilled dropwise, and be stirred continuously, until solid mixture is all wetted, obtain muddy mixture, wherein
Obtained muddy mixture is granulated by the weight ratio of dehydrated alcohol and the mixture of powders for 1: 10 by pelletizer, is obtained
Diameter is the spherical particle of 20mm；Spherical particle obtained is dry at 70 DEG C, under the protection of nitrogen, and ethyl alcohol is recycled, it obtains
Slow-releasing agent finished product for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization.
The slow-releasing agent finished product obtained for being used for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization is injected into underground water
In, period sampling measuring trichloro ethylene concentration and dissolved oxygen concentration, the trichloro ethylene removal rate in 18h are 90.5%, dissolved oxygen
Concentration is increased to 5mg/L from 0mg/L.
Embodiment 3:
Raw material is ground, 200 meshes are crossed, by weight percentage, according to following ratio mixed raw material: 40% peroxidating
Calcium, 20% sodium peroxydisulfate, 15% portland cement, 5% cyclodextrin, 20% iron tourmaline are mixed evenly, In
At 40 DEG C, dehydrated alcohol is instilled dropwise, and be stirred continuously, until solid mixture is all wetted, obtain muddy mixture,
In, obtained muddy mixture is granulated by the weight ratio of dehydrated alcohol and the mixture of powders for 1: 10 by pelletizer,
Obtain the spherical particle that diameter is 30mm；Spherical particle obtained is dry at 75 DEG C, under the protection of nitrogen, and recycle second
Alcohol obtains the slow-releasing agent finished product for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization.
The slow-releasing agent finished product obtained for being used for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization is injected into underground water
In, period sampling measuring trichloro ethylene concentration and dissolved oxygen concentration, the trichloro ethylene removal rate in 18h are 94.8%, dissolved oxygen
Concentration is increased to 6mg/L from 0mg/L.
Embodiment 4:
Raw material is ground, 200 meshes are crossed, by weight percentage, according to following ratio mixed raw material: 40% peroxidating
Calcium, 20% sodium peroxydisulfate, 15% chitosan, 4% cyclodextrin, 21% iron tourmaline are mixed evenly, at 50 DEG C
Under, dehydrated alcohol is instilled dropwise, and be stirred continuously, until solid mixture is all wetted, obtain muddy mixture, wherein
Obtained muddy mixture is granulated by the weight ratio of dehydrated alcohol and the mixture of powders for 3: 10 by pelletizer, is obtained
Diameter is the spherical particle of 40mm；Spherical particle obtained is dry at 80 DEG C, under the protection of nitrogen, and ethyl alcohol is recycled, it obtains
Slow-releasing agent finished product for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization.
The slow-releasing agent finished product obtained for being used for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization is injected into underground water
In, period sampling measuring tce concentration and dissolved oxygen concentration, the tetrachloro-ethylene removal rate in 18h are 94.5%, dissolved oxygen
Concentration is increased to 6mg/L from 0mg/L.
Embodiment 5:
Raw material is ground, 200 meshes are crossed, by weight percentage, according to following ratio mixed raw material: 30% peroxidating
Calcium, 30% sodium peroxydisulfate, 20% portland cement, 3% cyclodextrin, 17% iron tourmaline are mixed evenly, In
At 65 DEG C, dehydrated alcohol is instilled dropwise, and be stirred continuously, until solid mixture is all wetted, obtain muddy mixture,
In, obtained muddy mixture is granulated by the weight ratio of dehydrated alcohol and the mixture of powders for 1: 10 by pelletizer,
Obtain the spherical particle that diameter is 50mm；Spherical particle obtained is dry at 85 DEG C, under the protection of nitrogen, and recycle second
Alcohol obtains the slow-releasing agent finished product for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization.
The slow-releasing agent finished product obtained for being used for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization is injected into underground water
In, period sampling measuring tce concentration and dissolved oxygen concentration, the tetrachloro-ethylene removal rate in 18h are 93.8%, dissolved oxygen
Concentration is increased to 5mg/L from 0mg/L.
Claims (5)
1. a kind of slow-releasing agent for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization, which is characterized in that according to weight
Percentage, including peroxide 10%~40%, iron tourmaline 5%~30%, persulfate 20%~50%, surfactant
1%~5%, adhesive 5%~20%.
2. a kind of slow-releasing agent for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization according to claim 1,
It is characterized in that, the peroxide is peromag or calper calcium peroxide or both mixture.
3. a kind of slow-releasing agent for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization according to claim 2,
It is characterized in that, the persulfate is sodium peroxydisulfate or potassium peroxydisulfate or both mixture.
4. a kind of slow-releasing agent for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization according to claim 3,
It is characterized in that, the surfactant is cyclodextrin.
5. a kind of slow-releasing agent for deep layer mine chlorohydrocarbon polluted underground water in-situ immobilization according to claim 4,
It is characterized in that, the binder is portland cement or chitosan.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910724355.8A CN110407266A (en) | 2019-08-01 | 2019-08-01 | Slow-release medicament for in-situ remediation of underground water polluted by hydrochloric ether in deep mine |
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Cited By (1)
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| 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 |
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| CN102491502A (en) * | 2011-12-19 | 2012-06-13 | 南京大学 | Slow oxygen releasing material for repairing underground water and preparation method for slow oxygen releasing material |
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| 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 |
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