CN105293683B - A kind of infiltration type reaction wall composite for PAHs in groundwater pollution amelioration and its preparation method and application method - Google Patents
A kind of infiltration type reaction wall composite for PAHs in groundwater pollution amelioration and its preparation method and application method Download PDFInfo
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Abstract
The invention discloses a kind of infiltration type reaction wall composite for PAHs in groundwater pollution amelioration and its preparation method and application method, belong to groundwater remediation technical field.Composite includes kernel, packed layer and shell, and the composition material of the kernel is charcoal spherical particle thing, and packed layer includes：Oxygen release agent 15.09% ~ 15.85%, carbon raw material 30.19% ~ 31.7% is released, plasticity bonds raw material 15.09% ~ 15.85%, and high osmosis raw material 6.29% ~ 6.6%, surplus is adhesive；Shell includes：Plasticity bonds raw material 53.57% ~ 55.37%, and high osmosis raw material 6.43% ~ 6.64%, surplus is adhesive.Its preparation manipulation is easy, cost is low, reproducible and it has slowly release oxygen source, an effect of carbon source, environment friendly and pollution-free, stream few, and the removal to Organic Chemicals In Groundwater has great importance.
Description
Technical field
The present invention relates to polluted underground water recovery technique, and it is dirty to be used for PAHs in groundwater more specifically to one kind
Contaminate the infiltration type reaction wall composite repaired and its preparation method and application method.
Background technology
Underground water is drinking water source for the survival of mankind, but in human industryization, urbanization process, various organic wastes
Oozed under the discharge of water, resident living sewage, the rupture of underground oil pipeline and agricultural production process Pesticides and chemical fertilizer
It is a large amount of to use, result in the serious organic contamination of underground water.Ministry of Land and Resources starts national Groundwater Contamination Investigation and evaluation
As a result show, the local ground watering organic contamination such as the Delta of the Pearl River, Yangtze River Delta, plain in Huaihe River basin, North China Plain is bright
It is aobvious, and Organic Contamination of Groundwater is mainly half volatile organic contamination.
Organic contamination has larger harm to the mankind, especially into the organic matter overwhelming majority in drinking water water body to people
Body has acute or chronic, directly or indirectly pathogenic effects, changes the DNA structure of cell, and carcinogenesis are produced to tissue, are caused
Distortion and the effect of mutation.In numerous organic pollutions, polycyclic aromatic hydrocarbon（PAHs）It is a kind of lasting of generally existing in environment
Contact scar thing, it has " three cause " effect, huge harm is caused to human health and ecological environment, polycyclic aromatic hydrocarbons contaminated
The topics common as current home and abroad environment scientific circles and main attack focus are repaired, is degraded using microorganism under aerobic condition
Polycyclic aromatic hydrocarbon is to control polycyclic aromatic hydrocarbons contaminated main path at present.
At present, the groundwater remediation method commonly used both at home and abroad can be divided into showering and in-situ immobilization skill according to repair mode
Art.Showering mainly includes passive collection and pump-and-treat system, and run time takes several years or even decades, very expensive, simultaneously
It is little to the removal effect of nonaqueous phase liquid.Compared to showering technology, in-situ immobilization permeable reaction wall（PRB）Technology
Without additionaling power, operating cost is low, and reaction medium consumption is slow, there is several years even decades processing potentiality, long-term except needing
Monitoring is outer, is almost not required to operating cost, therefore more economical feasible.
China Patent No. ZL201110423562.3, invention and created name are：The carbon biological prosthetic for polluted underground water
Source slow-release material and preparation method thereof, including kernel, the shell of the cladding kernel；The kernel composition material is to account for interior caryoplasm
Release carbon raw material, 1 ~ 25% nutrient raw material, 5 ~ 45% plasticity that amount percentage is 40 ~ 86% bond raw material, 5 ~ 20% Thief zone
Property raw material, surplus is water；The shell composition material is that to account for outer cover quality percentage be 10 ~ 40% to release carbon raw material, 1 ~ 10%
Nutrient raw material, 20 ~ 80% plasticity bond raw material, 0 ~ 40% high osmosis raw material, and surplus is water.China Patent No.
ZL201410041339.6, invention and created name are：The composite functional material repaired for polluted underground water biochemistry joint
And preparation method thereof, including kernel, material packed layer and shell；The composition material of the kernel is wooden unit, material packed layer bag
Include：Carbon raw material 20% ~ 50% is released, plasticity bonds raw material 25% ~ 42.8%, and reduced iron powder 3.3% ~ 8%, surplus is natural glue；Outside
Shell includes：Plasticity bonds raw material 26.6% ~ 60%, and high osmosis raw material 12% ~ 40%, surplus is natural glue.Above two is sent out
Bright material only with the addition of carbon source or reduced iron powder, and its material has the requirement of certain mechanical strength and uniform sphericity, overcome often
The shortcomings that fast is lost in rule carbon source supplement, but the organic pollution such as polycyclic aromatic hydrocarbon utilizes under conditions of aerobic in underground water
Microorganism is just easy to thoroughly degrade by dioxygenase, monooxygenase process, the material in first two invention only add carbon source or
Iron powder, it is impossible to discharge oxygen source, build aerobic environment, and add reduced iron powder also built in underground water it is a kind of extremely strong
Anaerobic environment, the purpose of thoroughly degraded target contaminant is not reached.
The content of the invention
Invention technical problems to be solved
The present invention is directed to the existing restorative procedure of organic pollution such as polycyclic aromatic hydrocarbon in underground water and easily causes carbon source release not
The problems such as insufficient is supplied oxygen in easy to control, underground water, there is provided a kind of infiltration type for PAHs in groundwater pollution amelioration is anti-
Answer wall composite and its preparation method and application method, the PRB（Permeable reaction wall）Composite uses can be lasting
The charcoal of stable release carbon source and groundwater environment can be made to keep the calper calcium peroxide of certain aerobic environment and various inorganic
Bond, high osmosis raw material compound prescription, uniform-spherical is granulated, easy to operate, reproducible and environment friendly and pollution-free, water resistance coefficient
Small, good biocompatibility, nothing are streamed, and can efficiently, rapidly remove the target contaminants such as polycyclic aromatic hydrocarbon.
Technical scheme
To reach above-mentioned purpose, technical scheme provided by the invention is：
A kind of infiltration type reaction wall composite for PAHs in groundwater pollution amelioration, including kernel, packed layer
And shell；The composition material of the kernel is charcoal spherical particle thing；Packed layer is included by accounting for packed layer quality percentage as follows
The component of ratio：Oxygen release agent 15.09% ~ 15.85%, releases carbon raw material 30.19% ~ 31.7%, plasticity bond raw material attapulgite 15.09% ~
15.85%, high osmosis raw material 6.29% ~ 6.6%, surplus is adhesive；Shell includes the group by accounting for outer cover quality percentage as follows
Point：Plasticity bonds raw material attapulgite and cement 53.57% ~ 55.37%, high osmosis raw material 6.43% ~ 6.64%, and surplus is bonding
Agent.Oxygen release agent is calper calcium peroxide, and it is charcoal that carbon raw material is released in packed layer；High osmosis raw material is diatomite, described adhesive
For sodium alginate, the charcoal of the kernel is coconut husk charcoal or peach-pit charcoal.
For the preparation method of the infiltration type reaction wall composite of PAHs in groundwater pollution amelioration, its step is：
（1）80-100 mesh oxygen release agent is standby；
（2）It is standby that 80 ~ 100 mesh release carbon raw material；
（3）80 ~ 100 mesh plasticity bond raw material for standby；
（4）80 ~ 100 height of eye permeability raw material for standby；
（5）By adhesive sodium alginate and water in mass ratio 1:80 prepare slurries, by sodium alginate powder uniformly, thin layer
It is sprinkled into water, and constantly quick stirring, makes sodium alginate substantially uniformity soluble in water into thick, it is standby to be made into slurry；
（6）Charcoal is rolled in sugar coating machine kernel is made, natural air drying 2 ~ 3 days；
（7）The kernel prepared in step 6 is immersed in the slurry that step 5 prepares standby after 10 ~ 20min；
（8）By standby oxygen release agent, carbon raw material, high osmosis raw material and plasticity bonding raw material are released by the mass percent
Mixing material is made in mixing, and the mixing material is sprinkled into comminutor, and the kernel put into after step 7 immersion, is opened and is granulated
Machine rolls, and constantly adds mixing material, and sprays into adhesive, until the material packed layer is rolled to expected thickness, that is, includes interior
The structure of core and packed layer, particle diameter are about 0.7 ~ 1.2cm；
（9）The material natural air drying that step 8 is manufactured 2 ~ 3 days, then it is immersed in the slurry that step 5 prepares
10min, then it is sprinkled into comminutor and raw material attapulgite and cement, high osmosis raw material is bonded by institute by the plasticity crushed
State blending ingredients made of mass percent mixing and be put into soaked filling layer material and wherein roll together, rotating speed is
46r/min, the blending ingredients are to be mixed by the plasticity bonding raw material and high osmosis raw material crushed by the mass percent
It is even to be made, during producing material material, blending ingredients are constantly added, spray into adhesive, until the shell is rolled to expected thickness, about
0.7~1.2mm；
（10）The composite natural air drying prepared through step 9, which is placed in after 2 ~ 3 days in hermetic bag, conserves 7 days, after tested
The particle diameter of the packed layer containing core granule strength in 1cm reaches 53N/, and composite material granular intensity is about 60N/, and this is compound
The hardness of material can reach soaks 3 ~ 4 weeks not broken degree in water.
Comminutor is rolled with 46r/min rotating speeds in the step 8,9.
Infiltration type reaction wall composite of the present invention, applied to PAHs in groundwater pollution amelioration.
For the application process of the infiltration type reaction wall composite of PAHs in groundwater pollution amelioration, step is：
（1）By made PRB composites and coarse sand by volume 3:7~4:6 are mixed；
（2）Field is excavated, and it is 2.0~6.0 meters to set PRB buried depths, and landfill thickness is 1.5~2.0 meters, and width of wall body is
1.2~2.0 meters.
Beneficial effect
Using technical scheme provided by the invention, compared with existing known technology, there is following remarkable result：
（1）Composite packed layer of the present invention can slowly discharge oxygen source, carbon source, make up oxygen content deficiency in underground water
Shortcoming, it is possible to provide sufficient oxygen is utilized by microorganism, and good aerobic environment is provided for heterotrophic microorganism, so as to efficiently, soon
Speed, the organic pollution such as polycyclic aromatic hydrocarbon in underground water is contamination-freely removed, it is economical and environmentally friendly.
（2）Charcoal（biochar）Specific surface area is big, and surface is loose structure, and is rich in a variety of functional groups, it is easier to
Largely, firm adsorbed target pollutant.Compared with other release carbon raw material, its property is stable, can more persistently keep carbon source, environmental protection
It is pollution-free, greatly increased using the life-span.
（3）Composite of the present invention is notable to polycyclic aromatic hydrocarbon removal effect, and clearance is up to more than 90%, and removal effect
Permanently effective, when column experiments run to 350d, polycyclic aromatic hydrocarbon clearance still can reach more than 90% and remain stable, and pass through
Fig. 5 can be seen that polycyclic aromatic hydrocarbon pollutant has been degraded.
（4）The preparation manipulation of composite of the present invention is easy, cost is low, reproducible and its is environment friendly and pollution-free, streams less.
Brief description of the drawings
Fig. 1 be composite of the present invention complete one-dimensional diagrammatic cross-section, 1- kernels；2- packed layers；3- shells；
Fig. 2 is composite of the present invention to polycyclic aromatic hydrocarbon（It is luxuriant and rich with fragrance）It is static remove experiment effect figure, 1 is original on abscissa
Liquid；2 be only to add peach-pit biology carbon composite；3 be only to add coconut husk biology carbon composite；4 for add peach-pit charcoal and
Oxygen release agent composite；5 be addition coconut husk charcoal and oxygen release agent composite；
Fig. 3 is PRB column experiment device structural representations, and 4- is water sample interface, and 5- mixes to place composite and coarse sand
Place；
Fig. 4 is composite of the present invention to polycyclic aromatic hydrocarbon（It is luxuriant and rich with fragrance）Dynamic remove experiment effect figure, 1 is adds coconut husk in figure
Charcoal and oxygen release agent composite；2 be addition peach-pit charcoal and oxygen release agent composite；
Fig. 5 is14The luxuriant and rich with fragrance mark tracer experiment result figures of C-, Fig. 5（a）For stoste14C- phenanthrene goes out peak figure；Fig. 5（b）To add peach
Core charcoal and oxygen release agent composite outlet water sample14C- phenanthrene goes out peak figure；Fig. 5（c）Answered to add coconut husk charcoal and oxygen release agent
Condensation material exports water sample14C- phenanthrene goes out peak figure.
Embodiment
The reagent and device that following examples use
1st, reagent
Calper calcium peroxide（The mesh of Nanjing 80 ~ 100）；Charcoal（The mesh of Liyang 80 ~ 100）；Attapulgite powder（River
Soviet Union's mesh of Xuyi 80 ~ 100）；Diatomite powder（The mesh of Nanjing 80 ~ 100）；Finished ground cement（The mesh of Nanjing 80 ~ 100）；Sea
Mosanom（The mesh of Nanjing 80 ~ 100）；It is luxuriant and rich with fragrance（Sigma reagents 98%）
2nd, device
Sugar coating machine（BY-100 Taizhou Cities the Changjiang river pharmaceutical Co. Ltd）；Peristaltic pump（BT100-1L Baoding Lange constant flow pump
Co., Ltd）；Ultrasonic washing instrument（KQ-800KDE Kunshan Ultrasonic Instruments Co., Ltd.）；Multifunctional crusher（AD-03
Shanghai Ai De Science and Technology Ltd.s）；Water purification machine（Ai Kepu Chongqing Yi Yang enterprise developments Co., Ltd）；PRB posts as shown in Figure 4
Device（Laboratory is from designing, and glass material cylinder, internal diameter 4cm, high 50cm, upper end is delivery port, and lower end is water inlet,
Thief hatch is had per 10cm）；High performance liquid chromatograph（Agilent1200）
To further appreciate that present disclosure, the present invention is described in detail in conjunction with the accompanying drawings and embodiments, but and unlimited
The system present invention.
Embodiment 1
For the biological prosthetic composite of organic contamination ground water chemistry, its kernel is coconut husk charcoal spherical particle thing,
Its packed layer is made up of the component of following mass percent：Oxygen release agent calper calcium peroxide 15.85%, predominantly microbial degradation pollute
Thing provides oxygen；Carbon raw material coconut husk charcoal 31.7% is released, is mainly to maintain the carbon source needed for microorganism growth；Plasticity bonds former
Expect attapulgite 15.85%, mainly all raw materials are bonded and keep certain hardness；High osmosis raw material diatomite
6.6%, composite is kept cellular, oxygen source, carbon source can be sustained；Adhesive sodium alginate 29.98%.The shell
There is cladding protective effect, be made up of the component of following mass percent：Plasticity bonds raw material Portland cement 13.84%, recessed
Convex rod soil 41.53%, high osmosis raw material diatomite 6.64%, adhesive sodium alginate 37.98%.The complex function of the present embodiment
Oxygen release agent used in material, release carbon raw material, to bond raw material, high osmosis raw material, the particle diameter of sodium alginate be 80 mesh to plasticity.
The composite material preparation biological prosthetic for polycyclic aromatic hydrocarbons contaminated ground water chemistry be：
（1）80 mesh oxygen release agent are standby；
（2）It is standby that 80 mesh release carbon raw material；
（3）80 mesh plasticity bond raw material for standby；
（4）80 height of eye permeability raw material for standby；
（5）By sodium alginate and water in mass ratio 1:80 prepare slurries, by sodium alginate powder uniformly, thin layer be sprinkled into water
In, and constantly quickly stirred with glass bar, make sodium alginate substantially uniformity soluble in water into thick, it is standby to be made into slurry；
（6）Coconut husk charcoal is rolled in sugar coating machine kernel is made, particle size 0.3cm, natural air drying 2 days；
（7）The kernel is immersed in the slurry that step 5 prepares standby after 15min；
（8）By standby oxygen release agent, carbon raw material, high osmosis raw material, plasticity bonding raw material are released by the mass percent
Mixing material is made in mixing, and the mixing material part is sprinkled into comminutor, is opened and is made after the kernel that input step 7 is got ready
Grain machine is rolled with 46r/min rotating speeds, and constantly adds mixing material, sprays into adhesive, and the mixing material added every time is 10g,
The straying quatity of adhesive determines according to the dry and wet situation and bonding situation of the mixing material of rolling, treats that material outer newly superscribes one
4.28g or so natural glue is sprayed into after layer mixing material, until the material packed layer is rolled to expected thickness, i.e., including kernel
With the structure of packed layer, particle diameter is about 0.7cm；
（9）The material natural air drying that step 8 is manufactured 3 days, is then immersed in 10min in the slurry, then
It is sprinkled into comminutor and raw material attapulgite and cement, high osmosis raw material is bonded by the quality percentage by the plasticity crushed
It is put into and wherein rolls together than blending ingredients made of mixing and by soaked filling layer material, rotating speed 46r/min is described
Blending ingredients bond raw material and high osmosis raw material by the plasticity crushed and are made by mass percent mixing, producing material material
Period, blending ingredients are constantly added, spray into adhesive, the blending ingredients added every time are 5g, and the addition of adhesive is according to rolling
The dry and wet situation and bonding situation of dynamic mixing material determine, are sprayed into after material outer newly wraps up last layer mixing material
3.06g or so natural glues, until the shell is rolled to expected thickness, about 0.7mm；
（10）The composite natural air drying prepared through step 9 is placed in hermetic bag after 3 days and conserved 7 days, contains after tested
The particle diameter of core packed layer granule strength in 1cm reaches 53N/, and composite material granular intensity is about 60N/, and the composite wood
The hardness of material can reach soaks 3 ~ 4 weeks not broken degree in water.
Embodiment 2
The present embodiment is used for the biological prosthetic composite of organic contamination ground water chemistry, substantially with embodiment 1, difference
It is：Its kernel is peach-pit charcoal spherical particle thing, and particle diameter 0.5cm, its material packed layer is by following mass percent
Component forms：Oxygen release agent calper calcium peroxide 15.09%；Release carbon raw material peach-pit charcoal 30.19%；Plasticity bonds raw material attapulgite
15.09%；High osmosis raw material diatomite 6.29%,；Adhesive sodium alginate 33.33%.Described shell is by following quality percentage
The component composition of ratio：Plasticity bonds raw material Portland cement 13.39%, attapulgite 40.18%, high osmosis raw silicon
Diatomaceous earth 6.43%, adhesive sodium alginate 40%.Oxygen release agent used in the composite functional material of the present embodiment, release carbon raw material, plasticity
It is 90 mesh to bond raw material, high osmosis raw material, the particle diameter of sodium alginate.
The biological prosthetic composite material preparation of polycyclic aromatic hydrocarbons contaminated ground water chemistry that is used for of the present embodiment is：
（1）90 mesh oxygen release agent are standby；
（2）It is standby that 90 mesh release carbon raw material；
（3）90 mesh plasticity bond raw material for standby；
（4）90 height of eye permeability raw material for standby；
（5）By sodium alginate and water in mass ratio 1:80 prepare slurries, by sodium alginate powder uniformly, thin layer be sprinkled into water
In, and constantly quickly stirred with glass bar, make sodium alginate substantially uniformity soluble in water into thick, it is standby to be made into slurry；
（6）Peach-pit charcoal is rolled in sugar coating machine kernel is made, particle size 0.5cm, natural air drying 3 days；
（7）The kernel is immersed in the slurry that step 5 prepares standby after 15min；
（8）By standby oxygen release agent, carbon raw material, high osmosis raw material, plasticity bonding raw material are released by the mass percent
Mixing material is made in mixing, and the mixing material part is sprinkled into comminutor, is opened and is made after the kernel that input step 7 is got ready
Grain machine is rolled with 46r/min rotating speeds, and constantly adds mixing material, sprays into adhesive, and the mixing material added every time is 10g,
The straying quatity of adhesive determines according to the dry and wet situation and bonding situation of the mixing material of rolling, treats that material outer newly superscribes one
Spray into 5g or so natural glue after layer mixing material, until the material packed layer is rolled to expected thickness, i.e., including kernel and
The structure of packed layer, particle diameter are about 1.2cm；
（9）The material natural air drying that step 8 is manufactured 3 days, is then immersed in 10min in the slurry, then
It is sprinkled into comminutor and raw material attapulgite and cement, high osmosis raw material is bonded by the quality percentage by the plasticity crushed
It is put into and wherein rolls together than blending ingredients made of mixing and by soaked filling layer material, rotating speed 46r/min is described
Blending ingredients bond raw material and high osmosis raw material by the plasticity crushed and are made by mass percent mixing, producing material material
Period, blending ingredients are constantly added, spray into adhesive, the blending ingredients added every time are 5g, and the addition of adhesive is according to rolling
The dry and wet situation and bonding situation of dynamic mixing material determine, are sprayed into after material outer newly wraps up last layer mixing material
3.33g or so natural glues, until the shell is rolled to expected thickness, about 1.2mm；
（10）The composite natural air drying prepared through step 9 is placed in hermetic bag after 3 days and conserved 7 days, contains after tested
The particle diameter of core packed layer granule strength in 1cm reaches 53N/, and composite material granular intensity is about 60N/, and the composite wood
The hardness of material can reach soaks 3 ~ 4 weeks not broken degree in water.
Embodiment 3
The present embodiment is coconut husk charcoal spherical particle thing with embodiment 1, its kernel, and its packed layer is by following quality percentage
The component composition of ratio：Oxygen release agent calper calcium peroxide 15.50%；Release carbon raw material coconut husk charcoal 31%；Plasticity bonds raw material attapulgite
15.50%；High osmosis raw material diatomite 6.45%；Adhesive sodium alginate 31.52%.The shell has cladding protective effect, by
The component composition of following mass percent：Plasticity bonds raw material Portland cement 13.6%, attapulgite 40.8%, Thief zone
Property raw material diatomite 6.53%, adhesive sodium alginate 38.07%.Oxygen release agent used in the composite functional material of the present embodiment, release
It is 100 mesh that carbon raw material, plasticity, which bond raw material, high osmosis raw material, the particle diameter of sodium alginate,.
The biological prosthetic composite material preparation of polycyclic aromatic hydrocarbons contaminated ground water chemistry that is used for of the present embodiment is：
（1）100 mesh oxygen release agent are standby；
（2）It is standby that 100 mesh release carbon raw material；
（3）100 mesh plasticity bond raw material for standby；
（4）100 height of eye permeability raw material for standby；
（5）By sodium alginate and water in mass ratio 1:80 prepare slurries, by sodium alginate powder uniformly, thin layer be sprinkled into water
In, and constantly quickly stirred with glass bar, make sodium alginate substantially uniformity soluble in water into thick, it is standby to be made into slurry；
（6）Coconut husk charcoal is rolled in sugar coating machine kernel is made, particle size 0.4cm, natural air drying 2 days；
（7）The kernel is immersed in the slurry that step 5 prepares standby after 15min；
（8）By standby oxygen release agent, carbon raw material, high osmosis raw material, plasticity bonding raw material are released by the mass percent
Mixing material is made in mixing, and the mixing material part is sprinkled into comminutor, is opened and is made after the kernel that input step 7 is got ready
Grain machine is rolled with 46r/min rotating speeds, and constantly adds mixing material, sprays into adhesive, and the mixing material added every time is 10g,
The straying quatity of adhesive determines according to the dry and wet situation and bonding situation of the mixing material of rolling, treats that material outer newly superscribes one
4.6g or so natural glue is sprayed into after layer mixing material, until the material packed layer is rolled to expected thickness, i.e., including kernel
With the structure of packed layer, particle diameter is about 0.9cm；
（9）The material natural air drying that step 8 is manufactured 3 days, is then immersed in 10min in the slurry, then
It is sprinkled into comminutor and raw material attapulgite and cement, high osmosis raw material is bonded by the quality percentage by the plasticity crushed
It is put into and wherein rolls together than blending ingredients made of mixing and by soaked filling layer material, rotating speed 46r/min is described
Blending ingredients bond raw material and high osmosis raw material by the plasticity crushed and are made by mass percent mixing, producing material material
Period, blending ingredients are constantly added, spray into adhesive, the blending ingredients added every time are 5g, and the addition of adhesive is according to rolling
The dry and wet situation and bonding situation of dynamic mixing material determine, are sprayed into after material outer newly wraps up last layer mixing material
3.07g or so natural glues, until the shell is rolled to expected thickness, about 0.9mm；
（10）The composite natural air drying prepared through step 9 is placed in hermetic bag after 3 days and conserved 7 days, contains after tested
The particle diameter of core packed layer granule strength in 1cm reaches 53N/, and composite material granular intensity is about 60N/, and the composite wood
The hardness of material can reach soaks 3 ~ 4 weeks not broken degree in water.
Embodiment 4
Embodiment 1, embodiment 2 are made into composite Materials Design static experiment, detection composite removes polycyclic aromatic hydrocarbon etc.
The ability of organic pollution, by taking phenanthrene as an example, specific implementation step is as follows：
（1）Two kinds of composites weigh 2.0g in 100ml grournd glass conical flasks respectively, every kind of material do three it is parallel
Group；
（2）The 0.5mg/L phenanthrene solution configured is poured into each glass spinner flask respectively, volume 100mL, covers mill
Mouthful plug, and with sealed membrane good seal；
（3）Every the Sino-Philippines removal situation of 5d sampling monitorings water sample, and periodically（It is spaced 5d）Luxuriant and rich with fragrance solution is changed, i.e., to glass
The luxuriant and rich with fragrance solution newly prepared is added in conical flask.
Experimental result and analysis：
As seen from Figure 2, only add peach-pit charcoal and only add the composite and of the present invention two of coconut husk charcoal
Kind of composite compare it is not notable to the removal effect of phenanthrene, and two kinds of composites of the present invention to the removal effect of phenanthrene very
Significantly, and clearance is up to more than 90%.Because polycyclic aromatic hydrocarbon is easy to degrade under aerobic condition, first two material is not
Sufficient oxygen source can be provided for microbial degradation polycyclic aromatic hydrocarbon, and two kinds of materials of the present invention not only can slow release carbon source, it is heavier
What is wanted is that can be sustained oxygen source, so as to greatly improve the clearance to polycyclic aromatic hydrocarbon.
Embodiment 5
Embodiment 1, embodiment 2 are made into composite and coarse sand by volume 1:1 ratio fills PRB column experiments, specifically
Implementation steps are as follows：
（1）PRB column experiment device figures as shown in Figure 3, including for water sample interface 4 and place at composite and coarse sand mixing
5；Internal diameter 4cm, high 50cm, are above delivery port, and lower is water inlet, and the glass column device that 10cm intervals have thief hatch cleans up
And it is dried for standby；
（2）Diameter 1 ~ 3mm coarse sand running water is eluriated and is dried for standby；
（3）By by drying and composite and the coarse sand of maintenance by volume 1:1 is well mixed in clean pallet；
（4）The composite of mixing and coarse sand are poured slowly into glass column device with 50ml glass small beaker, while dress
Enter mixing material while being tamped in PRB glass column devices it with rubber hammer；
（5）Pure water is passed through with peristaltic pump to enter in device, and the fine impurities being mingled with composite and coarse sand are gone out, and
And allow in whole post system its keep water-filling coherent state；
（6）Finally, the luxuriant and rich with fragrance solution prepared with ultra-pure water is constantly passed through in glass column device by peristaltic pump, simulates underground
The flow velocity of water is 71.38 ~ 129.86uL/min, and the residence time is 34 ~ 41h, and infiltration coefficient is 29.27cm/d ~ 35.29cm/d.
Regular water receiving sample at regular intervals, the change of luxuriant and rich with fragrance concentration is imported and exported with high performance liquid chromatography measure.
Experimental result and analysis：
As shown in figure 4, two kinds of composites of the present invention are notable to the removal effect of phenanthrene, luxuriant and rich with fragrance clearance during operation
Up to more than 85%, and removal effect is permanently effective, and when column experiments run to 350d, luxuriant and rich with fragrance clearance still can reach more than 90% simultaneously
Remain stable.Because column experiments run the starting stage, luxuriant and rich with fragrance removal is mainly that the absorption property of composite in itself acts as
With, with the increase of running time, composite to phenanthrene absorption progressively reach saturation state, so just bring into operation one section when
Between after, luxuriant and rich with fragrance clearance has declined, but during 50d, luxuriant and rich with fragrance clearance is gradually increasing and reaches stable state again, maintains 90%
More than, because the degraded microbiologic populations for changing aromatic hydrocarbons gradually adapt to environment more, and biofilm system is formed, so that will be polycyclic
Aromatic hydrocarbons is efficient, steady removal.
Embodiment 6
（1）When PRB column experiments run 60d, added into initial luxuriant and rich with fragrance solution14C- is luxuriant and rich with fragrance, and initial activity size is
5000dpm/ml or so, after the 36h residence times, 100ml water samples are connect from each PRB column outlets, carry out experimental result measure.
（2）First, each outlet 100ml water samples are enriched with through SPE posts, method is as follows：It is C by filler18Enriching column
（200mg）Post bed first is cleaned with 2mL dichloromethane, evacuates efflux, then passes sequentially through 5mL methanol and 5mL water, is taken out in pillar
Unprecedented connect fills 100mL water sample bottles, clear with 5mL distilled water after water sample all exhausts with 5mL/min pumping speed loading
Cylinder is washed, and maintains vacuum 10min, is finally analyzed component with 10mL dichloromethane eluents, nitrogen blows, with methanol constant volume extremely
0.5mL。
（3）Finally each outlet water sample sample of enrichment is detected by radioactivity HPLC, whether checking phenanthrene degrades.
Experimental result and analysis：
By Fig. 5（Fig. 5（a）, Fig. 5（b）And Fig. 5（c））As can be seen that it is at the peak that 11.1min goes out14C- phenanthrene parent chemical combination
Thing, it is at the peak that 4.9min goes out14CMaterial caused by the degraded of-phenanthrene, it can be seen that, phenanthrene has been degraded to other materials.This be because
For under aerobic environment, polycyclic aromatic hydrocarbon is carried out oxygen-adding open loop degraded by microorganism by dioxygenase, monooxygenase process.
Embodiment 7
For the application process of the infiltration type reaction wall composite of PAHs in groundwater pollution amelioration, step is：
By made PRB composites and coarse sand by volume 3:7 are mixed, and field is excavated, and it is 3.0 to set PRB buried depths
Rice, landfill thickness are 1.5 meters, and width of wall body is 1.2 meters.
Embodiment 8
With embodiment 7, difference is, by made PRB composites and coarse sand by volume 1:1 is mixed, and field is opened
Dig, it is 4.0 meters to set PRB buried depths, and landfill thickness is 1.8 meters, and width of wall body is 1.5 meters.
Embodiment 9
With embodiment 7, difference is, by made PRB composites and coarse sand by volume 4:6 are mixed, and field is opened
Dig, it is 6.0 meters to set PRB buried depths, and landfill thickness is 2.0 meters, and width of wall body is 2.0 meters.
Claims (7)
1. a kind of infiltration type reaction wall composite for PAHs in groundwater pollution amelioration, including kernel, packed layer and
Shell；The composition material of the kernel is charcoal spherical particle thing；Packed layer includes the component by following mass percent：Release
Oxygen agent 15.09% ~ 15.85%, carbon raw material 30.19% ~ 31.7% is released, plasticity bonds raw material attapulgite 15.09% ~ 15.85%, hypertonic
Permeability raw material 6.29% ~ 6.6%, surplus are adhesive；Shell includes the component by following mass percent：It is recessed that plasticity bonds raw material
Convex rod soil and cement 53.57% ~ 55.37%, high osmosis raw material 6.43% ~ 6.64%, surplus is adhesive；Described oxygen release agent is
Calper calcium peroxide, it is charcoal to release carbon raw material in packed layer；High osmosis raw material is diatomite, and described adhesive is sodium alginate.
2. the infiltration type reaction wall composite according to claim 1 for PAHs in groundwater pollution amelioration, its
It is characterised by, the charcoal of described kernel is coconut husk charcoal or peach-pit charcoal.
3. the infiltration type reaction wall composite according to claim 1 for PAHs in groundwater pollution amelioration, its
It is characterised by, it is coconut husk charcoal or peach-pit charcoal that carbon raw material charcoal is released in described packed layer.
4. the system of the infiltration type reaction wall composite according to claim 1 for PAHs in groundwater pollution amelioration
Preparation Method, its step are：
（1）80-100 mesh oxygen release agent is standby；
（2）It is standby that 80 ~ 100 mesh release carbon raw material；
（3）80 ~ 100 mesh plasticity bond raw material for standby；
（4）80 ~ 100 height of eye permeability raw material for standby；
（5）Adhesive sodium alginate and water are prepared into slurry, by sodium alginate powder uniformly, thin layer be sprinkled into water, and constantly
Quick stirring, make sodium alginate substantially uniformity soluble in water into thick, it is standby to be made into slurry；
（6）Charcoal is rolled in sugar coating machine kernel is made, natural air drying；
（7）The kernel prepared in step 6 is immersed in the slurry that step 5 prepares standby after 10 ~ 20min；
（8）By standby oxygen release agent, carbon raw material, high osmosis raw material and plasticity bonding raw material attapulgite are released by the quality hundred
Divide and mixing material is made than mixing, the mixing material is sprinkled into comminutor, and the kernel put into after step 7 immersion, open
Comminutor rolls, and constantly adds mixing material, and sprays into adhesive, until the material packed layer is rolled to expected thickness, that is, wraps
The structure of kernel and packed layer is included, particle diameter is 0.7 ~ 1.2cm；
（9）The material natural air drying that step 8 is manufactured, 10min in the slurry that step 5 prepares then is immersed in, so
Raw material attapulgite and cement, high osmosis raw material are bonded by the quality hundred by the plasticity crushed after being sprinkled into comminutor
Divide than blending ingredients made of mixing and be put into soaked filling layer material and wherein roll together, during producing material material, constantly
Blending ingredients are added, spray into adhesive, until the shell is rolled to expected thickness, it is 0.7 ~ 1.2mm；
（10）It is placed in hermetic bag and conserves after the composite natural air drying prepared through step 9, after tested the packed layer containing core
Particle diameter granule strength in 1cm reaches 53N/, and composite material granular intensity is 60N/, and the hardness of the composite can reach
To soaking 3 ~ 4 weeks not broken degree in water.
5. the system of the infiltration type reaction wall composite according to claim 4 for PAHs in groundwater pollution amelioration
Preparation Method, it is characterised in that comminutor is rolled with 46r/min rotating speeds in the step 8,9.
6. the system of the infiltration type reaction wall composite according to claim 4 for PAHs in groundwater pollution amelioration
Preparation Method, it is characterised in that in the step 5, sodium alginate and water in mass ratio 1:80 prepare slurry.
7. the infiltration type reaction wall composite according to claim 1 for PAHs in groundwater pollution amelioration is answered
With method, step is：
（1）By made PRB composites and coarse sand by volume 3:7~4:6 are mixed；
（2）Field is excavated, and it is 2.0~6.0 meters to set PRB buried depths, and landfill thickness is 1.5~2.0 meters, and width of wall body is 1.2~
2.0 rice.
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| CN107265665B (en) * | 2017-08-04 | 2019-11-22 | 南京大学 | A kind of infiltration type reaction wall composite material and preparation method for underground water containing chlorine pollution amelioration containing nitro-aromatic |
| CN107235561B (en) * | 2017-08-04 | 2020-01-07 | 南京大学 | Permeable reaction wall composite material for groundwater polycyclic aromatic hydrocarbon pollution remediation and preparation method thereof |
| CN114105331B (en) * | 2021-11-29 | 2024-04-19 | 广东省环境科学研究院 | Preparation method and application of calcium peroxide composite sustained release agent |
| CN114275985A (en) * | 2021-12-28 | 2022-04-05 | 南京大学 | Material capable of blocking pollutant release from bottom to water body and preparation method and application thereof |
| CN115259544A (en) * | 2022-06-22 | 2022-11-01 | 中国石油大学(华东) | Permeable reactive barrier process for coupling aerobic microorganisms with adsorption media |
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