CN105621813B - The system that purified treatment is carried out to petrochemical wastewater using hydrophilic and oleophobic film - Google Patents
The system that purified treatment is carried out to petrochemical wastewater using hydrophilic and oleophobic film Download PDFInfo
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- CN105621813B CN105621813B CN201610124434.1A CN201610124434A CN105621813B CN 105621813 B CN105621813 B CN 105621813B CN 201610124434 A CN201610124434 A CN 201610124434A CN 105621813 B CN105621813 B CN 105621813B
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- 238000011282 treatment Methods 0.000 title claims abstract description 26
- 239000002351 wastewater Substances 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002699 waste material Substances 0.000 claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 claims abstract description 34
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 238000007664 blowing Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 230000007246 mechanism Effects 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 37
- 238000001556 precipitation Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229910000831 Steel Inorganic materials 0.000 claims description 23
- 239000010865 sewage Substances 0.000 claims description 23
- 239000010959 steel Substances 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 17
- 238000007598 dipping method Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 238000009287 sand filtration Methods 0.000 claims description 11
- 239000004519 grease Substances 0.000 claims description 9
- -1 polypropylene Polymers 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical group OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- NICLKHGIKDZZGV-UHFFFAOYSA-N 2-cyanopentanoic acid Chemical compound CCCC(C#N)C(O)=O NICLKHGIKDZZGV-UHFFFAOYSA-N 0.000 claims description 2
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 10
- 235000019198 oils Nutrition 0.000 description 35
- 239000012071 phase Substances 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 6
- 238000004925 denaturation Methods 0.000 description 5
- 230000036425 denaturation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical group O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229940005605 valeric acid Drugs 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/04—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The present invention relates to a kind of systems carrying out purified treatment to petrochemical wastewater using hydrophilic and oleophobic film, the feeding port of the magnetic biological adsorption agent for adding adsorpting lead ion/add mechanism is provided on ionic adsorption pond, air-blowing mouth is arranged in the bottom of pond in ionic adsorption pond, filter is set at air-blowing mouth, ionic adsorption pond is set side by side with multiple, and filter device is provided between ionic adsorption pond and oil-water separation tank.Above system can completely remove lead ion in leaded waste oil water, and reliably be detached to oily components and aqueous components, carry out fishing reuse to oily components, and reduce cost and the period of subsequent biochemical treatment, realize the efficient process of waste water.
Description
It is on December 10th, 2014 that the present invention, which is the applying date, entitled " a kind of application No. is 201410758357.6
The divisional application of the patent of invention of the efficient process system of petrochemical wastewater ".
Technical field
The present invention relates to sewage treatment fields, and in particular to a kind of to be carried out only to petrochemical wastewater using hydrophilic and oleophobic film
Change the system of processing.
Background technology
Petroleum chemical industry will produce a large amount of oily wastewater, simultaneously as the particularity of petroleum chemical industry, usually dirty
Also contain lead ion in water.Currently, also have the numerous method and systems for handling oily wastewater of document report, but its most nothing
Method is simultaneously handled lead ion, oily components, and often most lead ion is deposited in the precipitating sludge in subsequent biochemical pond
In, leaded sludge is formed, is more difficult to handle.
Invention content
It is to petrochemical wastewater progress purified treatment using hydrophilic and oleophobic film it is an object of the invention to provide a kind of
System, can recycle the oily components in oily waste water, while handling the lead ion in sewage.
To achieve the above object, present invention employs following technical schemes：
A kind of system that purified treatment being carried out to petrochemical wastewater using hydrophilic and oleophobic film, including set gradually, is front and back
The rough filtering device that coarse filtration is carried out to waste oil water of connection, to waste oil water neutralize the regulating reservoir of adjusting, in waste oil water
Ion precipitation pond/ionic adsorption pond that lead ion is detached, the water-oil separating that the oily components in waste oil water are detached
Pond, the sand filtration for carrying out the aeration tank of biochemical treatment to the sewage after separation and carrying out sand filtration to the sewage after biochemical treatment fill
It sets, hydrophilic and oleophobic filter device is arranged in the liquid outlet of oil-water separation tank, and oil-water separation tank is connected with oily components retracting device.
The oily components of oily components retracting device fishing recycling can be recycled.
Detailed scheme is：The throwing of the magnetic biological adsorption agent for adding adsorpting lead ion is provided on ionic adsorption pond
Material mouth/add mechanism, the bottom of pond in ionic adsorption pond is arranged air-blowing mouth, filter is arranged at air-blowing mouth, ionic adsorption pond is set up in parallel
Have multiple, filter device is provided between ionic adsorption pond and oil-water separation tank.Ion precipitation pond is above to be provided with for adding
The feeding port of flocculant/add mechanism is provided with the tracheae of vertical shape arrangement, is uniformly arranged on the tube wall of tracheae in ion precipitation pond
Filter is arranged at gas port for stomata, and precipitation separate tank is provided between ion precipitation pond and oil-water separation tank, and precipitation separate tank is arranged side by side
It is arranged multiple.Flocculant can be or mixtures thereof one kind in polyacrylamide, Sodium Polyacrylate.Multiple ionic adsorption ponds are set
Or the purpose of precipitation separate tank is mainly to ensure the continuity of sewage disposal, it is whole when avoiding carrying out precipitation process because of single pond body
The other equipment of a sewage disposal system is just out of service, improves the continuity and efficiency of whole system operation.Meanwhile aeration tank
Also it is set up in parallel multiple.
Hydrophilic and oleophobic filter device includes hydrophilic and oleophobic film, and hydrophilic and oleophobic film is obtained by operating as follows：Not by 600 purposes
Rust steel mesh first cleans 20min with dipping by lye, is then cleaned by ultrasonic 20min with organic solvent, by stainless (steel) wire after ultrasonic cleaning
It dries；Then stainless (steel) wire is placed in the first compositional liquor and is cleaned with deionized water after impregnating 54h, dipping and is dried in the air naturally
It is dry；Finally 20h will be impregnated in the second compositional liquor of steel wire, is cleaned with deionized water after taking-up and naturally dry, organic solvent are
Ethyl alcohol and acetone are according to 1.5:1 volume ratio is prepared to obtain, the first compositional liquor be trishydroxymethylaminomethane, Dopamine hydrochloride and
Hydrochloric acid solution is prepared to obtain, and trishydroxymethylaminomethane content is 8.2g/L in the first compositional liquor, Dopamine hydrochloride content is
5.6g/L, PH=8.5；Second compositional liquor is thioacetic acid, sulfosuccinic acid, sodium hydroxide are prepared to obtain, in the second compositional liquor
Thioacetic acid content is 2.48g/L, sulfosuccinic acid content is 3.8g/L, PH=12.5.
Hydrophilic and oleophobic film obtained above, by detection, the contact angle with water droplet is 0 °, and the contact angle with oil droplet is
142 °, when oil water mixture is filtered, oily components can be by effectively catching, and water phase components can then pass through,
Therefore, grease can quickly be detached.Meanwhile whether above-mentioned hydrophilic and oleophobic film can also eliminate the lead ion in sewage
It is detected, is eliminated if lead ion is unadsorbed, with the active group on hydrophilic and oleophobic film chelation reaction can occur for lead ion, with
The continuous absorption of lead ion, the hydrophily of hydrophilic and oleophobic film continuously decreases, lipophile gradually increases, and ultimately becomes oleophilic drainage
Film, in the process hydrophilic and oleophobic film can not just play the role of grease and efficiently separate.And for petrochemical plant, discharge
Waste water in plumbum ion concentration be unstable, when plumbum ion concentration changes greatly, the often throwing of adsorbent or precipitating reagent
Dosage will be very few, can not just eliminate lead ion at this time.Therefore, in the present invention, oil-water separation tank sewage flow direction is divided into phase
The section ponds A and B sections of ponds being mutually isolated, B sections of ponds are divided into the ponds B1 mutually completely cut off and the ponds B2, A sections of ponds open up respectively for the ponds B1
Hydrophilic and oleophobic filter device is respectively set at the first and second liquid outlet in the first and second liquid outlet being connected with the ponds B2.When in use
A pond in only B sections of pond is connected with A sections of ponds, and without using the hydrophilic and oleophobic filter device on liquid outlet on A sections of ponds
It is isolated with the pond liquid phase in A sections of ponds.When lead ion does not eliminate, the hydrophilic and oleophobic film that is contacted with the pond liquid phase in A sections of ponds because
Adsorpting lead ion make it is hydrophilic and oleophobic sexually revise, grease can not be efficiently separated, at this time part oily components will enter use
B sections pond in, therefore when there are oily components in detecting B sections of ponds, the system of front and continued is checked and/or is increased flocculation
Agent, adsorbent dosage so that lead ion eliminate completely.After above-mentioned measure obtains effect, then another pond B sections of is enabled, with
This to the B sections pond polluted by oily components clear up and replace the hydrophilic and oleophobic filter device of denaturation simultaneously, with
Standby next time uses.So that the oily components, water phase components in grease can be kept completely separate, lead ion can completely by except
It goes, ensures the reliable treatments of leaded waste oil water.
Rough filtering device, regulating reservoir, aeration tank, sand filtering device, filter device, precipitation separate tank, oily components retracting device
It can refer to and have existed equipment with the same function in existing sewage disposal system and implemented.
The efficient process system of above-mentioned petrochemical wastewater provided by the invention, can be complete to lead ion in leaded waste oil water
Full removal, and oily components and aqueous components are reliably detached, fishing reuse is carried out to oily components, and reduce
The cost of subsequent biochemical treatment and period realize the efficient process of waste water.
Description of the drawings
Fig. 1 is the schematic diagram of the first embodiment of waste water treatment system；
Fig. 2 is the schematic diagram of second of embodiment of waste water treatment system；
Fig. 3 is the structural schematic diagram of oil-water separation tank.
Specific implementation mode
In order to make objects and advantages of the present invention be more clearly understood, the present invention is carried out specifically with reference to embodiments
It is bright.It should be appreciated that following word is only used to one or more of specific embodiments of the description present invention, not to the present invention
The protection domain specifically asked carries out considered critical.
Implement 1
As shown in Figure 1,3, the efficient process system of petrochemical wastewater, including set gradually, is preceding latter linked to waste oil
Water carries out the rough filtering device 11 of coarse filtration, carries out neutralizing the regulating reservoir 12 for adjusting PH to waste oil water, to the lead ion in waste oil water
The 131/ ionic adsorption pond 132 of ion precipitation pond detached, the water-oil separating that the oily components in waste oil water are detached
Pond 15 carries out the aeration tank 16 of biochemical treatment to the sewage after separation and carries out the sand filtration of sand filtration to the sewage after biochemical treatment
Device 17, oil-water separation tank 15 are connected with oily components retracting device.It is provided on ionic adsorption pond 132 for adding absorption
The feeding port of the magnetic biological adsorption agent of lead ion/add mechanism, air-blowing mouth, air-blowing mouth is arranged in the bottom of pond in ionic adsorption pond 132
Place's setting filter, ionic adsorption pond 132 is set side by side with multiple, is provided between ionic adsorption pond 132 and oil-water separation tank 15
Filter device 141.15 sewage of oil-water separation tank flow direction is divided into the mutually isolated section ponds A and B sections of ponds, B sections of ponds be divided into mutually every
The exhausted ponds B1 and the ponds B2, A sections of ponds open up the first and second liquid outlet for being connected with the ponds B1 and the ponds B2 respectively.
Hydrophilic and oleophobic film is obtained by operating as follows：The stainless (steel) wire of 600 mesh is first cleaned into 20min with dipping by lye, so
It is cleaned by ultrasonic 20min with organic solvent afterwards, dries stainless (steel) wire after ultrasonic cleaning；Stainless (steel) wire is then placed in the first compounding
In liquid simultaneously naturally dry is cleaned with deionized water after dipping 54h, dipping；It will finally be impregnated in the second compositional liquor of steel wire
20h is cleaned with deionized water after taking-up and naturally dry, organic solvent is ethyl alcohol and acetone according to 1.5:1 volume ratio is prepared
It obtains, the first compositional liquor is that trishydroxymethylaminomethane, Dopamine hydrochloride and hydrochloric acid solution are prepared to obtain, three in the first compositional liquor
Hydroxymethyl aminomethane content is 8.2g/L, Dopamine hydrochloride content is 5.6g/L, PH=8.5；Second compositional liquor is sulfydryl second
Acid, sulfosuccinic acid, sodium hydroxide are prepared to obtain, and thioacetic acid content is 2.48g/L in the second compositional liquor, sulfosuccinic acid contains
Amount is 3.8g/L, PH=12.5.
Hydrophilic and oleophobic film is assembled on hydrophilic and oleophobic filter device 153, then hydrophilic and oleophobic filter device 153 is installed
At first and second liquid outlet in A sections of ponds.First liquid outlet 151 in A sections of ponds is enabled, the second liquid outlet 152 is closed, and is started thick
Filter device 11, regulating reservoir, ionic adsorption pond 132, filter device 141, A sections of ponds, the ponds B1, oil-water separation tank 15, aeration tank 16, sand
Device 17, oily components retracting device are filtered, leaded waste oil water, which is injected the system, carries out continuous processing.Go out in the ponds B1 if detecting
Existing oil phase component, then close the liquid outlet in the ponds B1, to the system of front and continued check and/or add the dosage of adsorbent, so that
Lead ion eliminates completely.After above-mentioned measure obtains effect, A sections of the first liquid outlets of pond 151 are closed, open the second liquid outlet 152,
Start B2 ponds to be run, operation while carries out cleaning and to the hydrophilic and oleophobic of denaturation to the ponds B1 polluted by oily components
Filter device 153 is replaced, and is used in case replacing B sections of ponds next time.Enable oily components, water phase components in grease complete
Fully separating, lead ion can be completely removed, and ensure the reliable treatments of leaded waste oil water.
Embodiment 2
As shown in Figure 2,3, the efficient process system of petrochemical wastewater, including set gradually, is preceding latter linked to waste oil
Water carries out the rough filtering device 11 of coarse filtration, carries out neutralizing the regulating reservoir 12 for adjusting PH to waste oil water, to the lead ion in waste oil water
The 131/ ionic adsorption pond 132 of ion precipitation pond detached, the water-oil separating that the oily components in waste oil water are detached
Pond 15 carries out the aeration tank 16 of biochemical treatment to the sewage after separation and carries out the sand filtration of sand filtration to the sewage after biochemical treatment
Device 17, oil-water separation tank 15 are connected with oily components retracting device.Ion precipitation pond 131 is above to be provided with for adding wadding
The feeding port of solidifying agent/add mechanism is provided with the tracheae of vertical shape arrangement, is uniformly set on the tube wall of tracheae in ion precipitation pond 131
Stomata is set, filter is set at gas port, precipitation separate tank 142, precipitation are provided between ion precipitation pond 131 and oil-water separation tank 15
Separate tank 142 is set up in parallel multiple.15 sewage of oil-water separation tank flow direction is divided into the mutually isolated section ponds A and B sections of ponds, B sections of ponds point
It is divided into the ponds B1 mutually completely cut off and the ponds B2, A sections of ponds open up the first and second liquid outlet for being connected with the ponds B1 and the ponds B2 respectively.
Hydrophilic and oleophobic film is obtained by operating as follows：The stainless (steel) wire of 600 mesh is first cleaned into 20min with dipping by lye, so
It is cleaned by ultrasonic 20min with organic solvent afterwards, dries stainless (steel) wire after ultrasonic cleaning；Stainless (steel) wire is then placed in the first compounding
In liquid simultaneously naturally dry is cleaned with deionized water after dipping 54h, dipping；It will finally be impregnated in the second compositional liquor of steel wire
20h is cleaned with deionized water after taking-up and naturally dry, organic solvent is ethyl alcohol and acetone according to 1.5:1 volume ratio is prepared
It obtains, the first compositional liquor is that trishydroxymethylaminomethane, Dopamine hydrochloride and hydrochloric acid solution are prepared to obtain, three in the first compositional liquor
Hydroxymethyl aminomethane content is 8.2g/L, Dopamine hydrochloride content is 5.6g/L, PH=8.5；Second compositional liquor is sulfydryl second
Acid, sulfosuccinic acid, sodium hydroxide are prepared to obtain, and thioacetic acid content is 2.48g/L in the second compositional liquor, sulfosuccinic acid contains
Amount is 3.8g/L, PH=12.5.
Hydrophilic and oleophobic film is assembled on hydrophilic and oleophobic filter device 153, then hydrophilic and oleophobic filter device 153 is installed
At first and second liquid outlet in A sections of ponds.First liquid outlet 151 in A sections of ponds is enabled, the second liquid outlet 152 is closed, and is started thick
Filter device 11, regulating reservoir, ion precipitation pond 131, precipitation separate tank 142, A sections of ponds, the ponds B1, oil-water separation tank 15, aeration tank 16,
Leaded waste oil water is injected the system and carries out continuous processing by sand filtering device 17, oily components retracting device.If detecting in the ponds B1
There is oil phase component, then close the liquid outlet in the ponds B1, to the system of front and continued check and/or add the dosage of adsorbent, so that
Lead ion eliminate completely.After above-mentioned measure obtains effect, A sections of the first liquid outlets of pond 151 are closed, open the second liquid outlet
152, start B2 ponds and run, operation while carries out cleaning and to the hydrophilic of denaturation to the ponds B1 polluted by oily components
Oleophobic filter device 153 is replaced, and is used in case replacing B sections of ponds next time.Enable oily components, water phase components in grease
Enough be kept completely separate, lead ion can be completely removed, ensure the reliable treatments of leaded waste oil water.
Embodiment 3
As shown in Figure 1,3, the efficient process system of petrochemical wastewater, including set gradually, is preceding latter linked to waste oil
Water carries out the rough filtering device 11 of coarse filtration, carries out neutralizing the regulating reservoir 12 for adjusting PH to waste oil water, to the lead ion in waste oil water
The 131/ ionic adsorption pond 132 of ion precipitation pond detached, the water-oil separating that the oily components in waste oil water are detached
Pond 15 carries out the aeration tank 16 of biochemical treatment to the sewage after separation and carries out the sand filtration of sand filtration to the sewage after biochemical treatment
Device 17, oil-water separation tank 15 are connected with oily components retracting device.It is provided on ionic adsorption pond 132 for adding absorption
The feeding port of the magnetic biological adsorption agent of lead ion/add mechanism, air-blowing mouth, air-blowing mouth is arranged in the bottom of pond in ionic adsorption pond 132
Place's setting filter, ionic adsorption pond 132 is set side by side with multiple, is provided between ionic adsorption pond 132 and oil-water separation tank 15
Filter device 141.15 sewage of oil-water separation tank flow direction is divided into the mutually isolated section ponds A and B sections of ponds, B sections of ponds be divided into mutually every
The exhausted ponds B1 and the ponds B2, A sections of ponds open up the first and second liquid outlet for being connected with the ponds B1 and the ponds B2 respectively.
Hydrophilic and oleophobic film is obtained by operating as follows：The stainless (steel) wire of 600 mesh is first cleaned into 20min with dipping by lye, so
It is cleaned by ultrasonic 20min with organic solvent afterwards, dries stainless (steel) wire after ultrasonic cleaning；Stainless (steel) wire is then placed in the first compounding
In liquid simultaneously naturally dry is cleaned with deionized water after dipping 54h, dipping；It will finally be impregnated in the second compositional liquor of steel wire
20h is cleaned with deionized water after taking-up and naturally dry, organic solvent is ethyl alcohol and acetone according to 1.5:1 volume ratio is prepared
It obtains, the first compositional liquor is that trishydroxymethylaminomethane, Dopamine hydrochloride and hydrochloric acid solution are prepared to obtain, three in the first compositional liquor
Hydroxymethyl aminomethane content is 8.2g/L, Dopamine hydrochloride content is 5.6g/L, PH=8.5；Second compositional liquor is polypropylene
Free radical polyalcohol, sulfosuccinic acid, sodium hydroxide are prepared to obtain, and polypropylene free radical polyalcohol content is in the second compositional liquor
4.5g/L, sulfosuccinic acid content are 1.25g/L, PH=13；Polypropylene free radical polyalcohol is that 1 parts by weight propylene acid monomers are molten
In the distilled water of 2.5 parts by weight, the bis- (cyanogen of 4,4'- azos of the n- dodecyl mereaptan and 0.025 parts by weight of 0.03 parts by weight are added
Base valeric acid), 0.8h is reacted at 55 DEG C under nitrogen protection, then be warming up to 75 DEG C of reaction 6.5h, be filtered, washed after reaction,
It is dry to be made.
Hydrophilic and oleophobic film is assembled on hydrophilic and oleophobic filter device 153, then hydrophilic and oleophobic filter device 153 is installed
At first and second liquid outlet in A sections of ponds.First liquid outlet 151 in A sections of ponds is enabled, the second liquid outlet 152 is closed, and is started thick
Filter device 11, regulating reservoir, ionic adsorption pond 132, filter device 141, A sections of ponds, the ponds B1, oil-water separation tank 15, aeration tank 16, sand
Device 17, oily components retracting device are filtered, leaded waste oil water, which is injected the system, carries out continuous processing.Go out in the ponds B1 if detecting
Existing oil phase component, then close the liquid outlet in the ponds B1, to the system of front and continued check and/or add the dosage of adsorbent, so that
Lead ion eliminates completely.After above-mentioned measure obtains effect, A sections of the first liquid outlets of pond 151 are closed, open the second liquid outlet 152,
Start B2 ponds to be run, operation while carries out cleaning and to the hydrophilic and oleophobic of denaturation to the ponds B1 polluted by oily components
Filter device 153 is replaced, and is used in case replacing B sections of ponds next time.Enable oily components, water phase components in grease complete
Fully separating, lead ion can be completely removed, and ensure the reliable treatments of leaded waste oil water.
Embodiment 4
As shown in Figure 2,3, the efficient process system of petrochemical wastewater, including set gradually, is preceding latter linked to waste oil
Water carries out the rough filtering device 11 of coarse filtration, carries out neutralizing the regulating reservoir 12 for adjusting PH to waste oil water, to the lead ion in waste oil water
The 131/ ionic adsorption pond 132 of ion precipitation pond detached, the water-oil separating that the oily components in waste oil water are detached
Pond 15 carries out the aeration tank 16 of biochemical treatment to the sewage after separation and carries out the sand filtration of sand filtration to the sewage after biochemical treatment
Device 17, oil-water separation tank 15 are connected with oily components retracting device.Ion precipitation pond 131 is above to be provided with for adding wadding
The feeding port of solidifying agent/add mechanism is provided with the tracheae of vertical shape arrangement, is uniformly set on the tube wall of tracheae in ion precipitation pond 131
Stomata is set, filter is set at gas port, precipitation separate tank 142, precipitation are provided between ion precipitation pond 131 and oil-water separation tank 15
Separate tank 142 is set up in parallel multiple.15 sewage of oil-water separation tank flow direction is divided into the mutually isolated section ponds A and B sections of ponds, B sections of ponds point
It is divided into the ponds B1 mutually completely cut off and the ponds B2, A sections of ponds open up the first and second liquid outlet for being connected with the ponds B1 and the ponds B2 respectively.
Hydrophilic and oleophobic film is obtained by operating as follows：The stainless (steel) wire of 600 mesh is first cleaned into 20min with dipping by lye, so
It is cleaned by ultrasonic 20min with organic solvent afterwards, dries stainless (steel) wire after ultrasonic cleaning；Stainless (steel) wire is then placed in the first compounding
In liquid simultaneously naturally dry is cleaned with deionized water after dipping 54h, dipping；It will finally be impregnated in the second compositional liquor of steel wire
20h is cleaned with deionized water after taking-up and naturally dry, organic solvent is ethyl alcohol and acetone according to 1.5:1 volume ratio is prepared
It obtains, the first compositional liquor is that trishydroxymethylaminomethane, Dopamine hydrochloride and hydrochloric acid solution are prepared to obtain, three in the first compositional liquor
Hydroxymethyl aminomethane content is 8.2g/L, Dopamine hydrochloride content is 5.6g/L, PH=8.5；Polypropylene in second compositional liquor
Free radical polyalcohol content is 4.5g/L, sulfosuccinic acid content is 1.25g/L, PH=13；Polypropylene free radical polyalcohol is 1
Parts by weight propylene acid monomers are dissolved in the distilled water of 2.5 parts by weight, and the n- dodecyl mereaptan and 0.025 weight of 0.03 parts by weight is added
4, the 4'- azos of part are bis- (cyanopentanoic acid), react 0.8h at 55 DEG C under nitrogen protection, then are warming up to 75 DEG C of reaction 6.5h, instead
Be filtered, washed after answering, dry it is obtained.
Hydrophilic and oleophobic film is assembled on hydrophilic and oleophobic filter device 153, then hydrophilic and oleophobic filter device 153 is installed
At first and second liquid outlet in A sections of ponds.First liquid outlet 151 in A sections of ponds is enabled, the second liquid outlet 152 is closed, and is started thick
Filter device 11, regulating reservoir, ion precipitation pond 131, precipitation separate tank 142, A sections of ponds, the ponds B1, oil-water separation tank 15, aeration tank 16,
Leaded waste oil water is injected the system and carries out continuous processing by sand filtering device 17, oily components retracting device.If detecting in the ponds B1
There is oil phase component, then close the liquid outlet in the ponds B1, to the system of front and continued check and/or add the dosage of adsorbent, so that
Lead ion eliminate completely.After above-mentioned measure obtains effect, A sections of the first liquid outlets of pond 151 are closed, open the second liquid outlet
152, start B2 ponds and run, operation while carries out cleaning and to the hydrophilic of denaturation to the ponds B1 polluted by oily components
Oleophobic filter device 153 is replaced, and is used in case replacing B sections of ponds next time.Enable oily components, water phase components in grease
Enough be kept completely separate, lead ion can be completely removed, ensure the reliable treatments of leaded waste oil water.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, after knowing content described in the present invention, without departing from the principle of the present invention, it can also be made several
Same transformation and replacement, these convert and substitute on an equal basis and also should be regarded as belonging to the scope of protection of the present invention.
Claims (1)
1. a kind of system that purified treatment being carried out to petrochemical wastewater using hydrophilic and oleophobic film, including set gradually, front and back connect
What is connect carries out waste oil water the rough filtering device of coarse filtration, to waste oil water neutralize the regulating reservoir of adjusting, to the lead in waste oil water
Ion precipitation pond/ionic adsorption pond that ion is detached, to the oil-water separation tank that the oily components in waste oil water are detached,
The aeration tank of biochemical treatment is carried out to the sewage after separation and carries out the sand filtering device of sand filtration, oil to the sewage after biochemical treatment
Hydrophilic and oleophobic filter device is arranged in the liquid outlet of water separation tank, and oil-water separation tank is connected with oily components retracting device；Ion
The feeding port of the magnetic biological adsorption agent for adding adsorpting lead ion/add mechanism, ionic adsorption pond is provided on adsorption tank
Bottom of pond air-blowing mouth is set, filter is set at air-blowing mouth, and ionic adsorption pond is set side by side with multiple, ionic adsorption pond and grease point
From being provided with filter device between pond；
Hydrophilic and oleophobic filter device includes hydrophilic and oleophobic film, and hydrophilic and oleophobic film is obtained by operating as follows：By the stainless steel of 600 mesh
Net first cleans 20min with dipping by lye, is then cleaned by ultrasonic 20min with organic solvent, dries stainless (steel) wire after ultrasonic cleaning；
Then stainless (steel) wire is placed in the first compositional liquor after impregnating 54h, dipping and cleans simultaneously naturally dry with deionized water；Finally
Stainless (steel) wire is impregnated into 20h in the second compositional liquor, cleans simultaneously naturally dry with deionized water after taking-up, organic solvent is ethyl alcohol
With acetone according to 1.5:1 volume ratio is prepared to obtain, and the first compositional liquor is trishydroxymethylaminomethane, Dopamine hydrochloride and hydrochloric acid
Solution is prepared to obtain, in the first compositional liquor trishydroxymethylaminomethane content be 8.2g/L, Dopamine hydrochloride content be 5.6g/L,
pH=8.5；Second compositional liquor is polypropylene free radical polyalcohol, sulfosuccinic acid, sodium hydroxide are prepared to obtain, the second compositional liquor
Middle polypropylene free radical polyalcohol content is 4.5g/L, sulfosuccinic acid content is 1.25g/L, pH=13；Polypropylene radical polymerization
Close object be 1 parts by weight propylene acid monomers be dissolved in the distilled water of 2.5 parts by weight, be added 0.03 parts by weight n- dodecyl mereaptan and
4, the 4'- azos of 0.025 parts by weight are bis- (cyanopentanoic acid), react 0.8h at 55 DEG C under nitrogen protection, then are warming up to 75 DEG C instead
Answer 6.5h, be filtered, washed after reaction, dry it is obtained.
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| CN201410758357.6A CN104529060B (en) | 2014-12-10 | 2014-12-10 | A kind of system that efficiently process of petrochemical wastewater |
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| CN201610124394.0A Active CN105621810B (en) | 2014-12-10 | 2014-12-10 | The system that hydrophilic and oleophobic film is used for petrochemical wastewater processing |
| CN201610124434.1A Expired - Fee Related CN105621813B (en) | 2014-12-10 | 2014-12-10 | The system that purified treatment is carried out to petrochemical wastewater using hydrophilic and oleophobic film |
| CN201410758357.6A Active CN104529060B (en) | 2014-12-10 | 2014-12-10 | A kind of system that efficiently process of petrochemical wastewater |
| CN201610126315.XA Active CN105693024B (en) | 2014-12-10 | 2014-12-10 | A kind of system that purified treatment is carried out to petrochemical wastewater |
| CN201610124420.XA Active CN105621812B (en) | 2014-12-10 | 2014-12-10 | A kind of system of the leaded petrochemical wastewater of processing |
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| CN104860444A (en) * | 2015-05-27 | 2015-08-26 | 张世文 | Device and method for recovering coal tar in semi-coke wastewater |
| CN107010748A (en) * | 2017-06-09 | 2017-08-04 | 四川力天世纪科技有限公司 | The processing system of sewage discharge can be controlled |
| CN108485789B (en) * | 2018-03-07 | 2021-03-09 | 浙江三基钢管有限公司 | Rolling mill oil circulation supply device and supply method |
| CN109052725A (en) * | 2018-09-10 | 2018-12-21 | 公安海警学院 | A kind of sewage-treatment plant on naval vessels |
| CN115947507A (en) * | 2023-03-10 | 2023-04-11 | 广东红海湾发电有限公司 | Oily wastewater treatment method based on industrial water recovery |
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| DD249378A3 (en) * | 1985-04-22 | 1987-09-09 | Petrolchemisches Kombinat | METHOD FOR THE CLEANING OF WASTEWATERS AND PROCESSING WATERS OF MICROBIOLOGICAL PROTEIN RECOVERY |
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| CN100509662C (en) * | 2006-07-31 | 2009-07-08 | 中国石油化工股份有限公司 | Oil refinery sewage treatment and reusing process system and operation method thereof |
| US20080060997A1 (en) * | 2006-09-07 | 2008-03-13 | Musale Deepak A | Method of heavy metals removal from municipal wastewater |
| US9056784B2 (en) * | 2006-09-19 | 2015-06-16 | Ken V. Pandya | High efficiency water-softening process |
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| Publication number | Publication date |
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| CN105621810A (en) | 2016-06-01 |
| CN105621810B (en) | 2018-10-19 |
| CN104529060B (en) | 2016-06-15 |
| CN105693024A (en) | 2016-06-22 |
| CN105621811A (en) | 2016-06-01 |
| CN105621811B (en) | 2018-05-11 |
| CN104529060A (en) | 2015-04-22 |
| CN105621812A (en) | 2016-06-01 |
| CN105621812B (en) | 2018-10-02 |
| CN105693024B (en) | 2018-10-02 |
| CN105621813A (en) | 2016-06-01 |
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