CN105923843A - Organic pollutant removal system and organic pollutant removal method - Google Patents
Organic pollutant removal system and organic pollutant removal method Download PDFInfo
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- CN105923843A CN105923843A CN201610471762.9A CN201610471762A CN105923843A CN 105923843 A CN105923843 A CN 105923843A CN 201610471762 A CN201610471762 A CN 201610471762A CN 105923843 A CN105923843 A CN 105923843A
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- degradation reaction
- adsorption column
- eluting
- molecular engram
- pond
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- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000002689 soil Substances 0.000 claims abstract description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 14
- 231100000719 pollutant Toxicity 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 claims description 89
- 239000007788 liquid Substances 0.000 claims description 59
- 238000003860 storage Methods 0.000 claims description 32
- 238000004062 sedimentation Methods 0.000 claims description 28
- 239000003480 eluent Substances 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 17
- 230000015556 catabolic process Effects 0.000 claims description 14
- 239000000356 contaminant Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000013517 stratification Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 2
- 239000006166 lysate Substances 0.000 claims 1
- 238000010828 elution Methods 0.000 abstract description 5
- 244000144972 livestock Species 0.000 abstract description 2
- 244000144977 poultry Species 0.000 abstract description 2
- 239000010802 sludge Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 18
- 229940124530 sulfonamide Drugs 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000004305 biphenyl 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
- 239000003431 cross linking reagent Substances 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
- 230000010355 oscillation Effects 0.000 description 4
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 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
- 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
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000009416 shuttering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZXWHANCSQZVZCM-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;methanol Chemical compound OC.OC(=O)CC(O)(C(O)=O)CC(O)=O ZXWHANCSQZVZCM-UHFFFAOYSA-N 0.000 description 1
- WWCDLXGTIXEJRY-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;propan-2-one Chemical compound CC(C)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O WWCDLXGTIXEJRY-UHFFFAOYSA-N 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
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction 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
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000003802 soil pollutant Substances 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
The invention relates to an organic pollutant removal system and an organic pollutant removal method. The organic pollutant removal system is characterized by comprising an organic pollutant loading container, a stirring pool, a settlement pool, a molecular imprinting elution and adsorption column, an elution agent container, and a degrading reaction pool. The organic pollutant removal system is characterized in that firstly, the organic pollutants in solid pollutants are dissolved into a dissolving agent by the stirring pool; after settling by the settlement pool, a solution containing organic pollutants is directionally and cyclically eluted by the molecular imprinting elution and adsorption column, and the organic pollutants in the solid pollutants are removed; the organic pollutants adsorbed into the molecular imprinting elution and adsorption column are enriched into the degrading reaction pool by an adsorbing agent; finally, the organic pollutants are quickly and effectively degraded by an ozone oxidizing method. The organic pollutant removal system has the advantages that the organic pollutants in the solid pollutants, such as soil, livestock and poultry excrement and sludge, are directionally removed, the organic pollutants in pollution wastewater can be directionally enriched and treated, and the removal rate is improved.
Description
Technical field
The present invention relates to environmental technology field, in particular organic pollution in a kind of soil, farm animal excrement and mud
Orientation, circulation removal system and organic pollutant removal method.
Background technology
Along with the development of livestock and poultry breeding industry, along with a large amount of uses of antibiotic, the former medicine of antibiotic not being absorbed and used can
To be entered the waste water in water body, bed mud and the soil, and sewage treatment plant in nature and mud by farm animal excrement
All there is various antibiotic, the report being related to antibiotic pollution environment gets more and more, although some antibiotic pollutant is dense
Spend low, but it still can constitute potential ecological threat to aquatile and terrestrial organism.For antibiotic polluter and generation
Problem of environmental pollution, there is presently no and the most effectively remove system and method.
Polychlorinated biphenyls is one of persistence organic pollutant, chemical products important for Zeng Zuowei be widely used in power industry,
The fields such as plastics industry, chemical industry and printing, the stacking of pollutant etc. causes Polychlorinated biphenyls to be discharged in environment, produces and pollutes.
Polycyclic aromatic hydrocarbon then can be produced by organic compound combustion, and enters soil by dried wet deposition, produces and pollutes.At present to many
Chlordiphenyl and polycyclic aromatic hydrocarbon are mainly microbial degradation or add chemical reagent degraded, and microbial degradation efficiency is low, chemistry examination
Agent degraded is easily generated secondary pollution.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of organic pollutant removal system and organic dirt
Dye thing minimizing technology.
The present invention is achieved by the following technical solutions:
A kind of organic pollutant removal system, its feature is, includes organic pollutants container, stirring pool, precipitation
Pond, molecular engram eluting adsorption column, eluant container, degradation reaction pond；
The discharging opening connection stirring pool of described organic pollution container, described stirring pool is provided with solvent filling opening, described
Solvent filling opening connects a multiple-limb feed tube, described multiple-limb feed tube include the first feed tube, the second feed tube,
Three feed tubes, each feed tube is respectively equipped with valve and effusion meter；
Described stirring pool is connected with sedimentation tank by pipeline, and the outlet of described sedimentation tank is adsorbed with molecular engram eluting by pipeline
The inlet connection of post, is provided with the first circulating pump connecting on the described sedimentation tank pipeline with molecular engram eluting adsorption column；
The bottom liquid outlet of described molecular engram eluting adsorption column returns liquid by being provided with the pipeline of the second circulating pump with stirring pool
Mouth connection；
Described molecular engram eluting adsorption column is additionally provided with eluant entrance and eluant outlet, and described eluant entrance is by setting
Having pipeline and the eluant reservoir of the 3rd circulating pump, described eluant container outlet is provided with the first control valve, and passes through
The inlet of the pipeline and degradation reaction pond that are provided with the 4th circulating pump connects.
Further, the pipeline that the bottom liquid outlet of described molecular engram eluting adsorption column is connected with stirring pool is additionally provided with first
Storage pool.
Further, the bottom of described molecular engram eluting adsorption column is additionally provided with a liquid outlet, described liquid outlet by pipeline with
Second storage pool connection, by being provided with the pipeline connection of the 5th circulating pump between described second storage pool and degradation reaction pond.
Further, described degradation reaction pond is provided with self-heating system, and described degradation reaction pond is provided with volatilization mouth, described volatilization
Mouth is connected with condenser by pipeline, and described pipeline is provided with the second control valve, and the outlet of described condenser is held with eluant
Device connects.
Further, described degradation reaction pond is provided with the pipeline being connected with the 3rd pump inlet, and described pipeline is provided with
Three control valves.
Further, it is additionally provided with filter between described stirring pool and sedimentation tank.
Further, described system also includes an ozonator, and described ozonator gas outlet is by being provided with the 4th control
The pipeline of valve connects with degradation reaction pond.
A kind of solid-state organic pollutant removal method, its feature is to comprise the steps:
A, solid contaminant is added in stirring pool, in stirring pool, then press mass volume ratio 1:5-1:10 add and dissolve
Agent, is sufficiently stirred for, and then stands；
B, after stratification, open stirring pool liquid outlet, supernatant flows into sedimentation tank after being filtered, heavy
Shallow lake stands in pond again；It is then turned on circulating pump one, the standing liquid in sedimentation tank is injected molecular engram eluting adsorption column,
After molecular engram eluting adsorption column adsorbs, eluent flows into storage pool one through liquid outlet one, more again flows through circulating pump two
Enter in stirring pool and be again stirring for the organic pollution for extracting in solid contaminant with the soil in stirring pool；
The every circulation primary of C, step B, closes the liquid outlet one and three of molecular engram eluting adsorption column, opens eluant and holds
The valve of device, injects molecular engram eluting adsorption column by circulating pump three by eluant, washes through molecular engram eluting adsorption column
After Tuo, eluent solution, by circulating pump four, flows into degradation reaction pond from the second liquid outlet；
Heating reaction tank, heating-up temperature is less than solvent boiling point 5-20 DEG C, simultaneously open cold condenser, degradation reaction
The heated rear volatilization of eluant in pond, flows in eluant pond after the condensation of condensed device；
D, repetition B and step C are repeatedly until the organic pollution removed in solid contaminant or pollutant levels are up to standard；
E, degradation reaction pond are before degradation reaction, by the primary response liquid (i.e. water) of storage in holding pond two by circulation
Pump four pumps in reaction tank and mixes with remaining eluent in degradation reaction pond (eluent: reactant liquor volume ratio≤1%),
Close all valves connected with degradation reaction pond, be then turned on ozonator, the ozone that ozonator produces is led to
Entering in the solution in degradation reaction pond, pressurization closed reacts 1-3 hour；
F, after the solution degradation in degradation reaction pond to organic pollution is up to standard, close eluant container lower valve,
ON cycle pump three, by reactant liquor through molecular blotting column, goes to storage by the liquid outlet three of molecular engram eluting adsorption column
Chi Erzhong stores, and waits and again carries out degradation reaction.
Described solid contaminant is the soil containing organic pollution, farm animal excrement or mud.
A kind of liquid organic pollutant removal method, its feature is to comprise the steps:
A, the sewage containing organic pollution is filtered after flow into sedimentation tank, in sedimentation tank stand one section time
Between；It is then turned on circulating pump one, the standing liquid in sedimentation tank is injected molecular engram eluting adsorption column, washes through molecular engram
After desorption attached column eluting, eluent flows into storage pool one once liquid outlet, then refills molecular engram eluting through circulating pump
Adsorption column；
The every circulation primary of B, step A, closes the liquid outlet one and three of molecular engram eluting adsorption column, opens eluant and holds
The valve of device, injects molecular engram eluting adsorption column by circulating pump three by eluant, washes through molecular engram eluting adsorption column
After Tuo, eluent solution, by circulating pump four, flows into degradation reaction pond from the second liquid outlet；
Heating reaction tank, heating-up temperature is less than solvent boiling point 5-20 DEG C, simultaneously open cold condenser, degradation reaction
The heated rear volatilization of eluant in pond, flows in eluant pond after the condensation of condensed device；
C, repetition A and step B are the most secondary until organic pollution or the concentration removed in solution are up to standard；
D, degradation reaction pond are before degradation reaction, by the primary response liquid (i.e. water) of storage in holding pond two by circulation
Pump four pumps in reaction tank and mixes with remaining eluent in degradation reaction pond (eluent: reactant liquor volume ratio≤1%),
Close all valves connected with degradation reaction pond, be then turned on ozonator, the ozone that ozonator produces is led to
Entering in the solution in degradation reaction pond, pressurization closed reacts 1-3 hour；
E, after the solution degradation in degradation reaction pond to organic pollution is up to standard, close eluant container lower valve,
ON cycle pump three, by reactant liquor through molecular blotting column, goes to storage by the liquid outlet three of molecular engram eluting adsorption column
Chi Erzhong stores, and waits and again carries out degradation reaction.
Compared to existing technology, a kind of organic pollutant removal system that the present invention provides has the beneficial effect that:
A kind of organic pollutant removal system of present invention offer and minimizing technology, first pass through stirring pool by solid contaminant
Organic pollution be dissolved in lytic agent, after then being precipitated by sedimentation tank, by undue for the solution containing organic pollution
Sub-trace eluting adsorption column is oriented recycling elution, removes the organic pollution in solid contaminant；And molecular engram is washed
The organic pollution eluting adsorbed in eluting post is enriched in degradation reaction pond, finally by desorption attached column again by eluant
By Ozone oxidation method, organic pollution is the most effectively degraded.
It is organic that present system both can be oriented removal to the such as solid contaminant such as soil, farm animal excrement and mud
Pollutant, it can also be used to the organic pollution in pollutant effluents is oriented enrichment and processes, improve removal efficiency.
Accompanying drawing explanation
Fig. 1 is present configuration schematic diagram.
Fig. 2 is multiple-limb feed tube structural representation of the present invention.
Fig. 3 is the impact of different solvents comparison sulfanilamide degraded.
Fig. 4 is the different pH impacts on sulfanilamide degradation effect.
Label in figure: 1 organic pollution container, 2 stirring pools, 20 multiple-limb feed tubes, 201 first feed tubes,
202 second feed tubes, 203 the 3rd feed tubes, 204 valves, 205 effusion meters, 3 sedimentation tanks, 4 molecular engram eluting are inhaled
Attached column, 5 eluant containers, 6 degradation reaction ponds, 71 first control valves, 72 second control valves, 73 the 3rd control valves,
74 the 4th control valves, 81 first circulating pumps, 82 second circulating pumps, 83 the 3rd circulating pumps, 84 the 4th circulating pumps, 85
5th circulating pump, 9 contaminant filter, 10 condensers, 11 first storage pools, 12 second storage pools, 13 ozone occur
Device.
Detailed description of the invention
Elaborating embodiments of the invention below, the present embodiment carries out reality under premised on technical solution of the present invention
Execute, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following enforcement
Example.
As it is shown in figure 1, a kind of organic pollutant removal system, include organic pollutants container 1, stirring pool 2,
Sedimentation tank 3, molecular engram eluting adsorption column 4, eluant container 5, degradation reaction pond 6, ozonator 13,
One circulating pump (includes first circulating pump the 81, second circulating pump the 82, the 3rd circulating pump the 83, the 4th circulating pump the 84, the 5th
Circulating pump 85.
Wherein, the discharging opening connection stirring pool 2 of organic pollution container 1, stirring pool 2 is provided with solvent filling opening,
Solvent filling opening connects a multiple-limb feed tube 20, and this multiple-limb feed tube is provided with first feed tube the 201, second feed tube
202, the 3rd feed tubes 203 etc., each feed tube is respectively equipped with valve 204 and effusion meter 205.
Being provided with agitator in stirring pool 2, stirring pool is connected with sedimentation tank by pipeline, and preferably sets on the pipeline of connection
Putting a contaminant filter 9, sedimentation tank 3 is exported and is connected by the inlet of pipeline with molecular engram eluting adsorption column 4,
Connection sedimentation tank is provided with the first circulating pump 81 with the pipeline of molecular engram eluting adsorption column.
The bottom liquid outlet of molecular engram eluting adsorption column 4 is by being provided with the pipeline of the second circulating pump 82 and stirring pool 2 times
Liquid mouth connects.
Molecular engram eluting adsorption column 4 is additionally provided with eluant entrance and eluant outlet, and eluant entrance is by being provided with the 3rd
The pipeline of circulating pump 83 connects with eluant container 5, and eluant container outlet is provided with the first control valve 71, and by setting
The pipeline of the 4th circulating pump 84 is had to connect with the inlet in degradation reaction pond 6.Eluant container 5 is provided with observation panel.
Further, the pipeline that the bottom liquid outlet of molecular engram eluting adsorption column is connected with stirring pool is additionally provided with the first storage
Pond 11.
Further, the bottom of molecular engram eluting adsorption column is additionally provided with a liquid outlet, and described liquid outlet passes through pipeline and second
Storage pool 12 connects, by being provided with the pipeline connection of the 5th circulating pump 85 between described second storage pool and degradation reaction pond.
Further, described degradation reaction pond is provided with self-heating system, and described degradation reaction pond is provided with volatilization mouth, described volatilization
Mouth is connected with condenser 10 by band valve pipeline, and described pipeline is provided with the second control valve 72, the outlet of described condenser
With eluant reservoir.
Further, degradation reaction pond 6 is provided with the pipeline being connected with the 3rd circulating pump 83 import, and described pipeline is provided with
3rd control valve 73.When the pollutant that the present invention orients removal are hydrophilic pollutant, it is possible to only with storage pool two
Middle reactant liquor is circulated eluting.
Further, present system also includes an ozonator 13, and ozonator 13 gas outlet is by being provided with the 4th
The pipeline of control valve 74 connects with degradation reaction pond 6.
Said system of the present invention both can process the solid-states such as soil, farm animal excrement and the mud containing organic pollution and pollute
Thing, it is also possible to process the liquid waste water containing organic pollution, below as a example by removing the pollutant in soil and mud,
The processing method of present system is provided further detailed protocol.
Embodiment 1
One, prepared by sulfanilamide molecularly imprinted polymer
It is dissolved in acetonitrile with sulfanilamide for template molecule and makes the concentration solution as 0.1M/L, add function monomer 2-vinyl
Pyridine (2-VP), at room temperature at sonic oscillation 45min, makes composite shuttering molecule fully be combined with function monomer；
It is subsequently adding cross-linking agent ethylene glycol dimethacrylate (EDMA)；Add azodiisobutyronitrile (AIBN) mixing all
Even, sonic oscillation 30min, at N2Protect heating 16h in underlying 60 DEG C of water-baths, obtain solid white polymer；Its
Template molecule: function monomer: cross-linking agent: the mol ratio of initiator is 1:5:25:1.The solid white polymer of gained
Pulverize, cross 200-250 mesh sieve after grinding simultaneously, be eluant with acetonitrile, the template molecule in eluted polymer, then use
Deionized water eluting, collect product in baking oven 60 DEG C be dried, standby.
Two, the impact experiment of different solvents comparison sulfanilamide degraded
Compound concentration 100.0mg/L sulfanilamide solution, take respectively 1.0mL add 0,1, distilled water constant volume after 3mL acetonitrile
To 100mL, it is thus achieved that containing 1%, 2% and 4% acetonitrile sulfanilamide solution, using ozone degradation, ozone flow is 10mL/min,
Ozonator yield of ozone is 30g/h, and degrade under room temperature normal pressure 1h, and result is shown in Fig. 3, and sulfanilamide degradation rate is respectively
82.56%, 77.26% and 59.3%.Illustrate to reduce along with organic solvent content increases degradation effect.
Three, the different pH impacts on sulfanilamide degradation effect
Compound concentration 100.0mg/L sulfanilamide solution, take respectively 1.0mL add different pH (pH=1,3,5,7,9,
11, pH use 0.1M sodium hydroxide and hydrochloric acid regulation) distilled water be settled to 100mL, use above-mentioned condition room temperature
Lower degraded 30min, result is shown in Fig. 4.Sulfanilamide degradation effect alkalescence condition is better than acid condition, and pH=11.0 condition declines
Solution rate is 86.5%.
Three, the minimizing technology of the sludge pollution thing containing sulfanilamide, comprises the steps:
A, the mud (dry weight, sulfanilamide content is 100mg/kg) polluted by 200g sulfanilamide add in stirring pool, then
1L citric acid methanol solution (0.1M/L aqueous citric acid solution and the mixing of methanol volume ratio 1:1) is added in stirring pool,
Soak 1h, after stirring 30min, stand 30min；
B, after stratification, open stirring pool liquid outlet, supernatant flows into sedimentation tank after being filtered, heavy
30min is again stood in pond, shallow lake；It is then turned on circulating pump one, by the standing liquid stream in sedimentation tank through sulfanilamide molecular blotting column,
Stand liquid and flow into storage pool through molecular blotting column liquid outlet one, then through circulating pump two back flow back in stirring pool with in stirring pool
Mud be again stirring for the organic pollution for extracting in Contaminated Sewage Sludge；
In above-mentioned sulfanilamide molecular blotting column, 1:5 in mass ratio is filled with sulfanilamide molecularly imprinted polymer and bead；
The every circulation primary of C, step B, closes the liquid outlet one of molecular engram eluting adsorption column, opens eluant container
Valve, injects molecular engram eluting by circulating pump three by eluant (eluant is the pure acetonitrile solution of 100mL) and adsorbs
Post, eluting solution flows into degradation reaction pond from the second liquid outlet of molecular engram eluting adsorption column；
Reaction tank is heated, reaches 65 DEG C to solution temperature, open cold condenser simultaneously, the eluting in degradation reaction pond
Volatilization after agent is heated, flows in eluant pond after the condensation of condensed device；
D, repeat B and step C 2 times, be 8.5mg/kg through surveying the organic pollution content in mud；
E, degradation reaction pond are before degradation reaction, by the primary response liquid (i.e. water) of storage in holding pond two by circulation
Pump four pumps in reaction tank that (eluent: reactant liquor volume ratio≤1%, makes second with remaining eluent in degradation reaction pond
The volumetric concentration of nitrile accounts for whole reactant liquor volume less than 1%) mix, and regulate the pH=11.0 of reactant liquor, close and drop
Solve all valves of reaction tank connection, be then turned on ozonator, the ozone that ozonator produces is passed through degraded anti-
In the solution of Ying Chi, confined reaction 1.0 hours under pressurization 0.1MPa；Ozone intake with the ratio of degraded solutions is
0.1g/L；Solution sulfanilamide content before measured reaction is 34.5mg/L, and the sulfanilamide content after degradation reaction is 0.1mg/L.
F, after the solution degradation in degradation reaction pond to organic pollution is up to standard, close eluant container lower valve,
ON cycle pump three, by reactant liquor through molecular blotting column, goes to storage by the liquid outlet three of molecular engram eluting adsorption column
The storage of Chi Erzhong, waits and again carries out degradation reaction.
Embodiment 2
One, biphenyl quasi-molecule imprinted polymer preparation method is as follows:
Be dissolved in acetonitrile with biphenyl or PCBs for template molecule and make the concentration solution as 0.1M/L, add function monomer α-
Methacrylic acid (MAA), at room temperature at sonic oscillation 45min, makes composite shuttering molecule fully tie with function monomer
Close；It is subsequently adding cross-linking agent ethylene glycol dimethacrylate (EDMA)；Add azodiisobutyronitrile (AIBN) to mix
Closing uniformly, sonic oscillation 30min, at N2Protect heating 16h in underlying 60 DEG C of water-baths, obtain solid white polymer；
Its template molecule: function monomer: cross-linking agent: the mol ratio of initiator is 1:5:40:1.The white solid polymerization of gained
Thing is pulverized, and crosses 200-250 mesh sieve simultaneously, be eluant with normal hexane after grinding, the template molecule in eluted polymer,
The most successively with acetone and deionized water eluting, collect product in baking oven 60 DEG C be dried, standby.
Two, the minimizing technology of a kind of soil pollutant containing Polychlorinated biphenyls, comprises the steps:
A, the soil (PCB28 content is 100mg/kg) of 200g pollution by polychlorinated biphenyles is added in stirring pool, then
2L citric acid acetone soln (0.1M/L aqueous citric acid solution and the mixing of acetone volume ratio 1:1) is added in stirring pool,
Soak 1.5h, after stirring 30min, stand 30min；
B, after stratification, open stirring pool liquid outlet, supernatant flows into sedimentation tank after being filtered, heavy
30min is again stood in pond, shallow lake；It is then turned on circulating pump, by the standing liquid stream in sedimentation tank through biphenyl quasi-molecule trace post,
Stand liquid and flow into storage pool through molecular blotting column liquid outlet one, then in circulating pump back flows back into stirring pool with in stirring pool
Soil is again stirring for the organic pollution for extracting in contaminated soil；
In above-mentioned biphenyl quasi-molecule trace post, 1:5 in mass ratio is filled with biphenyl quasi-molecule imprinted polymer and bead；
The every circulation primary of C, step B, closes the liquid outlet one of molecular engram eluting adsorption column, opens eluant container
Valve, injects molecular engram eluting adsorption column, eluting by circulating pump three by eluant (eluant is pure acetone solution)
Solution flows into degradation reaction pond from the second liquid outlet of molecular engram eluting adsorption column；
Reaction tank is heated, reaches 45 DEG C to solution temperature, open cold condenser simultaneously, the eluting in degradation reaction pond
Volatilization after agent is heated, flows in eluant pond after the condensation of condensed device；
D, repeat B and step C 3 times, be 6.9mg/kg through surveying the organic pollution PCB28 content in soil；
E, degradation reaction pond are before degradation reaction, by the primary response liquid (i.e. water) of storage in holding pond two by circulation
Pump four pumps in reaction tank that (eluent: reactant liquor volume ratio≤1%, makes third with remaining eluent in degradation reaction pond
The volumetric concentration of ketone accounts for whole reactant liquor volume less than 1%) mix, and regulate the pH=11.0 of reactant liquor, close and drop
Solve all valves of reaction tank connection, be then turned on ozonator, the ozone that ozonator produces is passed through degraded anti-
In the solution of Ying Chi, confined reaction 3.0 hours under pressurization 0.5MPa；Ozone intake with the ratio of degraded solutions is
0.1g/L；Solution PCB28 content before measured reaction is 37.1mg/L, and the PCB28 content after degradation reaction is
2.1mg/L。
F, after the solution degradation in degradation reaction pond to organic pollution is up to standard, close eluant container lower valve,
ON cycle pump three, by reactant liquor through molecular blotting column, goes to storage by the liquid outlet three of molecular engram eluting adsorption column
The storage of Chi Erzhong, waits and again carries out degradation reaction.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, and not
In the case of deviating from the spirit or essential attributes of the present invention, it is possible to realize the present invention in other specific forms.Therefore, nothing
Opinion from the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention by
Claims rather than described above limit, it is intended that will fall in the implication of equivalency of claim and scope
Interior all changes are included in the present invention.Should not be considered as limiting involved power by any reference in claim
Profit requirement.
Although moreover, it will be appreciated that this specification is been described by according to embodiment, but the most each embodiment only wraps
Containing an independent technical scheme, this narrating mode of description is only for clarity sake, and those skilled in the art should
When description can also be formed art technology through appropriately combined as an entirety, the technical scheme in each embodiment
Personnel may be appreciated other embodiments.
Claims (10)
1. an organic pollutant removal system, it is characterised in that include pollute organic pollution container (1),
Stirring pool (2), sedimentation tank (3), molecular engram eluting adsorption column (4), eluant container (5), degradation reaction
Pond (6)；
Discharging opening connection stirring pool (2) of described organic pollution container (1), described stirring pool (2) is provided with
Solvent filling opening, described solvent filling opening connects a multiple-limb feed tube (20), and described multiple-limb feed tube includes first
Feed tube (201), the second feed tube (202), the 3rd feed tube (203), each feed tube is respectively equipped with valve (204)
With effusion meter (205)；
Described stirring pool (2) connect with sedimentation tank (3) by pipeline, described sedimentation tank (3) export by pipeline and
The inlet connection of molecular engram eluting adsorption column (4), adsorbs with molecular engram eluting connecting described sedimentation tank (3)
The pipeline of post (4) is provided with the first circulating pump (81)；
The bottom liquid outlet of described molecular engram eluting adsorption column (4) by be provided with the pipeline of the second circulating pump (82) with
Stirring pool (2) liquid return hole connects；
Described molecular engram eluting adsorption column (4) is additionally provided with eluant entrance and eluant outlet, described eluant entrance
Connecting with eluant container (5) by being provided with the pipeline of the 3rd circulating pump (83), described eluant container outlet is provided with
First control valve (71), and the inlet of the pipeline Yu degradation reaction pond (6) by being provided with the 4th circulating pump (84)
Connection.
A kind of organic pollutant removal system the most according to claim 1, it is characterised in that described molecular engram
It is additionally provided with the first storage pool (11) on the pipeline that the bottom liquid outlet of eluting adsorption column (4) is connected with stirring pool (2).
A kind of organic pollutant removal system the most according to claim 1, it is characterised in that described molecular engram
The bottom of eluting adsorption column (4) is additionally provided with a liquid outlet, and described liquid outlet is connected by pipeline and the second storage pool (12)
Logical, by being provided with the pipeline of the 5th circulating pump (85) between described second storage pool (12) and degradation reaction pond (6)
Connection.
A kind of organic pollutant removal system the most according to claim 3, it is characterised in that described degradation reaction
Pond (6) is provided with self-heating system, and described degradation reaction pond (6) is provided with volatilization mouth, and described volatilization mouth passes through pipeline with cold
Condenser (10) connects, and described pipeline is provided with the second control valve (72).The outlet of described condenser (10) and eluting
Agent container (5) connects.
A kind of organic pollutant removal system the most according to claim 1, it is characterised in that described degradation reaction pond
(6) being provided with the pipeline being connected with the 3rd circulating pump (83) import, described pipeline is provided with the 3rd control valve (73).
A kind of organic pollutant removal system the most according to claim 1, it is characterised in that described stirring pool is with heavy
Shallow lake is additionally provided with filter between pond.
A kind of organic pollutant removal system the most according to claim 1, it is characterised in that described system also includes
One ozonator (13), described ozonator (13) gas outlet is by being provided with the pipeline of the 4th control valve (74)
Connect with degradation reaction pond (6).
8. a solid-state organic pollutant removal method, it is characterised in that comprise the steps:
A, solid contaminant is added in stirring pool, in stirring pool, then press mass volume ratio 1:5-1:10 add molten
Solve agent, be sufficiently stirred for, then stand；
B, after stratification, open stirring pool liquid outlet, supernatant flows into sedimentation tank after being filtered, heavy
Shallow lake stands in pond again；It is then turned on circulating pump one, the standing liquid in sedimentation tank is injected molecular engram eluting adsorption column,
Pollutant are after molecular engram eluting adsorption column adsorbs, and lysate flows into storage pool one through liquid outlet one, then through circulating pump two
Back flow back in stirring pool and be again stirring for the organic pollution for extracting in solid contaminant with the soil in stirring pool；
The every circulation primary of C, step B, closes the liquid outlet one and three of molecular engram eluting adsorption column, opens eluant and holds
The valve of device, injects molecular engram eluting adsorption column by circulating pump three by eluant, eluting molecular engram eluting adsorption column,
Eluent solution, by circulating pump four, flows into degradation reaction pond from the second liquid outlet；
Heating reaction tank, heating-up temperature is less than solvent boiling point 5-20 DEG C, simultaneously open cold condenser, degradation reaction
The heated rear volatilization of eluant in pond, flows in eluant pond after the condensation of condensed device；
D, repetition B and step C are repeatedly until the organic pollution removed in solid contaminant or pollution concentration are up to standard；
E, degradation reaction pond are before degradation reaction, by the primary response liquid (i.e. water) of storage in holding pond two by circulation
Pump four pump in reaction tank with remaining eluent in degradation reaction pond (6) (eluent: reactant liquor volume ratio≤1%)
Mixing, closes all valves connected with degradation reaction pond (6), is then turned on ozonator, by ozonator
The ozone produced is passed through in the solution in degradation reaction pond, and pressurization closed reacts 1-3 hour；
F, after the solution degradation in degradation reaction pond to organic pollution is up to standard, close eluant container (5) lower section
Valve, ON cycle pump three, by reactant liquor through molecular blotting column, by the liquid outlet three turns of molecular engram eluting adsorption column
Store to storage pool two, wait and again carry out degradation reaction.
A kind of solid-state organic pollutant removal method the most according to claim 8, it is characterised in that described solid-state
Pollutant are the soil containing organic pollution, farm animal excrement or mud.
10. a liquid organic pollutant removal method, it is characterised in that comprise the steps:
A, the sewage containing organic pollution is filtered after flow into sedimentation tank, in sedimentation tank stand one section time
Between；It is then turned on circulating pump one, the standing liquid in sedimentation tank is injected molecular engram eluting adsorption column, washes through molecular engram
After desorption attached column eluting, eluent flows into storage pool one once liquid outlet, then refills molecular engram eluting through circulating pump
Adsorption column；
The every circulation primary of B, step A, closes the liquid outlet one and three of molecular engram eluting adsorption column, opens eluant and holds
The valve of device, injects molecular engram eluting adsorption column by circulating pump three by eluant, washes through molecular engram eluting adsorption column
After Tuo, eluent solution, by circulating pump four, flows into degradation reaction pond from the second liquid outlet；
Heating reaction tank, heating-up temperature is less than solvent boiling point 5-20 DEG C, simultaneously open cold condenser, degradation reaction
The heated rear volatilization of eluant in pond, flows in eluant pond after the condensation of condensed device；
C, repetition A and step B are repeatedly until the organic pollution removed in soil or pollutant levels are up to standard；
D, degradation reaction pond are before degradation reaction, by the primary response liquid (i.e. water) of storage in holding pond two by circulation
Pump four pump in reaction tank with remaining eluent in degradation reaction pond (6) (eluent: reactant liquor volume ratio≤1%)
Mixing, closes all valves connected with degradation reaction pond (6), is then turned on ozonator, by ozonator
The ozone produced is passed through in the solution in degradation reaction pond, and pressurization closed reacts 1-3 hour；
E, after the solution degradation in degradation reaction pond to organic pollution is up to standard, close eluant container (5) lower section
Valve, ON cycle pump three, by reactant liquor through molecular blotting column, by the liquid outlet three turns of molecular engram eluting adsorption column
Store to storage pool two, wait and again carry out degradation reaction.
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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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| CN105923843B (en) | 2018-10-26 |
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