CN105923843B - A kind of organic pollutant removal system and organic pollutant removal method - Google Patents
A kind of organic pollutant removal system and organic pollutant removal method Download PDFInfo
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- CN105923843B CN105923843B CN201610471762.9A CN201610471762A CN105923843B CN 105923843 B CN105923843 B CN 105923843B CN 201610471762 A CN201610471762 A CN 201610471762A CN 105923843 B CN105923843 B CN 105923843B
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- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 80
- 238000010828 elution Methods 0.000 claims abstract description 61
- 238000001179 sorption measurement Methods 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 239000003480 eluent Substances 0.000 claims abstract description 42
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 238000004062 sedimentation Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims description 44
- 238000003860 storage Methods 0.000 claims description 21
- 230000004087 circulation Effects 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000008676 import Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 14
- 239000000356 contaminant Substances 0.000 abstract description 13
- 239000002689 soil Substances 0.000 abstract description 13
- 239000010802 sludge Substances 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000002101 lytic effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 45
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 37
- 229940124530 sulfonamide Drugs 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000015556 catabolic process Effects 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- BZTYNSQSZHARAZ-UHFFFAOYSA-N 2,4-dichloro-1-(4-chlorophenyl)benzene Chemical compound C1=CC(Cl)=CC=C1C1=CC=C(Cl)C=C1Cl BZTYNSQSZHARAZ-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 4
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000013517 stratification Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 acetonitrile sulfanilamide Chemical compound 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000003802 soil pollutant Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
A kind of organic pollutant removal system and organic pollutant removal method, which is characterized in that including pollution organic pollution container, stirring pool, sedimentation basin, molecular engram elution adsorption column, elution agent container, degradation reaction pond.Organic pollutant removal system of the present invention, it first passes through stirring pool the organic pollution in solid contaminant is dissolved in lytic agent, then after being precipitated by sedimentation basin, solution containing organic pollution is crossed into molecular engram elution adsorption column and is oriented recycling elution, removes the organic pollution in solid contaminant；And the organic pollution elution being adsorbed in elution adsorption column is enriched in degradation reaction pond by eluant, eluent by molecular engram elution column again, is quickly and effectively degraded to organic pollution finally by Ozone oxidation method.The present invention both can be oriented removal organic polluter to solid contaminants such as soil, farm animal excrement and sludge, it can also be used to be oriented enrichment processing to the organic pollution in pollutant effluents, improve removal efficiency.
Description
Technical field
The present invention relates to organic contamination in environmental technology field more particularly to a kind of soil, farm animal excrement and sludge
Object orientation, cycle removal system and organic pollutant removal method.
Background technology
With the development of livestock and poultry breeding industry, along with a large amount of uses of antibiotic, the antibiotic active compound that is not absorbed and used
The waste water and sludge in the water body in nature, bed mud and soil and sewage treatment plant can be entered by farm animal excrement
There are various antibiotic, the report that environment is polluted about antibiotic is more and more, although some antibiotic pollutant concentrations
It is low, but it still can constitute potential ecological threat to aquatile and terrestrial organism.For antibiotic pollution sources and the ring of generation
Border pollution problem, there is presently no targetedly effectively remove system and method.
Polychlorinated biphenyls is one of persistence organic pollutant, is once widely used in electric power work as important chemical products
The stacking etc. in the fields such as industry, plastics industry, chemical industry and printing, pollutant causes Polychlorinated biphenyls can be discharged into environment, and generates pollution.
Polycyclic aromatic hydrocarbon can then be generated by organic compound combustion, and enter soil by dried wet deposition, generate pollution.More chlorine are joined at present
Benzene and polycyclic aromatic hydrocarbon are mainly microbial degradation or addition chemical reagent degradation, and microbial degradation efficiency is low, chemical reagent degradation
It is also easy to produce secondary pollution.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of organic pollutant removal systems and organic
Contaminant removal process.
The present invention is achieved by the following technical solutions：
A kind of organic pollutant removal system, feature are, including organic pollution container, stirring pool, precipitation
Pond, molecular engram elution adsorption column, elution agent container, degradation reaction pond；
The discharge port of the organic pollution container is connected to stirring pool, and the stirring pool is equipped with solvent filling opening, institute
It states solvent filling opening and connects a multiple-limb inlet tube, the multiple-limb inlet tube includes the first inlet tube, the second inlet tube, third
Inlet tube, each inlet tube are respectively equipped with valve and flowmeter；
The stirring pool is connected to by pipeline with sedimentation basin, and the sedimentation basin outlet is inhaled by pipeline and molecular engram elution
The inlet of attached column is connected to, and being equipped with first circulation on being connected to pipeline of the sedimentation basin with molecular engram elution adsorption column pumps；
The bottom liquid outlet of the molecular engram elution adsorption column is returned by the pipeline pumped equipped with second circulation with stirring pool
Liquid mouth is connected to；
The molecular engram elution adsorption column is additionally provided with eluant, eluent entrance and eluant, eluent outlet, and the eluant, eluent entrance passes through
Pipeline equipped with third circulating pump and eluant, eluent reservoir, the eluant, eluent container outlet is equipped with the first control valve, and passes through
Pipeline equipped with the 4th circulating pump is connected to the inlet in degradation reaction pond.
Further, the is additionally provided on the pipeline that the bottom liquid outlet of molecular engram elution adsorption column is connect with stirring pool
One storage pool.
Further, the bottom of the molecular engram elution adsorption column is additionally provided with a liquid outlet, and the liquid outlet passes through pipeline
It is connected to the second storage pool, passes through the pipeline connection equipped with the 5th circulating pump between second storage pool and degradation reaction pond.
Further, the degradation reaction pond is equipped with self-heating system, and the degradation reaction pond is equipped with volatilization mouth, the volatilization
Mouth is connected to by pipeline with condenser, and the pipeline is equipped with the second control valve, outlet and the elution agent container of the condenser
Connection.
Further, the degradation reaction pond is equipped with the pipeline being connected with third pump inlet, and the pipeline is equipped with
Third control valve.
Further, it is additionally provided with filter between the stirring pool and sedimentation basin.
Further, the system also includes an ozone generators, and the ozone generator gas outlet is by being equipped with the 4th control
The pipeline of valve processed is connected to degradation reaction pond.
A kind of solid-state organic pollutant removal method, feature are to include the following steps：
A, solid contaminant is added in stirring pool, mass volume ratio 1 is then pressed into stirring pool:5-1:10 are added dissolving
Agent is sufficiently stirred, and is then allowed to stand；
B, after stratification, stirring pool liquid outlet is opened, supernatant flows into sedimentation basin after being filtered, precipitating
It is stood again in pond；It is then turned on circulating pump one, the standing liquid injection molecular engram in sedimentation basin is eluted into adsorption column, through molecule
After trace elutes adsorption column absorption, eluent flows into storage pool one through liquid outlet one, then back flows back into stirring pool through circulating pump two
In be again stirring for the soil in stirring pool for extracting the organic pollution in solid contaminant；
C, step B closes the liquid outlet one and three of molecular engram elution adsorption column per circulation primary, opens elution agent container
Valve, by circulating pump three by eluant, eluent inject molecular engram elute adsorption column, through molecular engram elution adsorption column elution after,
Eluent solution is flowed into from the second liquid outlet in degradation reaction pond by circulating pump four；
Reaction tank is heated, heating temperature is less than 5-20 DEG C of solvent boiling point, while opening condenser, degradation reaction pond
In eluant, eluent it is heated after volatilization, flowed into eluant, eluent pond after the condensation of condensed device；
D, B and step C are repeated repeatedly until organic pollution or pollutant concentration in removal solid contaminant are up to standard；
E, the initial reaction liquid (i.e. water) stored in holding pond two is passed through circulating pump by degradation reaction pond before degradation reaction
Four are pumped into reaction tank and remaining eluent (eluent in degradation reaction pond：Reaction solution volume ratio≤1%) mixing, close with
All valves of degradation reaction pond connection, are then turned on ozone generator, and it is anti-that the ozone that ozone generator generates is passed through degradation
In the solution of Ying Chi, pressurization closed reacts 1-3 hours；
F, after the solution degradation in degradation reaction pond is up to standard to organic pollution, elution agent container lower valve is closed,
Open the circulation pump three, by reaction solution through molecular blotting column, the liquid outlet three that adsorption column is eluted by molecular engram goes to storage pool
It is stored in two, waiting carries out degradation reaction again.
The solid contaminant is the soil containing organic pollution, farm animal excrement or sludge.
A kind of liquid organic pollutant removal method, feature are to include the following steps：
A, sedimentation basin is flowed into after being filtered the sewage containing organic pollution, when standing one section in sedimentation basin
Between；It is then turned on circulating pump one, the standing liquid injection molecular engram in sedimentation basin is eluted into adsorption column, elutes and inhales through molecular engram
After attached column elution, eluent flows into storage pool one once liquid outlet, then refills molecular engram through circulating pump and elute adsorption column；
B, step A closes the liquid outlet one and three of molecular engram elution adsorption column per circulation primary, opens elution agent container
Valve, by circulating pump three by eluant, eluent inject molecular engram elute adsorption column, through molecular engram elution adsorption column elution after,
Eluent solution is flowed into from the second liquid outlet in degradation reaction pond by circulating pump four；
Reaction tank is heated, heating temperature is less than 5-20 DEG C of solvent boiling point, while opening condenser, degradation reaction pond
In eluant, eluent it is heated after volatilization, flowed into eluant, eluent pond after the condensation of condensed device；
C, repeating A and step B, repeatedly secondary organic pollution or concentration up in removal solution is up to standard；
D, the initial reaction liquid (i.e. water) stored in holding pond two is passed through circulating pump by degradation reaction pond before degradation reaction
Four are pumped into reaction tank and remaining eluent (eluent in degradation reaction pond：Reaction solution volume ratio≤1%) mixing, close with
All valves of degradation reaction pond connection, are then turned on ozone generator, and it is anti-that the ozone that ozone generator generates is passed through degradation
In the solution of Ying Chi, pressurization closed reacts 1-3 hours；
E, after the solution degradation in degradation reaction pond is up to standard to organic pollution, elution agent container lower valve is closed,
Open the circulation pump three, by reaction solution through molecular blotting column, the liquid outlet three that adsorption column is eluted by molecular engram goes to storage pool
It is stored in two, waiting carries out degradation reaction again.
Compared with prior art, a kind of organic pollutant removal system provided by the invention has the beneficial effect that：
A kind of organic pollutant removal system provided by the invention and minimizing technology, first pass through stirring pool by solid contaminant
In organic pollution be dissolved in lytic agent, it is after then being precipitated by sedimentation basin, the solution containing organic pollution is excessive
Sub- trace elution adsorption column is oriented recycling elution, removes the organic pollution in solid contaminant；And molecular engram elutes
The organic pollution elution being adsorbed in elution column is enriched in degradation reaction pond by eluant, eluent by adsorption column again, finally by
Ozone oxidation method quickly and effectively degrades to organic pollution.
Present system both can be oriented removal to solid contaminants such as soil, farm animal excrement and sludge to be had
Machine pollutant, it can also be used to enrichment processing is oriented to the organic pollution in pollutant effluents, improve removal efficiency.
Description of the drawings
Fig. 1 is schematic structural view of the invention.
Fig. 2 is multiple-limb inlet tube structural schematic diagram of the present invention.
Fig. 3 is the influence that different solvents compare sulfanilamide (SN) degradation.
Fig. 4 is influences of the different pH to sulfanilamide (SN) degradation effect.
Figure label：1 organic pollution container, 2 stirring pools, 20 multiple-limb inlet tubes, 201 first inlet tubes,
202 second inlet tubes, 203 third inlet tubes, 3 sedimentation basins, 4 molecular engrams elution adsorption column, 5 elution agent containers, 6 degradations it is anti-
Ying Chi, 71 first control valves, 72 second control valves, 73 third control valves, 74 the 4th control valves, 81 first circulations pump, 82 second
Circulating pump, 83 third circulating pumps, 84 the 4th circulating pumps, 85 the 5th circulating pumps, 9 contaminant filters, 10 condensers, 11 first storages
Deposit pond, 12 second storage pools, 13 ozone generators.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
As shown in Figure 1, a kind of organic pollutant removal system, including organic pollution container 1, stirring pool 2, precipitation
Pond 3, molecular engram elution adsorption column 4, elution agent container 5, degradation reaction pond 6, ozone generator 13, first circulation pump (including
First circulation pump 81, second circulation pump 82, third circulating pump 83, the 4th circulating pump 84, the 5th circulating pump 85.
Wherein, the discharge port of organic pollution container 1 is connected to stirring pool 2, and stirring pool 2 is equipped with solvent filling opening, molten
Agent filling opening connect a multiple-limb inlet tube 20, the multiple-limb inlet tube be equipped with the first inlet tube 201, the second inlet tube 202,
Third inlet tube 203 etc., each inlet tube are respectively equipped with valve and flowmeter.
Blender is equipped in stirring pool 2, stirring pool is connected to by pipeline with sedimentation basin, and is preferably set from the pipeline of connection
A contaminant filter 9 is set, the inlet that the outlet of sedimentation basin 3 elutes adsorption column 4 by pipeline with molecular engram is connected to, heavy in connection
The pipeline of shallow lake pond and molecular engram elution adsorption column is equipped with first circulation and pumps 81.
The bottom liquid outlet of molecular engram elution adsorption column 4 is returned by the pipeline equipped with second circulation pump 82 with stirring pool 2
Liquid mouth is connected to.
Molecular engram elution adsorption column 4 is additionally provided with eluant, eluent entrance and eluant, eluent outlet, and eluant, eluent entrance is by being equipped with the
The pipeline of three circulating pumps 83 be connected to elution agent container 5, and eluant, eluent container outlet is equipped with the first control valve 71, and by being equipped with the
The pipeline of four circulating pumps 84 is connected to the inlet in degradation reaction pond 6.It elutes agent container 5 and is equipped with observation panel.
Further, the first storage is additionally provided on the pipeline that the bottom liquid outlet of molecular engram elution adsorption column is connect with stirring pool
Deposit pond 11.
Further, the bottom of molecular engram elution adsorption column is additionally provided with a liquid outlet, and the liquid outlet passes through pipeline and the
Two storage pools 12 are connected to, and pass through the pipeline connection equipped with the 5th circulating pump 85 between second storage pool and degradation reaction pond.
Further, the degradation reaction pond is equipped with self-heating system, and the degradation reaction pond is equipped with volatilization mouth, the volatilization
Mouthful be connected to condenser 10 by band valve pipeline, the pipeline equipped with the second control valve 72, the outlet of the condenser with wash
De- agent container connection.
Further, degradation reaction pond 6 is equipped with the pipeline that is connected with 83 import of third circulating pump, and the pipeline is equipped with the
Three control valves 73.It, also can be only with being reacted in storage pool two when the pollutant of present invention orientation removal is hydrophily pollutant
Liquid carries out recycling elution.
Further, present system further includes an ozone generator 13, and 13 gas outlet of ozone generator is by being equipped with the 4th
The pipeline of control valve 74 is connected to degradation reaction pond 6.
Above system of the present invention can both handle the dirt of the solid-states such as the soil containing organic pollution, farm animal excrement and sludge
Object is contaminated, the liquid waste water containing organic pollution can also be handled, it is right below for removing the pollutant in soil and sludge
The processing method of present system provides further detailed protocol.
Embodiment 1
One, prepared by sulfanilamide (SN) molecularly imprinted polymer
It is dissolved in the solution that a concentration of 0.1M/L is made in acetonitrile by template molecule of sulfanilamide (SN), function monomer 2- vinyl is added
Pyridine (2-VP) makes composite template molecule fully be combined with function monomer at room temperature in sonic oscillation 45min；Then it is added
Crosslinking agent ethylene glycol dimethacrylate (EDMA)；It adds azodiisobutyronitrile (AIBN) to be uniformly mixed, sonic oscillation
30min, in N2It protects in underlying 60 DEG C of water-baths and heats 16h, obtain solid white polymer；Its template molecule：Function monomer：It hands over
Join agent：The molar ratio of initiator is 1:5:25:1.The solid white polymer of gained crushes, and crosses 200-250 mesh after grinding simultaneously
Sieve, be eluant, eluent with acetonitrile, the template molecule in eluted polymer, then be washed with deionized water it is de-, collect product 60 in baking oven
DEG C drying, it is spare.
Two, different solvents compare the influence experiment of sulfanilamide (SN) degradation
Compound concentration 100.0mg/L sulfanilamide (SN) solution, distilled water is settled to after taking 1.0mL additions 0,1,3mL acetonitriles respectively
100mL is obtained and is contained 1%, 2% and 4% acetonitrile sulfanilamide (SN) solution, and using ozone degradation, ozone flow is 10mL/min, and ozone occurs
Device yield of ozone is 30g/h, and degrade 1h under room temperature normal pressure, as a result sees that Fig. 3, sulfanilamide (SN) degradation rate are respectively 82.56%, 77.26%
With 59.3%.Illustrate to reduce as organic solvent content increases degradation effect.
Three, influences of the difference pH to sulfanilamide (SN) degradation effect
Compound concentration 100.0mg/L sulfanilamide (SN) solution takes 1.0mL that different pH (pH=1,3,5,7,9,11, pH are added respectively
Adjusted using 0.1M sodium hydroxides and hydrochloric acid) distilled water be settled to 100mL, degraded at room temperature 30min using above-mentioned condition, knot
Fruit sees Fig. 4.Sulfanilamide (SN) degradation effect alkaline condition is better than acid condition, and degradation rate is 86.5% under the conditions of pH=11.0.
Three, the minimizing technology of the sludge pollution object containing sulfanilamide (SN), includes the following steps：
A, the sludge (dry weight, sulfanilamide (SN) content be 100mg/kg) polluted 200g sulfanilamide (SN) is added in stirring pool, then to stirring
Mix addition 1L citric acids methanol solution (0.1M/L aqueous citric acid solutions and methanol volume ratio 1 in pond:1 mixing), impregnate 1h, stirring
After 30min, 30min is stood；
B, after stratification, stirring pool liquid outlet is opened, supernatant flows into sedimentation basin after being filtered, precipitating
30min is stood in pond again；It is then turned on circulating pump one, by the standing liquid stream in sedimentation basin through sulfanilamide (SN) molecular blotting column, is stood
Liquid through molecular blotting column liquid outlet one flow into storage pool, then through circulating pump two back flow back into stirring pool with the sludge in stirring pool
It is again stirring for for extracting the organic pollution in Contaminated Sewage Sludge；
In mass ratio 1 in above-mentioned sulfanilamide (SN) molecular blotting column:5 are filled with sulfanilamide (SN) molecularly imprinted polymer and bead；
C, step B closes the liquid outlet one of molecular engram elution adsorption column, opens the valve of elution agent container per circulation primary
Eluant, eluent (eluant, eluent is the pure acetonitrile solutions of 100mL) injection molecular engram is eluted adsorption column by door by circulating pump three, and elution is molten
The second liquid outlet that liquid elutes adsorption column from molecular engram flows into degradation reaction pond；
Reaction tank is heated, until solution temperature reaches 65 DEG C, while opening condenser, the elution in degradation reaction pond
Volatilization after agent is heated flows into after condensed device condensation in eluant, eluent pond；
D, B and step C 2 times are repeated, the organic pollution content through surveying in sludge is 8.5mg/kg；
E, the initial reaction liquid (i.e. water) stored in holding pond two is passed through circulating pump by degradation reaction pond before degradation reaction
Four are pumped into reaction tank and remaining eluent (eluent in degradation reaction pond：Reaction solution volume ratio≤1% makes the body of acetonitrile
Product concentration accounts for 1% or less entire reaction solution volume) mixing, and the pH=11.0 of reaction solution is adjusted, it closes and connects with degradation reaction pond
Logical all valves, are then turned on ozone generator, and the ozone that ozone generator generates is passed through in the solution in degradation reaction pond,
Confined reaction 1.0 hours under pressurization 0.1MPa；The ratio of ozone intake and degraded solutions is 0.1g/L；Before surveying reaction
Solution sulfanilamide (SN) content is 34.5mg/L, and the sulfanilamide (SN) content after degradation reaction is 0.1mg/L.
F, after the solution degradation in degradation reaction pond is up to standard to organic pollution, elution agent container lower valve is closed,
Open the circulation pump three, by reaction solution through molecular blotting column, the liquid outlet three that adsorption column is eluted by molecular engram goes to storage pool
Storage in two, waiting carry out degradation reaction again.
Embodiment 2
One, biphenyl class molecularly imprinted polymer preparation method is as follows：
It is dissolved in the solution that a concentration of 0.1M/L is made in acetonitrile as template molecule using biphenyl or PCBs, function monomer α-is added
Methacrylic acid (MAA) makes composite template molecule fully be combined with function monomer at room temperature in sonic oscillation 45min；Then
Crosslinking agent ethylene glycol dimethacrylate (EDMA) is added；It adds azodiisobutyronitrile (AIBN) to be uniformly mixed, ultrasound is shaken
30min is swung, in N2It protects in underlying 60 DEG C of water-baths and heats 16h, obtain solid white polymer；Its template molecule：Function monomer：
Crosslinking agent：The molar ratio of initiator is 1:5:40:1.The solid white polymer of gained crushes, and crosses 200-250 after grinding simultaneously
Mesh sieves, and is eluant, eluent with n-hexane, the template molecule in eluted polymer, then is eluted successively with acetone and deionized water, collects
Product 60 DEG C of dryings in baking oven, it is spare.
Two, a kind of minimizing technology of the soil pollutant containing Polychlorinated biphenyls, includes the following steps：
A, the soil of 200g pollution by polychlorinated biphenyles (PCB28 contents be 100mg/kg) is added in stirring pool, then to stirring
Mix addition 2L citric acids acetone soln (0.1M/L aqueous citric acid solutions and acetone volume ratio 1 in pond:1 mixing), 1.5h is impregnated, is stirred
After mixing 30min, 30min is stood；
B, after stratification, stirring pool liquid outlet is opened, supernatant flows into sedimentation basin after being filtered, precipitating
30min is stood in pond again；It is then turned on circulating pump, by the standing liquid stream in sedimentation basin through biphenyl class molecular blotting column, is stood
Liquid flows into storage pool through molecular blotting column liquid outlet one, then is back flowed back into stirring pool with the soil in stirring pool again through circulating pump
Secondary stirring is for extracting the organic pollution in contaminated soil；
In mass ratio 1 in above-mentioned biphenyl class molecular blotting column:5 are filled with biphenyl class molecularly imprinted polymer and bead；
C, step B closes the liquid outlet one of molecular engram elution adsorption column, opens the valve of elution agent container per circulation primary
Eluant, eluent (eluant, eluent be pure acetone solution) injection molecular engram is eluted adsorption column by door by circulating pump three, elution solution from
The second liquid outlet that molecular engram elutes adsorption column flows into degradation reaction pond；
Reaction tank is heated, until solution temperature reaches 45 DEG C, while opening condenser, the elution in degradation reaction pond
Volatilization after agent is heated flows into after condensed device condensation in eluant, eluent pond；
D, B and step C 3 times are repeated, the organic pollution PCB28 contents through surveying in soil are 6.9mg/kg；
E, the initial reaction liquid (i.e. water) stored in holding pond two is passed through circulating pump by degradation reaction pond before degradation reaction
Four are pumped into reaction tank and remaining eluent (eluent in degradation reaction pond：Reaction solution volume ratio≤1% makes the body of acetone
Product concentration accounts for 1% or less entire reaction solution volume) mixing, and the pH=11.0 of reaction solution is adjusted, it closes and connects with degradation reaction pond
Logical all valves, are then turned on ozone generator, and the ozone that ozone generator generates is passed through in the solution in degradation reaction pond,
Confined reaction 3.0 hours under pressurization 0.5MPa；The ratio of ozone intake and degraded solutions is 0.1g/L；Before surveying reaction
Solution PCB28 contents are 37.1mg/L, and the PCB28 contents after degradation reaction are 2.1mg/L.
F, after the solution degradation in degradation reaction pond is up to standard to organic pollution, elution agent container lower valve is closed,
Open the circulation pump three, by reaction solution through molecular blotting column, the liquid outlet three that adsorption column is eluted by molecular engram goes to storage pool
Storage in two, waiting carry out degradation reaction again.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.
Claims (5)
1. a kind of organic pollutant removal system, which is characterized in that including pollution organic pollution container (1), stirring pool
(2), sedimentation basin (3), molecular engram elution adsorption column (4), elution agent container (5), degradation reaction pond (6)；
The discharge port connection stirring pool (2) of the organic pollution container (1), the stirring pool (2) are equipped with solvent liquid feeding
Mouthful, the solvent filling opening connects a multiple-limb inlet tube (20), the multiple-limb inlet tube include the first inlet tube (201),
Second inlet tube (202), third inlet tube (203), each inlet tube are respectively equipped with valve and flowmeter；
The stirring pool (2) is connected to by pipeline with sedimentation basin (3), and sedimentation basin (3) outlet passes through pipeline and molecular engram
The inlet connection for eluting adsorption column (4), on being connected to pipeline of the sedimentation basin (3) with molecular engram elution adsorption column (4)
(81) are pumped equipped with first circulation；
The bottom liquid outlet of the molecular engram elution adsorption column (4) pumps the pipeline and stirring pool of (82) by being equipped with second circulation
(2) liquid return hole is connected to；
The molecular engram elution adsorption column (4) is additionally provided with eluant, eluent entrance and eluant, eluent outlet, and the eluant, eluent entrance passes through
Pipeline equipped with third circulating pump (83) is connected to elution agent container (5), and the eluant, eluent container outlet is equipped with the first control valve
(71), the eluant, eluent outlet is connected to by being equipped with the pipeline of the 4th circulating pump (84) with the inlet of degradation reaction pond (6)；
It is additionally provided with the first storage on the pipeline that the bottom liquid outlet of the molecular engram elution adsorption column (4) is connect with stirring pool (2)
Deposit pond (11)；
The bottom of the molecular engram elution adsorption column (4) is additionally provided with a liquid outlet, and the liquid outlet is store by pipeline and second
Pond (12) connection is deposited, by being equipped with the pipe of the 5th circulating pump (85) between second storage pool (12) and degradation reaction pond (6)
Road is connected to.
2. a kind of organic pollutant removal system according to claim 1, which is characterized in that the degradation reaction pond (6)
Equipped with self-heating system, the degradation reaction pond (6) is equipped with volatilization mouth, and the volatilization mouth is connected by pipeline and condenser (10)
Logical, the pipeline is equipped with the second control valve (72)；The outlet of the condenser (10) is connected to elution agent container (5).
3. a kind of organic pollutant removal system according to claim 1, which is characterized in that the degradation reaction pond (6)
Equipped with the pipeline being connected with third circulating pump (83) import, the pipeline is equipped with third control valve (73).
4. a kind of organic pollutant removal system according to claim 1, which is characterized in that the stirring pool and sedimentation basin
Between be additionally provided with filter.
5. a kind of organic pollutant removal system according to claim 1, which is characterized in that smelly the system also includes one
Oxygen Generator (13), ozone generator (13) gas outlet is by being equipped with the pipeline of the 4th control valve (74) and degradation reaction pond
(6) it is connected to.
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| CN201610471762.9A CN105923843B (en) | 2016-06-23 | 2016-06-23 | A kind of organic pollutant removal system and organic pollutant removal method |
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| CN110080702B (en) * | 2019-05-21 | 2021-04-09 | 成都西南石大石油工程技术有限公司 | Compound solvent for vibrating screen slurry leakage while-drilling treatment and treatment device |
| CN111151570A (en) * | 2020-02-11 | 2020-05-15 | 南京怡可帮生态环境科技有限公司 | Development and application of rapid and efficient in-situ circulating repair system for organic pollution active oxygen of field soil and underground water |
| CN113501616B (en) * | 2021-09-10 | 2021-11-19 | 北京乾合晶芯电子技术有限公司 | Organic sewage treatment equipment and method |
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| CN105923843A (en) | 2016-09-07 |
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Effective date of registration: 20200716 Address after: 250101 1711, unit 1, building 3, Longao North Road, Jinan area, China (Shandong) pilot Free Trade Zone, Jinan City, Shandong Province Patentee after: Shandong green vision Environmental Protection Engineering Co.,Ltd. Address before: 230036 No. 130 Changjiang West Road, Shushan District, Anhui, Hefei Patentee before: Anhui Agricultural University |