阅读说明：本技术 一种修复含氯有机溶剂污染地下水的方法 (A method of repairing chloro-carbon solvent polluted underground water ) 是由 李静文 吕正勇 倪鑫鑫 生贺 秦森 李淑彩 于 2019-09-02 设计创作，主要内容包括：本发明公开了一种修复含氯有机溶剂污染地下水的方法,利用维生素B12作为电子中间传递体的催化传递电子能力,促进微米零价铁对含氯有机溶剂的还原脱氯作用；通过原位加压注入或异位抽出后加入两种方式向污染地下水中添加一定量的微米级还原铁粉及维生素B12,使含氯有机溶剂脱氯还原,可实现处理后含氯有机溶剂如1,2,3-三氯丙烷的脱氯效率达到80％以上。相较于微米零价铁体系,本方法对于含氯有机溶剂污染物的脱氯效率可提高30％以上。本发明可应用于污染场地修复,独特的优势和良好得修复能力使微米零价铁/维生素B12在含氯有机溶剂污染地下水的脱氯还原处置过程中具有极好的应用前景。(The invention discloses a kind of methods for repairing chloro-carbon solvent polluted underground water, transmit electronic capability using vitamin B12 as the catalysis of electronics intermediate transfer body, promote micron Zero-valent Iron to the reductive dechlorination of chloro-carbon solvent；By add in-place pressure injection enter or dystopy extraction after be added two ways a certain amount of micron order reduced iron powder and vitamin B12 are added into polluted underground water, make chloro-carbon solvent dechlorination, chloro-carbon solvent such as 1 after handling can be achieved, the dechlorination efficiency of 2,3- trichloropropanes reaches 80% or more.Compared to micron Zero-valent Iron system, this method can be improved 30% or more for the dechlorination efficiency of chloro-carbon solvent pollutant.Present invention can apply to contaminated site reparation, unique advantage and the good repair ability that obtains make micron Zero-valent Iron/vitamin B12 have fabulous application prospect in the dechlorination disposal process of chloro-carbon solvent polluted underground water.)

1. a kind of method for repairing chloro-carbon solvent polluted underground water, which is characterized in that entered using add in-place pressure injection or dystopy The mode being added after extraction adds micron Zero-valent Iron and vitamin B12 in chloro-carbon solvent polluted underground water, utilizes micron Some catalytic effects that Zero-valent Iron is formed under vitamin B12 catalytic action carry out dechlorination to chloro-carbon solvent.

2. the method as described in claim 1, which is characterized in that the Zero-valent Iron is commercially available reduced iron powder, the vitamin B12 For delicatessen food grade vitamin B12, the content range of vitamin B12 is 1%~99%.

3. the method as described in claim 1, which is characterized in that the additive amount of the micron Zero-valent Iron is organic in reaction system 10~300 times of chlorine molal quantity；

Entered using add in-place pressure injection, the dosage of the vitamin B12 is the 0.5%~3% of anaerobic condition dry weight；Using different The mode being added after the extraction of position, the dosage of the vitamin B12 are dispose polluted-water quality 0.5%~3%.

4. the method as described in claim 1, which is characterized in that the method for in-situ immobilization chloro-carbon solvent polluted underground water Are as follows:

By the mixed solution of micron Zero-valent Iron and vitamin B12 using injection device pressurization injection water table Polluted area.

5. method as claimed in claim 4, which is characterized in that the specific reality of in-situ immobilization chloro-carbon solvent polluted underground water Apply step are as follows:

Step 1 passes through and collects place data and on-site land survey, investigates contaminated site soil and underground water pollution situation, Collection site soil and groundwater sample include chlorine organic solvent pollution situation to place and carry out entry evaluation；

Step 2 monitors underground in place in three mouthfuls of groundwater monitoring wells of place target area construction in conjunction with contaminated sites situation The variation of water pollutant concentration；

Micron Zero-valent Iron/vitamin B12 medicament is injected into contaminated site region of interest within using injection device pressurization by step 3；

Step 4, the to schedule groundwater sample in interval acquisition place target area, analysis wherein target contaminant Changes of contents and corresponding physical and chemical parameter, and medicament after-teeming is suitably carried out in conjunction with monitoring result.

6. the method as described in claim 1, which is characterized in that the method for showering chloro-carbon solvent underground water are as follows:

After the extraction of chloro-carbon solvent polluted underground water, the micron Zero-valent Iron and vitamin B12 are added in water body, and will Above-mentioned system, which is placed in closed stirring container under room temperature, is reacted.

7. method as claimed in claim 6, which is characterized in that the speed of agitator of the closed stirring container is 10~100r/ min。

8. the method as described in claim 1, which is characterized in that content of organic chloride range is 5~2500mg/L in body of groundwater.

Technical field

The invention belongs to pollute organic pollution recovery technique field in environment, it is dirty to be related to a kind of reparation chloro-carbon solvent Contaminate the method for underground water, and in particular to a kind of to repair chloro-carbon solvent polluted underground water using micron Zero-valent Iron/vitamin B12 Method.

Background technique

With Urbanization in China quickening and chemical industry extensive style development, Which Ecological Environment Faced serious danger Machine.Organic dirt will lead to for the unreasonable storage disposition of organic solvent, discharge and unexpected leakage etc. in chemical production process Dye object enters groundwater environment, seriously endangers and arrives the ecological balance and human health.Since its specific gravity is greater than 1, heavy nonaqueous phase liquid When body penetrates into earth's surface or underground, it would be possible to which the downward infiltration migration in soil/body of groundwater causes serious pollution.Contain The chloro-carbon solvent of one or more chlorine bromine atoms is common heavy nonaqueous phase liquid, since it is removed with good Lipid energy is widely used in electronics industry, chemical industry manufacture, printing and dyeing coating, pharmaceutical synthesis and metal industry.Correlative study table Bright, most of chloro-carbon solvents have carcinogenic, teratogenesis and mutagenic " three cause " effect to human body, are listed in the U.S., Europe With the Environment Priority monitoring control pollutant of multiple countries and regions such as China.In recent years, about the pollution of chloro-carbon solvent People are caused more widely to pay close attention to.

Currently, from underground water remove chloro-carbon solvent main method include physical absorption, electronation oxidation and Microbial degradation etc..Wherein, physisorphtion is adsorbed organic molten containing chlorine using the active force between adsorbent and adsorption molecule Agent, absorption disposition speed is fast, but chloro-carbon solvent is not removed in treatment process, and the toxic pollutant being adsorbed also relatively holds Easily desorb；Microbial degradation method repairing efficiency is longer, receives water body environment factor and is affected.

Compared to above two method, electronation oxidizing process is very fast to chloro-carbon solvent degradation rate, leads in environmental protection Domain is widely used.In view of the presence of chlorine element in chloro-carbon solvent keeps its betatopic oxidation difficulty larger, mesh Preceding main use electronation technology carries out dechlorination to chloro-carbon solvent.Zeroth order is proposed from Gillham in 1994 et al. Since iron reduction dechlorination technical treatment organic chloride, Zero-valent Iron recovery technique because of the features such as its is from a wealth of sources, simple process, Have become a kind of more potential chloro-carbon solvent recovery technique.For zeroth order iron material, the Zero-valent Iron of Nano grade Grain has very strong adsorption capacity and reactivity, but since the effects of its high surface energy, magnetic interaction and Van der Waals force leads The unstability for causing nano zero-valence iron particle, to seriously constrain its efficiency applied in polluted underground water；In addition, high Master Cost be also to limit the obstacle applied in environmental pollution reparation of nano zero-valence iron particle.In contrast, micron order zero Valence iron material specific surface area is larger, low in cost, is more suitable for large-scale application in pollution amelioration industry；However, correlative study table Bright, disposal efficiency of the micron order zeroth order iron material in chloro-carbon solvent reduction application be not high, in particular for chloralkane Equal organic compounds, since its structure is relatively stable, reduction dechlorination efficiency is more limited.Therefore, to Zero-valent Iron recovery technique into Row improvement, and it is applied to the reparation of chloro-carbon solvent, it is of great significance to contaminated site repairing and treating.

Summary of the invention

In order to overcome the shortcomings of that existing chloro-carbon solvent polluted underground water repairs that difficulty is big, low efficiency, at high cost, this hair Bright to provide a kind of method for repairing chloro-carbon solvent polluted underground water, cost is controllable, material is easy to get, is easy to operate, repairs It is high-efficient.

The invention discloses a kind of methods for repairing chloro-carbon solvent polluted underground water, are entered using add in-place pressure injection or different The mode being added after the extraction of position adds micron Zero-valent Iron and vitamin B12 in chloro-carbon solvent polluted underground water, and utilization is micro- Some catalytic effects that rice Zero-valent Iron is formed under vitamin B12 catalytic action carry out dechlorination to chloro-carbon solvent.

As a further improvement of the present invention, the Zero-valent Iron is commercially available reduced iron powder, and the vitamin B12 is commercially available food Grade vitamin B12, the content range of vitamin B12 are 1%~99%.

As a further improvement of the present invention, the additive amount of the micron Zero-valent Iron is organochlorine molal quantity in reaction system 10~300 times；

Entered using add in-place pressure injection, the dosage of the vitamin B12 is the 0.5%~3% of anaerobic condition dry weight；It adopts The mode being added after being extracted out with dystopy, the dosage of the vitamin B12 are dispose polluted-water quality 0.5%~3%.

As a further improvement of the present invention, the method for in-situ immobilization chloro-carbon solvent polluted underground water are as follows:

By the mixed solution of micron Zero-valent Iron and vitamin B12 using injection device pressurization injection water table contaminated area Domain.

As a further improvement of the present invention, the specific implementation step of in-situ immobilization chloro-carbon solvent polluted underground water Are as follows:

Step 1 passes through and collects place data and on-site land survey, adjusts to contaminated site soil and underground water pollution situation It looks into, collection site soil and groundwater sample, chlorine organic solvent pollution situation is included to place and carries out entry evaluation；

Step 2 monitors in place in conjunction with contaminated sites situation in three mouthfuls of groundwater monitoring wells of place target area construction The variation of pollutant concentration in underground water；

Micron Zero-valent Iron/vitamin B12 medicament is injected into target in contaminated site using injection device pressurization by step 3 Region；

Step 4, the to schedule groundwater sample in interval acquisition place target area, analyze wherein target stains The changes of contents of object and corresponding physical and chemical parameter, and medicament after-teeming is suitably carried out in conjunction with monitoring result.

As a further improvement of the present invention, the method for showering chloro-carbon solvent underground water are as follows:

After the extraction of chloro-carbon solvent polluted underground water, the micron Zero-valent Iron and vitamin B12 are added in water body, And above-mentioned system is placed in closed stirring container under room temperature and is reacted.

As a further improvement of the present invention, the speed of agitator of the closed stirring container is 10~100r/min.

As a further improvement of the present invention, content of organic chloride range is 5~2500mg/L in body of groundwater.

Compared with prior art, the invention has the benefit that

1, operating procedure is simple: restorative procedure of the invention only needs to add into chloro-carbon solvent polluted underground water body A certain amount of micron of Zero-valent Iron and vitamin B12 are not necessarily to other complex appts；It is catalyzed using micron Zero-valent Iron in vitamin B12 The lower some catalytic effects formed of effect, carry out dechlorination to chloro-carbon solvent；

2, repair materials are safe: the micron zero-valent iron particle and vitamin B12 added in restorative procedure of the invention are Nontoxic chemicals, repair materials safety non-pollution.

3, rehabilitation cost is low: restorative procedure of the invention is inexpensively easy using micron order reduced iron powder and vitamin B12 material , compared to nano zero valence iron recovery technique, rehabilitation cost is substantially reduced.

4, applied widely: restorative procedure of the invention is covered add in-place pressure injection and is entered and two kinds of processing of disposition after dystopy extraction Method, strong flexibility can be widely applied to the reparation of chloro-carbon solvent polluted underground water, while in 5 DEG C or so of low temperature item Also there is good repairing effect under part, can effectively solve the problems, such as that conventional biochemical restorative procedure is not low temperature resistant.

5, remediation efficiency is high: the addition of vitamin B12 catalyst in restorative procedure of the invention, being capable of effective Accelerating reduction The transfer rate of electronics during dechlorination reaction, and then promote micron Zero-valent Iron to the reduction dechlorination rate of chloro-carbon solvent, The more simple micron Zero-valent Iron treatment effect of the degradation efficiency of chloro-carbon solvent can be improved 30% or more after processing.

Detailed description of the invention

Fig. 1 be the embodiment of the present invention 1 disclosed in be individually added into micron order Zero-valent Iron and mixing be added micron order Zero-valent Iron and After vitamin B12, to the degradation rate comparison diagram of 1,2,3- trichloropropane of pollutant；

Fig. 2 be the embodiment of the present invention 1 disclosed in be individually added into micron order Zero-valent Iron and mixing be added micron order Zero-valent Iron and After vitamin B12, to pollutant 1, the degradation rate comparison diagram of 2- dichloropropane；

Fig. 3 be the embodiment of the present invention 1 disclosed in be individually added into micron order Zero-valent Iron and mixing be added micron order Zero-valent Iron and After vitamin B12, to pollutant 1, the degradation rate comparison diagram of 3- dichloropropane；

Fig. 4 is after micron order Zero-valent Iron and vitamin B12 is added in the disclosed mixing of the embodiment of the present invention 2, to 1,2- dichloro The degradation rate schematic diagram of ethane；

Fig. 5 be the embodiment of the present invention 3 disclosed in be individually added into micron order Zero-valent Iron and mixing be added micron order Zero-valent Iron and After vitamin B12, to the degradation rate comparison diagram of 1,2- dichloroethanes.

Specific embodiment

In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is A part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.

The present invention is described in further detail with reference to the accompanying drawing:

The present invention provides a kind of method for repairing chloro-carbon solvent polluted underground water, is entered using add in-place pressure injection or dystopy The mode being added after extraction adds micron Zero-valent Iron and vitamin B12 in chloro-carbon solvent polluted underground water, utilizes micron Some catalytic effects that Zero-valent Iron is formed under vitamin B12 catalytic action carry out dechlorination to chloro-carbon solvent.Its In:

Commercially available reduced iron powder can be used in micron Zero-valent Iron of the invention, reduced iron powder when pressing injection mode using add in-place Diameter can meet 1000-3000 mesh, and preferable particle size is 2500 meshes；Reduced iron powder when adding manner after being extracted out using dystopy Diameter can meet 200-300 mesh, preferably 200 meshes.For guarantee Zero-valent Iron dispose effect, can first with organic solvent as just oneself Alkane, acetone etc. are by micron order zeroth order iron surface greasy dirt washes clean that may be present.Delicatessen food grade dimension can be used in vitamin B12 Raw element B12, vitamin B12 content range are 1%~99%, and preferred content is 5%~10%.

The additive amount of micron Zero-valent Iron is organochlorine mole in reaction system when the present invention uses add in-place to press injection mode Several 50~300 times, preferred scope are 150~200 times；Vitamin B12 dosage is the 0.5%~3% of water-bearing layer dry weight, excellent Selecting range is 1%；After using dystopy to extract out when adding manner micron Zero-valent Iron additive amount for organochlorine mole in reaction system Several 10~200 times, preferred scope are 50~100 times；Vitamin B12 dosage is the 0.5%~2% of polluted-water quality, Preferred scope is 1%.

Content of organic chloride range is 5~2500mg/L in body of groundwater of the invention.

When the present invention is using chloro-carbon solvent reparation is applied to after dystopy extraction, by chloro-carbon solvent polluted underground water It is drawn in closed stirring container and adds micron Zero-valent Iron and vitamin B12 in water body, carry out confined reaction under room temperature；It is close Closing speed of agitator in stirring container is 10~200r/min, and preferably speed of agitator is 100r/min.

When the present invention uses in-situ immobilization chloro-carbon solvent polluted underground water, micron Zero-valent Iron is mixed with vitamin B12 Solution is closed using Geoprobe or other injection devices pressurization injection water table Polluted area.