CN107309268A - A kind of nanometer ferron injection device in situ and method for implanting - Google Patents
A kind of nanometer ferron injection device in situ and method for implanting Download PDFInfo
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- CN107309268A CN107309268A CN201710651691.5A CN201710651691A CN107309268A CN 107309268 A CN107309268 A CN 107309268A CN 201710651691 A CN201710651691 A CN 201710651691A CN 107309268 A CN107309268 A CN 107309268A
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- medicament
- biliquid
- injecting cavity
- inner tube
- plunger pump
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- 238000002347 injection Methods 0.000 title claims abstract description 76
- 239000007924 injection Substances 0.000 title claims abstract description 76
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 40
- ZBJWWKFMHOAPNS-UHFFFAOYSA-N loretin Chemical compound C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 ZBJWWKFMHOAPNS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229950010248 loretin Drugs 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003814 drug Substances 0.000 claims abstract description 138
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000000243 solution Substances 0.000 claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 claims abstract description 53
- 238000005553 drilling Methods 0.000 claims abstract description 44
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 42
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 42
- 239000002689 soil Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 22
- 230000008878 coupling Effects 0.000 claims description 14
- 238000010168 coupling process Methods 0.000 claims description 14
- 238000005859 coupling reaction Methods 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 239000002828 fuel tank Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 229910052603 melanterite Inorganic materials 0.000 claims description 4
- 208000002925 dental caries Diseases 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005067 remediation Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 description 9
- 231100000719 pollutant Toxicity 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 238000002161 passivation Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003895 groundwater pollution Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003900 soil pollution Methods 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010412 perfusion Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 108091092584 GDNA Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229940059939 kayexalate Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Abstract
The invention discloses a kind of nanometer ferron injection device in situ and method, belong to environment remediation technical field.The nanometer ferron of present invention injection device in situ, including biliquid syringe pump and biliquid injection drilling rod, the biliquid syringe pump includes the first plunger pump and the second plunger pump, provided with the first medicament injecting cavity and second medicament injecting cavity mutually separated in biliquid injection drilling rod, and first the agent outlet of plunger pump be connected with the inlet of the first medicament injecting cavity, the agent outlet of second plunger pump is connected with the inlet of second medicament injecting cavity, pass through above-mentioned two plunger pump and the first medicament injecting cavity in the presence of hydraulic control system, second medicament injecting cavity injects FeSO into soil to be repaired respectively4And NaBH4Solution.It can realize that the ground in-situ of Nanoscale Iron is prepared and repaired using technical scheme, reduce before Nanoscale Iron is contacted with pollution body and occur oxidation, the possibility reunited, so as to which its repairing effect is effectively ensured.
Description
Technical field
The invention belongs to environment remediation technical field, repaiied more specifically to a kind of soil and groundwater pollution original position
Apparatus for coating and technique.
Background technology
In-situ chemical reduction repair be a kind of conventional effective based technique for in-situ remediation, wherein nano-iron material with particle diameter it is small,
The features such as specific surface area is big, surface-active is high, reducing power is strong, can effectively organics removal, heavy metal and nitrate etc. it is many
Pollutant is planted, the research of soil and groundwater pollution amelioration is more and more applied to.
Research shows both at home and abroad, and Nanoscale Iron is used for rehabilitating soil and the mechanism of underground water pollution is：In FeO-H2In O systems
Three kinds of reducing agents, respectively FeO, Fe (II) and hydrogen are there are, the reduction of pollutant may be due to the different of reducing agent
In the presence of three kinds of approach.Nanoscale Iron has higher specific surface area, excellent adsorption ability and reactivity simultaneously, promotes
The generation of iron rot reaction, the substantial amounts of Fe (II) and hydrogen of generation can as pollutant reduction process electron donor, that is, react
An environmental system for constantly having electron donor to give is created in a short time, so as to improve the reduction efficiency of pollutant.
But, application of the current Nanoscale Iron in groundwater environmental repairing is remained in some problems：
(1) because nano zero valence iron granularity is small, specific surface area big, surface can be big and itself there is magnetic, thus it is easy to
Reunite, its particle diameter is just changed into micron order from nanoscale, greatly reduce the specific surface area of reaction, so as to cause degradation efficiency
Reduction；(2) easily it is oxidized in atmosphere, forms passivation layer and reduce activity, what is had even can occurs spontaneous combustion, Nanoscale Iron
It is huge from the transportation challenge for being prepared into the scene of reparation, nano zero valence iron is so limited in underground water and soil remediation
Application.
In order to solve these above-mentioned problems, increasing nano zero valence iron modification technology arises at the historic moment, such as passivation nanometer
Zero-valent Iron, load nano zero valence iron and stabilizer transformation Nanoscale Iron, wherein the research for transforming Nanoscale Iron with stabilizer is more, and by
This generates a variety of Nanoscale Iron modification stabilizers, such as starch, kayexalate.Such as, Chinese Patent Application No. is
201010221529.8 application case disclose a kind of method of nano-iron slurry reaction zone in-situ immobilization nitrobenzene contamination underground water,
This application case is to beat a bite above injection well and inspection well in underground water pollution area, by nano-iron slurry or starch well prepared in advance
Modified Nano iron slurry pours into injection well, target contaminant in inspection well is monitored during perfusion in real time, when reaching expected treatment effect
Stop perfusion.This application case is that processing is modified to Nanoscale Iron using starch, so as to can improve institute to a certain extent
The specific surface area of nano-iron material is obtained, improves its repairing effect.And for example, Chinese Patent Application No. is 201210445834.4 Shen
Please case disclose a kind of preparation method of the modification zeroth order Nanoscale Iron suitable for underwater prevention, this application case is to use polyphenyl second
Alkene sodium sulfonate is modified processing to nano-iron material it is hereby achieved that metastable scattered zeroth order Nanoscale Iron.
Existing research at present is concentrated mainly on the holding original reactivity of Nanoscale Iron and with the abundant contact of pollutant etc.
In problem, but most of research is also only limitted to the laboratory research stage, is applied in actual treatment technique effect and little,
The passivation inactivation of nano-iron material can not be still prevented effectively from.Therefore, nano-iron material how is enable to be efficiently applied to actual work
Skill process, and ensure its popularization of the repair process effect for nano-iron material in underground water and soil remediation to pollutant
It is also the technical barrier that current domestic and international researcher is badly in need of solving using just most important.
The content of the invention
1. the invention technical problem to be solved
It is an object of the invention to overcome nano-iron material is applied into soil and groundwater pollution amelioration in the prior art
When, passivation inactivation easily occurs in preparation, transportation for nano-iron material so that influence its repairing effect it is not enough there is provided
A kind of nanometer ferron injection device in situ and method for implanting.The underground of Nanoscale Iron can be realized using technical scheme
Original position prepares and repaired, and reduces before Nanoscale Iron is contacted with pollution body and occurs oxidation, the possibility reunited, so as to effectively guarantor
Demonstrate,prove its repairing effect.
2. technical scheme
To reach above-mentioned purpose, the technical scheme that the present invention is provided is：
A kind of nanometer ferron of present invention injection device in situ, including biliquid syringe pump and biliquid injection drilling rod, it is described
Biliquid syringe pump be connected with hydraulic control system, the biliquid syringe pump include the first plunger pump and the second plunger pump, it is described
Provided with the first medicament injecting cavity and second medicament injecting cavity mutually separated in biliquid injection drilling rod, and the medicament of the first plunger pump
Outlet is connected with the inlet of the first medicament injecting cavity, the agent outlet of the second plunger pump and the inlet of second medicament injecting cavity
It is connected, passes through above-mentioned two plunger pump and the first medicament injecting cavity, second medicament injecting cavity in the presence of hydraulic control system
Respectively FeSO is injected into soil to be repaired4And NaBH4Solution.
Further, described hydraulic control system includes hydraulic cylinder, reversal valve and oil pump, wherein, the oil-feed of oil pump
Mouth is connected with fuel tank, and on the one hand its oil-out is connected with two cavitys of hydraulic cylinder respectively by reversal valve, is on the other hand passed through
Overflow valve is connected with fuel tank；The piston of the hydraulic cylinder by piston rod respectively with the first plunger pump and the plunger of the second plunger pump
It is fixedly linked.
Further, described biliquid injection drilling rod is designed as double-layer hollow sleeve structure, and the inside of inner layer sleeve is set
There are formation second medicament injecting cavity between the first medicament injecting cavity, two layers of sleeve pipe, and the first medicament injecting cavity and second medicament note
It is open top, the cavity of bottom lock to penetrate chamber.
Further, the bottom of biliquid injection drilling rod is provided with drill bit assembly, and drill bit assembly is provided with respectively with the
Two groups of jets that one medicament injecting cavity is connected with second medicament injecting cavity, the height of two groups of jets is different, two groups of injections
Mouth is correspondingly provided with the first medicament nozzle and second medicament nozzle, and the first medicament spray being connected with the first medicament injecting cavity respectively
Mouth is inclined upwardly setting, and the second medicament nozzle being connected with second medicament injecting cavity tilts down setting.
Further, described biliquid injection drilling rod includes top outer tube and top inner tube, and top outer tube and drill bit assembly it
Between provided with lengthening outer bar, provided with lengthening inner tube between top inner tube and drill bit assembly, top outer tube, top inner tube, lengthen outer bar and lengthening
Inner tube collectively forms double-layer hollow sleeve structure；Pass through screw thread between described lengthening outer bar and lengthening inner tube and drill bit assembly
Connection, and the inwall bottom of lengthening outer bar extends inwardly to form step, the internal diameter size of the step and the outer diameter ruler for lengthening inner tube
It is very little to match, it is provided with the second sealing ring between the inwall and lengthening outer wall of inner tube of above-mentioned step；The inside of the drill bit assembly is set
There is the cavity with top inner tube and the intracavity inter-connection for lengthening inner tube, the cavity and the inner chamber of top inner tube and lengthening inner tube are collectively constituted
First medicament injecting cavity.
Further, the top of the top inner tube is connected with one end of hydraulic tube, and the other end of hydraulic tube passes through right angle
Joint is connected with top external pipe thread, and described angle coupling is connected by the second connecting tube with the agent outlet of the first plunger pump；
Described top outer tube is provided with the straight coupling with its intracavity inter-connection, and the straight coupling passes through the second connecting tube and the second plunger
The agent outlet of pump is connected.
Further, the bottom of the drill bit assembly internal cavities be provided with back-moving spring and check-valves, and check-valves with
The first sealing ring is provided between drill bit assembly inner chamber；The end for lengthening outer bar and lengthening inner tube is disposed as tenon structure,
Its one end is male, and the other end is female, and the bottom of top outer tube and top inner tube is provided with respectively with lengthening outer bar and lengthening inner tube
The female or male head structure matched.
A kind of nanometer ferron of present invention method for implanting in situ, starts the nanometer ferron original position injection dress of the present invention
Put, under the control of hydraulic control system, injected and injected respectively in the different injecting cavities of drilling rod to biliquid by biliquid syringe pump
FeSO4Solution and NaBH4Solution, controls FeSO4·7H2O and NaBH4The mol ratio of injection is 1:3, then injected and bored by biliquid
Bar is by FeSO4Solution and NaBH4Solution is ejected into soil to be repaired respectively, FeSO4Solution and NaBH4Solution is mixed and reacted
Nanoscale Iron is generated, so that the polluter treated in rehabilitating soil carries out deoxidization, degradation, the reparation of contaminated soil is realized.
Further, a kind of nanometer of ferron of the invention method for implanting in situ is concretely comprised the following steps：
(1) drill bit assembly is installed on environment rig, the drill bit of drill bit assembly is pierced into underground using environment rig, when
When drill bit reaches underground pollution position, the inlet of the first medicament injecting cavity is set to pass through external pipe and the medicament of the first plunger pump
Outlet is connected, and the inlet of second medicament injecting cavity is connected by external pipe with the agent outlet of the second plunger pump；
(2) under the control of hydraulic control system, the first plunger pump sucks FeSO by its medicament inlet pipeline4Solution,
And the first medicament injecting cavity injection FeSO of drilling rod is injected to biliquid by its agent outlet pipeline4Solution；Second plunger pump leads to
Cross its medicament inlet pipeline suction NaBH4Solution, and noted by the second medicament of its agent outlet pipeline to biliquid injection drilling rod
Penetrate chamber injection NaBH4Solution；
FeSO in (3) first medicament injecting cavities4Solution is ejected into soil to be repaired, the second medicine by the first medicament nozzle
NaBH in agent injecting cavity4Solution is ejected into soil to be repaired, FeSO by second medicament nozzle4Solution and NaBH4Solution is in medicine
Agent flour mixed with adulterants mixes and reacts generation Nanoscale Iron, and Nanoscale Iron is under the driving of injection pressure and fluid dynamic difference, with injection mouth region
The polluter contact in domain, so that the polluter treated in rehabilitating soil carries out deoxidization, degradation.
Further, the medicament inlet pipeline and FeSO of first plunger pump4Pharmacy jar is connected, second plunger
The medicament inlet pipeline and NaBH of pump4Pharmacy jar is connected；The FeSO4It is the poly- of 5g/L that volumetric concentration is also added with pharmacy jar
Vinylpyrrolidone or by 1:5 ratio is used as stabilizer added with mass percent for 0.6% cmc soln.
3. beneficial effect
The technical scheme provided using the present invention, compared with prior art, with following remarkable result：
(1) a kind of nanometer ferron of the invention injection device in situ, including biliquid syringe pump and biliquid injection drilling rod, it is double
Provided with the first medicament injecting cavity and second medicament injecting cavity mutually separated, the first medicament injecting cavity and second in liquid injection drilling rod
The first plunger pump, the second plunger pump of medicament injecting cavity respectively with biliquid syringe pump are connected, and thereby may be ensured that to contaminated soil
FeSO is inside injected respectively4And NaBH4Solution, the ground in-situ for realizing Nanoscale Iron is prepared and repaired, and reduces Nanoscale Iron and pollution
Oxidation, the possibility reunited occur before body contact, and then improves in-situ immobilization effect.
(2) a kind of nanometer ferron of the invention injection device in situ, the bottom of the biliquid injection drilling rod is provided with drill bit
Component so that biliquid injection drilling rod is both the carrier of medicament, is also the actuator of drilling, perforating, is easy to repairing for contaminated soil
Multiple operation.Above-mentioned drill bit assembly is provided with two groups of injections being connected respectively with the first medicament injecting cavity and second medicament injecting cavity
Mouthful, the height of two groups of jets is different, and two groups of jets are correspondingly provided with the first medicament nozzle and second medicament nozzle respectively, and with
The first medicament nozzles inclined upwards that first medicament injecting cavity is connected are set, the second medicine being connected with second medicament injecting cavity
Agent nozzle tilts down setting, so that medicament ejector can be mixed quickly to after polluting body, it is ensured that the conjunction of nanometer ferron
Into speed and the remediation efficiency of soil.Angle, spacing and the quantity of above-mentioned first medicament nozzle and second medicament nozzle can roots
Factually border geological conditions is adjusted.
(3) a kind of nanometer ferron of the invention injection device in situ, described biliquid injection drilling rod include top outer tube and
Push up to be provided between inner tube, and top outer tube and drill bit assembly and lengthen outer bar, provided with inner tube is lengthened between top inner tube and drill bit assembly, push up
Outer tube, top inner tube, lengthening outer bar and lengthening inner tube collectively form double-layer hollow sleeve structure, so as to need choosing according to reparation
Select the lengthening outer bar for installing different hop counts and lengthen inner tube, so as to meet the reparation demand of different depth soil.
(4) a kind of nanometer ferron of the invention method for implanting in situ, drilling rod is injected by biliquid syringe pump to biliquid
FeSO is injected respectively in different injecting cavities4Solution and NaBH4Solution, then injects drilling rod by FeSO by biliquid4Solution with
NaBH4Solution is ejected into soil to be repaired respectively, FeSO4Solution and NaBH4Solution mixing and reaction in-situ generation Nanoscale Iron,
Deoxidization, degradation is carried out so as to treat the polluter in rehabilitating soil, the reparation of contaminated soil is realized, so as to be prevented effectively from
Oxidation, the phenomenon reunited easily occur before Nanoscale Iron is contacted with pollution body in the prior art, it is ensured that the reparation to contaminated soil is imitated
Really.
Brief description of the drawings
Fig. 1 is the structural representation of the nanometer ferron in-situ injection device of the present invention；
Fig. 2 is the schematic diagram of the hydraulic system of the syringe pump of the present invention；
Fig. 3 is the structural representation for injecting drilling rod of the invention；
The mplifying structure schematic diagram that Fig. 4 is region A in Fig. 3；
Fig. 5 injects the operating diagram of drilling rod for the present invention.
Label declaration in accompanying drawing：
1st, environment rig；2nd, the first connecting tube；3rd, biliquid syringe pump；301st, the first plunger pump；302nd, the second plunger pump；4、
Second connecting tube；5th, biliquid injection drilling rod；6th, angle coupling；7th, straight coupling；8th, hydraulic tube；9th, outer tube is pushed up；10th, inner tube is pushed up；
11st, outer bar is lengthened；12nd, inner tube is lengthened；13rd, drill bit assembly；14th, drill bit；15th, back-moving spring；16th, the first sealing ring；17th, non-return
Valve；18th, the first medicament injecting cavity；19th, the first medicament nozzle；20th, second medicament injecting cavity；21st, second medicament nozzle；22nd,
Two sealing rings；23rd, medicament flour mixed with adulterants；24th, hydraulic cylinder；25th, reversal valve；26th, oil pump；27th, overflow valve.
Embodiment
To further appreciate that present disclosure, in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
As Figure 1-Figure 4, a kind of nanometer ferron of the present embodiment injection device in situ, including the He of biliquid syringe pump 3
Biliquid injects drilling rod 5, and described biliquid syringe pump 3 is connected with hydraulic control system, and the biliquid syringe pump 3 includes the first plunger pump
301 and second plunger pump 302, provided with the first medicament injecting cavity 18 and second mutually separated in described biliquid injection drilling rod 5
Medicament injecting cavity 20, and the agent outlet of the first plunger pump 301 is connected with the inlet of the first medicament injecting cavity 18, the second plunger
The agent outlet of pump 302 is connected with the inlet of second medicament injecting cavity 20, by above-mentioned in the presence of hydraulic control system
Two plunger pumps and the first medicament injecting cavity 18, second medicament injecting cavity 20 inject FeSO into soil to be repaired respectively4With
NaBH4Solution, utilizes FeSO4With excessive NaBH4Solution is reacted to prepare Nanoscale Iron.The present embodiment passes through two plungers
The compartmentalized design of different agents injecting cavity can effectively ensure that two kinds of solution are being sprayed in the setting of pump and biliquid injection drilling rod 5
It is relatively isolated, is contacted with each other after being ejected from injection drilling rod 5 before being mapped to underground pollution medium, can be complete within the several seconds
Nanoscale Iron is generated into reaction, reaction rate is fast, higher to soil remediation efficiency, because prepared by the ground in-situ for realizing Nanoscale Iron
With reparation, reduce and oxidation, the possibility reunited occur before Nanoscale Iron is contacted with pollution body, and then improve in-situ immobilization effect
Really.
Embodiment 2
As Figure 1-Figure 4, a kind of nanometer ferron of the present embodiment injection device in situ, including environment rig 1, biliquid
Syringe pump 3 and biliquid injection drilling rod 5, wherein, the hydraulic control system of the biliquid syringe pump 3 is located on environment rig 1, this pair
Liquid syringe pump 3 includes being provided with what is mutually separated in the first plunger pump 301 and the second plunger pump 302, described biliquid injection drilling rod 5
First medicament injecting cavity 18 and second medicament injecting cavity 20, and the agent outlet of the first plunger pump 301 and the first medicament injecting cavity
18 inlet is connected, and the agent outlet of the second plunger pump 302 is connected with the inlet of second medicament injecting cavity 20, in hydraulic pressure control
By above-mentioned two plunger pump and the first medicament injecting cavity 18, second medicament injecting cavity 20 respectively to be repaired in the presence of system processed
Injection FeSO in earth backing earth4And NaBH4Solution.
As shown in Fig. 2 the hydraulic control system of the present embodiment includes hydraulic cylinder 24, reversal valve 25 and oil pump 26, wherein, oil
The oil inlet of pump 26 is connected with the fuel tank of rig 1, two chambers of its oil-out on the one hand by reversal valve 25 respectively with hydraulic cylinder 24
Body phase connects, and is on the other hand connected by overflow valve 27 with fuel tank.The piston of the hydraulic cylinder 24 is by piston rod respectively with first
The plunger of the plunger pump 302 of plunger pump 301 and second is fixedly linked, i.e., described biliquid syringe pump 3 is the spare interface warp by rig 1
The hydraulic power supply direct drive of the steady pressure all the way provided after pressure-reducing valve and overflow valve 27 and flow, pumping hole overflow valve are provided
27 setting mainly plays safeguard protection, and the flow of pumping hole enters the double-acting hydraulic cylinder 24 of single plunger by reversal valve 25
Two chambers, because the first plunger pump 301 and the second plunger pump 302 of hydraulic cylinder 24 and biliquid syringe pump 3 are rigidly connected, therefore
The alternate injection of two kinds of liquid can be achieved by the reciprocating motion of hydraulic cylinder 24.The P mouths of reversal valve 25 and oil in the present embodiment
The oil-out of pump 26 is connected, and its T mouthful is connected with fuel tank, and its A mouthfuls, B mouthfuls passes through two of the first connecting tube 2 and hydraulic cylinder 24 respectively
Cavity is connected.The specific operation of the biliquid syringe pump 3 is as follows：When hydraulic cylinder 24 is moved right, a left side for reversal valve 25
Position is connected, and moving right for hydraulic cylinder 24 is realized in the left position oil-feed of hydraulic cylinder 24, right position oil return.In motion process, second is driven
Plunger pump 302 is moved to right, due to the effect of pressure differential, and a, c, e, g check valve are opened, and b, d, f, h closed check valve, a check valves are opened
Open, FeSO4Into the left chamber of the second plunger pump 302, c check valves are opened, FeSO4Injected；E check valves are opened, NaBH4Enter
Enter the left chamber of the first plunger pump 301, g check valves are opened, NaBH4Injected.When the right chamber liquid of the second plunger pump 302 is drained
When, hydraulic cylinder 24 can touch the right side brake pin on reversal valve 25, make hydraulic cylinder 24 stop moving to right, while reversal valve 25
Start commutation, the right position of reversal valve 25 is connected, and hydraulic cylinder 24 starts to move to left.During moving to left, b, d, f, h check valve are opened, a,
C, e, g closed check valve.B check valves are opened, FeSO4/NaBH4Into the right chamber of the second plunger pump 302, d check valves are opened,
FeSO4Injected；F check valves are opened, NaBH4Into the right chamber of the first plunger pump 301, h check valves are opened, NaBH4Noted
Penetrate.The reciprocating motion of cylinder realizes FeSO4/NaBH4And NaBH4/FeSO4Continuous injection.When the left chamber liquid of plunger pump is drained
When, hydraulic cylinder 24 can touch the left hand brake pin on reversal valve 25, and hydraulic cylinder 24 stops moving to left, and now reversal valve 25 starts to change
To the left position of reversal valve 25 is connected.And so on, the continuous injection of two kinds of liquid is realized.
With reference to Fig. 3, Fig. 4, the biliquid injection drilling rod 5 of the present embodiment is designed as double-layer hollow sleeve structure, inner layer sleeve
Inside, which is provided between the first medicament injecting cavity 18, two layers of sleeve pipe, forms second medicament injecting cavity 20, and the first medicament injecting cavity 18
With second medicament injecting cavity 20 be open top, bottom lock cavity.The bottom of above-mentioned biliquid injection drilling rod 5 is provided with drill bit
Component 13, drill bit assembly 13 is provided with two groups of sprays being connected respectively with the first medicament injecting cavity 18 and second medicament injecting cavity 20
Loophole, the height of two groups of jets is different, and the jet being connected with the first medicament injecting cavity 18 is inclined upwardly setting, with second
The jet that medicament injecting cavity 20 is connected tilts down setting, so that medicament ejector can be mixed quickly to after polluting body
Close, the number of two groups of jets can specifically be set to 2-5 according to actual conditions.Above-mentioned two groups of jets are correspondingly provided with respectively
One medicament nozzle 19 and second medicament nozzle 21.The present embodiment is by controlling different two groups of medicament nozzles of pressure and regulation
Angle and spacing, it is possible to achieve the in-situ immobilization of different depth soil.
Embodiment 3
The basic be the same as Example 2 of structure of the nanometer ferron of the present embodiment injection device in situ, more specifically, such as Fig. 3, figure
Shown in 4, the biliquid injection drilling rod 5 of the present embodiment includes top outer tube 9 and top inner tube 10, and top outer tube 9 and top inner tube 10 pass through screw thread
Connection, and push up provided with outer bar 11 is lengthened between outer tube 9 and drill bit assembly 13, provided with lengthening between top inner tube 10 and drill bit assembly 13
Inner tube 12, top outer tube 9, top inner tube 10, lengthening outer bar 11 and lengthening inner tube 12 collectively form double-layer hollow sleeve structure.It is above-mentioned to add
It is threadedly coupled between long outer bar 11 and drill bit assembly 13 with NPT, lengthens and regular screw threads are used between inner tube 12 and drill bit assembly 13
Connection, and the inwall bottom of lengthening outer bar 11 extends inwardly to form step, the internal diameter size of the step is with lengthening the outer of inner tube 12
Footpath size matches, and the second sealing ring 22 is provided between the inwall and the lengthening outer wall of inner tube 12 of above-mentioned step.Above-mentioned step is with adding
The outer wall of long inner tube 12 together closes the cavity bottom between outer tube and inner tube, and ensures that it is sealed by the second sealing ring 22
Property, it is consequently formed second medicament injecting cavity 20.The inside of the drill bit assembly 13 is provided with pushing up inner tube 10 and lengthening inner tube 12
The cavity of intracavity inter-connection, the cavity and the inner chamber of top inner tube 10 and lengthening inner tube 12 collectively constitute the first medicament injecting cavity 18,
And first medicament injecting cavity 18 and the relative closure of second medicament injecting cavity 20, so as to FeSO4And NaBH4Two kinds of medicaments point
Do not conveyed.
The bottom of the above-mentioned internal cavities of drill bit assembly 13 is additionally provided with back-moving spring 15 and check-valves 17, so as to prevent underground
Water flows back, and is provided with the first sealing ring 16 between check-valves 17 and the inner chamber of drill bit assembly 13 to ensure its sealing.Work as NaBH4Note
Penetrate intracavitary medicament reach setting pressure when, non-return valve pocket, NaBH can be opened4It can be sprayed from jet, when pressure is less than setting
During pressure, back-moving spring 15 resets non-return valve pocket, and can block jet prevents backflow of underground water.The lengthening outer bar 11 is with adding
The end of long inner tube 12 is disposed as tenon structure, and its one end is male, and the other end is female, and top outer tube 9 and top inner tube 10
Bottom provided with respectively with lengthening outer bar 11 and lengthening the female that matches of inner tube 12 or male head structure, so as to according to drilling well
Depth, which is overlapped, to be used, and meets the reparation requirement of different depth soil.
The top that inner tube 10 is pushed up in the present embodiment is connected with one end of hydraulic tube 8, and the other end of hydraulic tube 8 passes through heading joint
First 6 are connected with the top screw thread of outer tube 9, and the hydraulic tube 8 is flexible pipe, because can adjust the cumulative length between inner and outer tubes in its length
Difference.Described angle coupling 6 is connected by the second connecting tube 4 with the agent outlet of the first plunger pump 301；Described top outer tube 9
On be welded with straight coupling 7 with its intracavity inter-connection, the straight coupling 7 passes through the second connecting tube 4 and the second plunger pump 302
Agent outlet is connected.
The nanometer ferron of the present embodiment method for implanting in situ, starts the nanometer ferron original position injection dress of the present embodiment
Put, under the control of hydraulic control system, injected and noted respectively in the different injecting cavities of drilling rod 5 to biliquid by biliquid syringe pump 3
Penetrate FeSO4Solution and NaBH4Solution, then injects drilling rod 5 by FeSO by biliquid4Solution and NaBH4Solution is ejected into treats respectively
In rehabilitating soil, FeSO4Solution and NaBH4Solution mixes and reacts generation Nanoscale Iron, so as to treat the pollutant in rehabilitating soil
Matter carries out deoxidization, degradation, realizes the reparation of contaminated soil.Received using the nanometer ferron of the present embodiment injection device in situ
What rice ferron original position was injected concretely comprises the following steps：
(1) above-mentioned improved drill bit assembly 13 is installed on environment rig 1, using environment rig 1 by drill bit assembly 13
Drill bit 14 pierce underground, the depth pierced as needed can connect lengthening outer bar 11 and lengthen interior bar 12.Underground is reached when boring
During gdna contamination, when drill bit 14 reaches underground pollution position, lead to the angle coupling 6 at the inlet of the first medicament injecting cavity 18
The agent outlet that external pipe is crossed with the first plunger pump 301 is connected, and makes the straight coupling 7 at the inlet of second medicament injecting cavity 20
It is connected by external pipe with the agent outlet of the second plunger pump 302.
The medicament inlet pipeline and FeSO of above-mentioned first plunger pump 3014Pharmacy jar is connected, FeSO4FeSO in solution4It is dense
Spend for 0.01mol/L, the FeSO4Also stabilization is used as in pharmacy jar added with volumetric concentration for 5g/L polyvinylpyrrolidone
Agent, specifically can also add carboxymethyl cellulose that mass percent is 2.4% as stabilizer, carboxymethyl cellulose with
FeSO4·7H2O mixing ratio is 1:5, so as to make Nanoscale Iron obtained by preparation keep higher reproducibility, it can be situated between in pollution
Parent pollutant is gone back in matter.The medicament inlet pipeline and NaBH of above-mentioned second plunger pump 3024Pharmacy jar is connected, NaBH4In solution
NaBH4Concentration be 0.03mol/L.Pass through FeSO4And NaBH4The flowmeter of pharmacy jar outlet accurately can measure and adjust two
Plant the injection ratio of medicament.
(2) under the control of hydraulic control system, the first plunger pump 301 sucks FeSO by its medicament inlet pipeline4It is molten
Liquid, and the first medicament injecting cavity 18 for injecting drilling rod 5 to biliquid by its agent outlet pipeline injects FeSO4Solution；Second post
Fill in pump 302 and NaBH is sucked by its medicament inlet pipeline4Solution, and drilling rod 5 is injected to biliquid by its agent outlet pipeline
Second medicament injecting cavity 20 injects NaBH4Solution, wherein FeSO4·7H2O and NaBH4The mol ratio of injection is 1:3.
(3) as shown in figure 5, FeSO in the first medicament injecting cavity 184Solution is ejected into by the first medicament nozzle 19 and treated
NaBH in rehabilitating soil, second medicament injecting cavity 204Solution is ejected into soil to be repaired, FeSO by second medicament nozzle 214
Solution and NaBH4Solution mixes in medicament flour mixed with adulterants 23 and reacts generation Nanoscale Iron, and Nanoscale Iron is in injection pressure and fluid dynamic
Under the driving of difference, contacted with the polluter in injection port region, so that the polluter treated in rehabilitating soil carries out reduction drop
Solution.
The method for implanting easy construction in situ of the nanometer ferron of the present embodiment, realizes the medicament system of in-situ chemical reduction
Standby, drilling, perforating, injection are repaired integration, and can solved by the application of result of laboratory research into actual place reparation
Passivation deactivation prob of the Nanoscale Iron in preparation, transportation so that Nanoscale Iron maintains the optimal property of medicine when being contacted with pollution body,
Reach best repair effect.FeSO4And NaBH4Medicament is sprayed by respective conveyor chamber from its jet, is mixed at medicament flour mixed with adulterants
Close, Nanoscale Iron can be produced in the short time, while iron rot reaction also produces substantial amounts of Fe (II) and hydrogen, can be as pollutant also
The electron donor of former process.The reducing substances such as FeO, Fe (II) and hydrogen, under the driving of injection pressure and fluid dynamic difference,
Contacted with the polluter in injection port region, deoxidization, degradation polluter, the reparation pollution time is effectively ensured, solved medicament and lose
The problem of passivation living, it is ensured that remediation efficiency.
Schematical above that the present invention and embodiments thereof are described, the description does not have restricted, institute in accompanying drawing
What is shown is also one of embodiments of the present invention, and actual structure is not limited thereto.So, if the common skill of this area
Art personnel are enlightened by it, without departing from the spirit of the invention, are designed and the technical scheme without creative
Similar frame mode and embodiment, all should belong to protection scope of the present invention.
Claims (10)
1. a kind of nanometer of ferron injection device in situ, it is characterised in that：Including biliquid syringe pump (3) and biliquid injection drilling rod
(5), described biliquid syringe pump (3) is connected with hydraulic control system, and the biliquid syringe pump (3) includes the first plunger pump (301)
With the second plunger pump (302), provided with the first medicament injecting cavity (18) mutually separated and the in described biliquid injection drilling rod (5)
Two medicament injecting cavities (20), and the agent outlet of the first plunger pump (301) is connected with the inlet of the first medicament injecting cavity (18),
The agent outlet of second plunger pump (302) is connected with the inlet of second medicament injecting cavity (20).
2. a kind of nanometer ferron injection device in situ according to claim 1, it is characterised in that：Described hydraulic control
System includes hydraulic cylinder (24), reversal valve (25) and oil pump (26), wherein, the oil inlet of oil pump (26) is connected with fuel tank, and it goes out
On the one hand hydraulic fluid port is connected with two cavitys of hydraulic cylinder (24) respectively by reversal valve (25), on the other hand passes through overflow valve (27)
It is connected with fuel tank；The piston of the hydraulic cylinder (24) by piston rod respectively with the first plunger pump (301) and the second plunger pump
(302) plunger is fixedly linked.
3. a kind of nanometer ferron injection device in situ according to claim 1 or 2, it is characterised in that：Described biliquid
Injection drilling rod (5) is designed as double-layer hollow sleeve structure, and the inside of inner layer sleeve is provided with the first medicament injecting cavity (18), two layers set
Second medicament injecting cavity (20) is formed between pipe, and the first medicament injecting cavity (18) and second medicament injecting cavity (20) they are top
Opening, the cavity of bottom lock.
4. a kind of nanometer ferron injection device in situ according to claim 3, it is characterised in that：The biliquid injection is bored
The bottom of bar (5) be provided with drill bit assembly (13), drill bit assembly (13) provided with respectively with the first medicament injecting cavity (18) and second
Two groups of jets that medicament injecting cavity (20) is connected, the height of two groups of jets is different, with first medicament injecting cavity (18) phase
The jet of connection is inclined upwardly setting, and the jet being connected with second medicament injecting cavity (20) tilts down setting, and two
Group jet is correspondingly provided with the first medicament nozzle (19) and second medicament nozzle (21) respectively.
5. a kind of nanometer ferron injection device in situ according to claim 4, it is characterised in that：Described biliquid injection
Drilling rod (5), which includes being provided between top outer tube (9) and top inner tube (10), and top outer tube (9) and drill bit assembly (13), lengthens outer bar
(11), push up provided with inner tube (12) is lengthened between inner tube (10) and drill bit assembly (13), top outer tube (9), top inner tube (10), lengthening are outer
Bar (11) and lengthening inner tube (12) collectively form double-layer hollow sleeve structure；Described lengthening outer bar (11) and lengthening inner tube (12)
It is connected through a screw thread between drill bit assembly (13), and lengthens the inwall bottom of outer bar (11) and extends inwardly to form step, should
The internal diameter size of step matches with lengthening the outside dimension of inner tube (12), and the inwall of above-mentioned step is with lengthening inner tube (12) outer wall
Between be provided with the second sealing ring (22)；The inside of the drill bit assembly (13) is provided with pushing up inner tube (10) and lengthening inner tube (12)
The cavity of intracavity inter-connection, the cavity and the inner chamber of top inner tube (10) and lengthening inner tube (12) collectively constitute the first medicament injecting cavity
(18)。
6. a kind of nanometer ferron injection device in situ according to claim 5, it is characterised in that：The top inner tube (10)
Top be connected with one end of hydraulic tube (8), the other end of hydraulic tube (8) passes through angle coupling (6) and top outer tube (9) screw thread phase
Even, described angle coupling (6) is connected by the second connecting tube (4) with the agent outlet of the first plunger pump (301)；Described top
Outer tube (9) passes through the second connecting tube (4) and second provided with the straight coupling (7) with its intracavity inter-connection, the straight coupling (7)
The agent outlet of plunger pump (302) is connected.
7. a kind of nanometer ferron injection device in situ according to claim 5, it is characterised in that：The drill bit assembly
(13) bottom of internal cavities is provided with back-moving spring (15) and check-valves (17), and check-valves (17) and drill bit assembly (13) inner chamber
Between be provided with the first sealing ring (16)；The end for lengthening outer bar (11) and lengthening inner tube (12) is disposed as tenon structure,
Its one end is male, and the other end is female, and the bottom of top outer tube (9) and top inner tube (10) is provided with respectively with lengthening outer bar (11)
And lengthen female or male head structure that inner tube (12) matches.
8. a kind of nanometer of ferron method for implanting in situ, it is characterised in that：Start the nanometer any one of claim 1-7
Ferron original position injection device, under the control of hydraulic control system, drilling rod (5) is injected by biliquid syringe pump (3) to biliquid
Different injecting cavities in inject FeSO respectively4Solution and NaBH4Solution, FeSO4·7H2O and NaBH4The mol ratio of injection is 1:3,
Then drilling rod (5) is injected by FeSO by biliquid4Solution and NaBH4Solution is ejected into soil to be repaired respectively, FeSO4Solution
With NaBH4Solution mixes and reacts generation Nanoscale Iron, so that the polluter treated in rehabilitating soil carries out deoxidization, degradation, realizes
The reparation of contaminated soil.
9. a kind of nanometer ferron method for implanting in situ according to claim 8, it is characterised in that it is concretely comprised the following steps：
(1) drill bit assembly (13) is installed on environment rig (1), using environment rig (1) by the drill bit of drill bit assembly (13)
(14) pierce underground, when drill bit (14) reach underground pollution position when, make the first medicament injecting cavity (18) inlet pass through it is outer
Adapter road is connected with the agent outlet of the first plunger pump (301), the inlet of second medicament injecting cavity (20) is passed through extension tube attached
Road is connected with the agent outlet of the second plunger pump (302)；
(2) under the control of hydraulic control system, the first plunger pump (301) sucks FeSO by its medicament inlet pipeline4Solution,
And the first medicament injecting cavity (18) injection FeSO of drilling rod (5) is injected to biliquid by its agent outlet pipeline4Solution；Second post
Fill in pump (302) and NaBH is sucked by its medicament inlet pipeline4Solution, and drilling rod is injected to biliquid by its agent outlet pipeline
(5) second medicament injecting cavity (20) injection NaBH4Solution；
FeSO in (3) first medicament injecting cavities (18)4Solution is ejected into soil to be repaired by the first medicament nozzle (19), the
NaBH in two medicament injecting cavities (20)4Solution is ejected into soil to be repaired, FeSO by second medicament nozzle (21)4Solution with
NaBH4Solution mixes in medicament flour mixed with adulterants (23) and reacts generation Nanoscale Iron, and Nanoscale Iron is in injection pressure and fluid dynamic difference
Under driving, contacted with the polluter in injection port region, so that the polluter treated in rehabilitating soil carries out deoxidization, degradation.
10. a kind of nanometer ferron method for implanting in situ according to claim 9, it is characterised in that：First plunger
The medicament inlet pipeline and FeSO of pump (301)4Pharmacy jar be connected, the medicament inlet pipeline of second plunger pump (302) with
NaBH4Pharmacy jar is connected, and the FeSO4Also added with volumetric concentration is 5g/L polyvinylpyrrolidone or presses in pharmacy jar
1:5 ratio is used as stabilizer added with mass percent for 0.6% cmc soln.
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| CN108982145A (en) * | 2018-06-06 | 2018-12-11 | 江苏省环境科学研究院 | A kind of vehicular unified platform collecting soil collection, detection, improvement |
| CN111744954A (en) * | 2020-06-11 | 2020-10-09 | 昆明学院 | Soil prosthetic devices based on microbial remediation |
| CN111889503A (en) * | 2020-07-31 | 2020-11-06 | 上海化工研究院有限公司 | Sampling and in-situ remediation device for volatile organic compound contaminated soil and application thereof |
| CN112246856A (en) * | 2020-09-29 | 2021-01-22 | 徐州徐工环境技术有限公司 | Pollute original flavor of soil and restore injection device |
| CN112246857A (en) * | 2020-09-29 | 2021-01-22 | 徐州徐工环境技术有限公司 | Soil normal position injection is restoreed and smell restraines integrated device |
| CN112875874A (en) * | 2021-01-12 | 2021-06-01 | 江苏省环境科学研究院 | In-situ reinforced repair method for underground water polluted by chlorohydrocarbon |
| CN112974504A (en) * | 2021-01-20 | 2021-06-18 | 中国环境科学研究院 | In-situ reduction targeted injection repair method for difficult-to-oxidize organic contaminated site |
| CN113414229A (en) * | 2021-06-18 | 2021-09-21 | 上海格林曼环境技术有限公司 | Method for repairing soil groundwater by adopting double-fluid injection integrated system |
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| CN112246857A (en) * | 2020-09-29 | 2021-01-22 | 徐州徐工环境技术有限公司 | Soil normal position injection is restoreed and smell restraines integrated device |
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| CN113414229A (en) * | 2021-06-18 | 2021-09-21 | 上海格林曼环境技术有限公司 | Method for repairing soil groundwater by adopting double-fluid injection integrated system |
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Application publication date: 20171103 |