CN109260962A - A kind of method of the composite membrane and its application of the efficient rapid acquiring of heavy metal in complex system - Google Patents
A kind of method of the composite membrane and its application of the efficient rapid acquiring of heavy metal in complex system Download PDFInfo
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- CN109260962A CN109260962A CN201811382575.9A CN201811382575A CN109260962A CN 109260962 A CN109260962 A CN 109260962A CN 201811382575 A CN201811382575 A CN 201811382575A CN 109260962 A CN109260962 A CN 109260962A
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- composite membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002351 wastewater Substances 0.000 claims abstract description 26
- 230000008929 regeneration Effects 0.000 claims abstract description 25
- 238000011069 regeneration method Methods 0.000 claims abstract description 25
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229960003638 dopamine Drugs 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000001179 sorption measurement Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 14
- 230000000536 complexating effect Effects 0.000 claims description 14
- 230000035515 penetration Effects 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000000108 ultra-filtration Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229910021432 inorganic complex Inorganic materials 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- -1 ether sulfone Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical group 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 6
- 150000004696 coordination complex Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000012459 cleaning agent Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 239000011975 tartaric acid Substances 0.000 description 6
- 235000002906 tartaric acid Nutrition 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000007781 pre-processing Methods 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229960005404 sulfamethoxazole Drugs 0.000 description 3
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
Classifications
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention belongs to heavy metal containing wastewater treatment field, in particular to the composite membrane of the efficient rapid acquiring of heavy metal and its method of application in a kind of complex system；The step of wastewater treatment are as follows: (1) heavy metal complex waste water is pumped into the system equipped with composite membrane and carries out purified treatment, (2) use diluted acid to regenerate as cleaning agent to used composite membrane, and the composite membrane after regeneration is reusable；The composite membrane is to deposit dopamine by blending graphene oxide, surface and produce, and is prepared simple, easy to operate, it is easy to accomplish polymorphic, multivalent state heavy metal separation, enrichment and recycling are suitable for all kinds of heavy metals and wastewater treatment are complexed, have broad spectrum activity.
Description
Technical field
The invention belongs to heavy metal containing wastewater treatment field, in particular to the efficient rapid acquiring of heavy metal in a kind of complex system
Composite membrane and its application method.
Background technique
By biochemical degradation or oxygenolysis form or variation of valence, water environment can not only occur for representative heavy metal in environment
Middle heavy metal had not only had poisonous effect outstanding, but also had the main features such as generality, complexity, latent long, control difficulty.It is such
Pollutant is usually present in the industrial wastewaters such as plating, chemical industry, process hides, in landfill leachate and surface water of getting dirty, underground water, and
With various organic or inorganic complex compounds and deposit, leading to conventional water treatment technology, (such as neutralization precipitation method, electrochemical process and biology are repaired
Multiple method etc.) there are heavy metals removal effects, and poor, medicament or energy consumption are big, investment and operating cost are high, operation operation is difficult, secondary
Pollution many deficiencies such as again.
Domestic and international patent and literature survey are shown, can be removed using after abolishing complex compound by the method adsorbed or precipitated
Heavy metal, such as discloses that a kind of light promotees contact break composite drug and UV combination is dropped application No. is 201810414764.3 Chinese patent
The method for solving copper complex and synchronous copper removal is irradiated by UV and is dropped after adding light rush contact break composite drug into complexing waste water
Heavy metal complex is solved and removes, this method complex process, medicament energy consumption is high, and has the risk of secondary pollution.Application is inhaled at present
Attached method removal heavy metal complex receives significant attention, and such as application No. is 201210360056.9 Chinese patents to disclose one kind
Heavy metal-EDTA chelates the processing method of waste water, after adjusting pH sediment fraction heavy metal, adds calcite, dolomite
Equal medicaments further remove removing heavy metals, and this method is complicated for operation, and secondary pollution can be brought by introducing medicament, and not consider heavy metal
Recycling.Electrolytic aluminium work is had studied Deng (Chemical Engineering Journal, 2013,214,327-335)
Absorption of the industry red soil to heavy metal and citric acid combined pollutant, although material source is cheap, process adaptability is good, adsorbent
Physicochemical property be difficult to ensure that recycling is not easy, and do not consider the resource reclaim of pollutant.Therefore, it is difficult to promote and apply.Application number
A kind of utilize in chelating resin selective extraction heavy metal-ammonia complexing waste water is disclosed for 201610197130.8 Chinese patent
The method of heavy metal, by the removal of achievable heavy metal-organic complex heavy metal in waste water and being returned using chelating resin
It receives, and the resin after regeneration may be reused, it is without secondary pollution, but resin adsorption method treating capacity is limited, limits its scale
Change application.
The high efficiency that heavy metal can be achieved, large capacity separation removal were reported about the research of composite membrane in recent years, were pollutions
The innoxious preferred material with recycling of object, but the removal of heavy metal in complex system is had not been reported.Therefore a kind of network is developed
The composite membrane of the efficient rapid acquiring of the heavy metal and its method of application has important practical significance and application value in zoarium system.
Summary of the invention
For the prior art to containing heavy metal complexing waste water there are load resistance abilities poor, poor processing effect, secondary pollution weight
The defects of, the present invention provides a kind of method of the composite membrane and its application of the efficient rapid acquiring of heavy metal in complex system.The party
Method is using composite membrane while to remove the heavy metal in waste water and its complex compound, meets purification of water quality requirement, then full to absorption
Composite membrane with after is regenerated using conventional dilute acid soln, realizes the resource utilization of heavy metal, while compound after regeneration
Film is repeatable to be recycled.
Technical scheme is as follows:
A kind of composite membrane, the composite membrane is that flat sheet membrane is made with graphene oxide doped matrix, in the flat sheet membrane
Surface deposits poly-dopamine and is made.
A kind of preparation method of composite membrane, comprising the following steps:
A, it after the graphene oxide powder of the solvent of 57~91.9 mass parts and 0.1~5 mass parts being mixed dispersion, is added
The film matrix powder of 7~18 mass parts and the pore-foaming agent of 1~20 mass parts obtain casting solution, casting solution is stirred to react 5~
48h, reaction temperature control are 50~100 DEG C, form diaphragm using thermotropic phase method after standing and defoaming, then diaphragm is put into distilled water
Middle immersion, the flat sheet membrane through dry obtained graphene oxide doped；
B, flat sheet membrane made from step A is placed in ultrafiltration cup, the dopamine that 0.5~5g/L of 50~500mL is added is molten
Liquid, deposition is dry after the completion to be made composite membrane.
Preferably, the film matrix is Kynoar (PVDF), polyether sulfone (PES), polyacrylonitrile (PAN) and polysulfones
(PS) any one or several in.
Preferably, the solvent is n,N-Dimethylformamide, triethyl phosphate, n,N-dimethylacetamide, neck benzene two
Any one or a few in formic acid dimethyl ester, trimethylolpropane.
Preferably, the pore-foaming agent is polyvinylpyrrolidone, any one in polyethylene glycol.
Preferably, effective depositional area of the ultrafiltration cup film is 30cm2, water discharge speed is 1~50.0Lm-2·h-1。
Above-mentioned composite membrane can be used for the rapid acquiring of heavy metal in complex system；Method particularly includes:
Heavy metal complexing wastewater pH to be processed is adjusted to 2~10 by step 1, is pumped into the filtering body equipped with the composite membrane
System, by adsorption temp control be 5~45 DEG C, flow control is 0.1~20.0Lm-2·h-1, until adsorption penetration；
After step 2, adsorption penetration, diluted acid is pumped into the filtration system in step 1 and is regenerated, the composite membrane after regeneration can
It reuses.
Preferably, heavy metal complexing waste water includes heavy metal and organic or inorganic complex compound, the heavy metal
It is Cu for heavy metal cation2+、Ni2+、Zn2+、Cd2+、Pb2+In it is any one or several；The organic complex is organic
Acid, dyestuff or antibiotic, such as tartaric acid, oxalic acid, citric acid, ethylenediamine tetra-acetic acid, acid black, tetracycline, sulfamethoxazole；Institute
The inorganic complex stated is ammonia, pyrophosphoric acid.
Preferably, in step 2, the diluted acid is hydrochloric acid, nitric acid or the sulfuric acid solution that mass fraction is 1%~10%, then
Raw temperature is 5~50 DEG C, and flow velocity is 0.1~30Lm-2·h-1。
Compared with the existing technology, advantages of the present invention is as follows,
(1) present invention recycles two process processing heavy metals complexing waste water using reinforcing removal and regeneration, can substantially cut
Heavy metal concentration in waste reduction water, the complexing suitable for a variety of common heavy metals and organic or inorganic compound wastewater, in waste water
Agent can strengthen the removal of heavy metal, have broad spectrum activity；
(2) the compound membrane preparation method in the present invention is simple, by graphene oxide doped in film matrix, efficiently solves
The problem of nanoscale materials engineeringization application；Surface deposited the composite membrane of dopamine, can play the functions polymerization of olefin using catalyst such as nitrogen oxygen simultaneously
Effect and fenestra crown_interception improve trapping rate, enhance heavy metal accumulation ability；
(3) present invention can not only realize the recycling of heavy metal as regenerative agent using conventional diluted acid, but also can realize compound
Film recycles, and composite membrane preparation cost is cheap, and application operating is easy；
(4) recycling benefits of the present invention are significant, have a extensive future.
Detailed description of the invention
Fig. 1 is embodiment 1-11 composite membrane to heavy metal treatment effect table in complex system.
Specific embodiment:
Embodiment 1
The method of the composite membrane and its application of the efficient rapid acquiring of heavy metal, the steps include: in a kind of complex system
(1) by the compound wastewater of lead and tartaric acid to be processed, (initial concentration of lead is 10mg/L, and the starting of tartaric acid is dense
Degree is 10mg/L) pH to 5 is adjusted, it is then pumped into the filtration system of filling composite membrane, control adsorption temp is 30 DEG C, water discharge speed
For 15.0Lm-2·h-1, until adsorption penetration.
(2) after adsorption saturation, the filtration system that the hydrochloric acid that mass fraction is 10% is pumped into step (1) is regenerated,
Controlling regeneration temperature is 25 DEG C, water discharge speed 30.0Lm-2·h-1, the composite membrane after regeneration is washed till neutrality with clear water, obtains
Regenerated composite membrane.
Composite membrane in the present embodiment the preparation method comprises the following steps:
(A) N,N-dimethylformamide of 81 mass parts and the graphene oxide powder of 2 mass parts are added in the reactor
After mixing well dispersion, the PEG of PVDF powder and 5 mass parts that 12 mass parts are added obtains casting solution, and casting solution is being reacted
It is stirred to react in device for 24 hours, reaction temperature control is 80 DEG C, forms diaphragm using thermotropic phase method after standing and defoaming, then diaphragm is put
Enter and is impregnated in distilled water for 24 hours, the flat sheet membrane through dry obtained graphene oxide doped；
(B) flat sheet membrane made from step A is placed in ultrafiltration cup, the dopamine solution of the 2g/L of 250mL is added, wherein surpassing
Effective depositional area of filter bowl film is 30cm2, water discharge speed 25.0Lm-2·h-1, deposition is dry after the completion to be made composite membrane.
Embodiment 2
With embodiment 1, except that: the initial concentration of lead is 5mg/L in step (1), and acid black replaces tartaric acid, and
Initial concentration is 20mg/L, and it is 2 that preprocessing process, which adjusts pH value, and control adsorption temp is 45 DEG C, water discharge speed 20.0Lm-2·h-1N, step (2) are regenerated using the dust technology that mass fraction is 5%, and regeneration temperature is 35 DEG C, flow velocity 10.0Lm-2·
h-1。
Embodiment 3
With embodiment 1, except that: the initial concentration of lead is 20mg/L in step (1), and oxalic acid replaces tartaric acid, and
Initial concentration is 2mg/L, and it is 6 that preprocessing process, which adjusts pH value, and control adsorption temp is 5 DEG C, water discharge speed 0.1Lm-2·
h-1, the dilute sulfuric acid regeneration that step (2) regenerative process is 2% using mass fraction, regeneration temperature is 50 DEG C, flow velocity 0.1Lm-2·h-1。
Embodiment 4
With embodiment 1, except that: the initial concentration of lead is 50mg/L in step (1), and tetracycline replaces tartaric acid,
And concentration is 50mg/L, it is 4 that preprocessing process, which adjusts pH value, and control adsorption temp is 40 DEG C, water discharge speed 1.0Lm-2·
h-1, step (2) regenerative process is the regeneration of 5% dilute hydrochloric acid using mass fraction, and regeneration temperature is 25 DEG C, flow velocity 10.0Lm-2·h-1。
Embodiment 5
With embodiment 1, except that: to be processed in step (1) is Nanjing waste water from plating plant, and initial pH is 4.7, copper
Concentration be 9.8mg/L, citric acid concentration 13.6mg/L.Regenerative process is the regeneration of 1% dilute sulfuric acid, regeneration using mass fraction
Flow velocity is 5.0Lm-2·h-1。
Embodiment 6
The method of the composite membrane and its application of the efficient rapid acquiring of heavy metal, the steps include: in a kind of complex system
(1) by the compound wastewater of nickel and sulfamethoxazole to be processed, (initial concentration of nickel is 5mg/L, sulfamethoxazole
Initial concentration be 3mg/L) adjust pH to 8, by pretreated heavy metal complexing waste water be pumped into filling composite membrane filtering body
System, control adsorption temp are 45 DEG C, water discharge speed 0.5Lm-2·h-1, until adsorption penetration.
(2) after adsorption saturation, the filtration system that 8% hydrochloric acid is pumped into step (1) is regenerated, controls regeneration temperature
It is 5 DEG C, water discharge speed 2.0Lm-2·h-1, the composite membrane after regeneration is washed till neutrality with clear water, obtains regenerated composite membrane.
Composite membrane in the present embodiment the preparation method comprises the following steps:
(A) graphene oxide powder of triethyl phosphate and 0.1 parts by weight that 91.9 parts by weight are added in the reactor is filled
Divide after mixing dispersion, the PVP of PAN powder and 1 parts by weight that 7 parts by weight are added obtains casting solution, in the reactor by casting solution
It is stirred to react for 24 hours, reaction temperature control is 100 DEG C, forms diaphragm using thermotropic phase method after standing and defoaming, then diaphragm is put into steaming
It is impregnated in distilled water for 24 hours, the flat sheet membrane through dry obtained graphene oxide doped；
(B) flat sheet membrane made from step A is placed in ultrafiltration cup, the dopamine solution of the 5g/L of 500mL is added, wherein surpassing
Effective depositional area of filter bowl film is 30cm2, water discharge speed 50.0Lm-2·h-1, deposition is dry after the completion to be made composite membrane.
Embodiment 7
The method of the composite membrane and its application of the efficient rapid acquiring of heavy metal, the steps include: in a kind of complex system
(1) by the compound wastewater of cadmium and ethylenediamine tetra-acetic acid to be processed, (initial concentration of cadmium is 50mg/L, ethylenediamine tetraacetic
The initial concentration of acetic acid is 100mg/L) pH to 7 is adjusted, pretreated heavy metal complexing waste water is pumped into filling composite membrane
Filtration system, control adsorption temp are 5 DEG C, water discharge speed 0.5Lm-2·h-1, until adsorption penetration.
(2) after adsorption saturation, the filtration system that 10% dust technology is pumped into step (1) is regenerated, control regeneration
Temperature is 25 DEG C, water discharge speed 0.1Lm-2·h-1, the composite membrane after regeneration is washed till neutrality with clear water, obtains regenerated multiple
Close film.
Composite membrane in the present embodiment the preparation method comprises the following steps:
(A) oxidation of the DMAC N,N' dimethyl acetamide that mass fraction is 57 parts by weight and 5 parts by weight is added in the reactor
After graphene powder mixes well dispersion, the PEG of PS powder and 20 parts by weight that 18 parts by weight are added obtains casting solution, by casting film
Liquid is stirred to react for 24 hours in the reactor, and reaction temperature control is 50 DEG C, forms diaphragm using thermotropic phase method after standing and defoaming, then
Diaphragm is put into distilled water and is impregnated for 24 hours, the flat sheet membrane through dry obtained graphene oxide doped；
(B) flat sheet membrane made from step A is placed in ultrafiltration cup, the dopamine solution of the 1g/L of 50mL is added, wherein surpassing
Effective depositional area of filter bowl film is 30cm2, water discharge speed 1.0Lm-2·h-1, deposition is dry after the completion to be made composite membrane.
Embodiment 8
The method of the composite membrane and its application of the efficient rapid acquiring of heavy metal, the steps include: in a kind of complex system
(1) by the compound wastewater of zinc and sodium citrate to be processed, (initial concentration of zinc is 5mg/L, and sodium citrate rises
Beginning concentration is 30mg/L) pH to 5 is adjusted, pretreated heavy metal complexing waste water is pumped into the filtration system of filling composite membrane,
Controlling adsorption temp is 40 DEG C, water discharge speed 10.0Lm-2·h-1, until adsorption penetration.
(2) after adsorption saturation, the filtration system that 2% dilute sulfuric acid is pumped into step (1) is regenerated, control regeneration temperature
Degree is 50 DEG C, water discharge speed 5.0Lm-2·h-1, the composite membrane after regeneration is washed till neutrality with clear water, obtains regenerated compound
Film.
Composite membrane in the present embodiment the preparation method comprises the following steps:
(A) graphite oxide of the trimethylolpropane that mass fraction is 74 parts by weight and 3 parts by weight is added in the reactor
After alkene powder mixes well dispersion, the PEG of PES powder and 8 parts by weight that 15 parts by weight are added obtains casting solution, and casting solution is existed
It is stirred to react in reactor for 24 hours, reaction temperature control is 75 DEG C, forms diaphragm using thermotropic phase method after standing and defoaming, then by film
Piece, which is put into distilled water, to be impregnated for 24 hours, the flat sheet membrane through dry obtained graphene oxide doped；
(B) flat sheet membrane made from step A is placed in ultrafiltration cup, the dopamine solution of the 0.5g/L of 300mL is added, wherein
Effective depositional area of ultrafiltration cup film is 30cm2, water discharge speed 30.0Lm-2·h-1, drying is made compound to deposition after the completion
Film.
Embodiment 9
With embodiment 8, except that: the initial concentration of nickel is 35mg/L in step (1), and the initial concentration of ammonia is
50mg/L, it is 10 that preprocessing process, which adjusts pH value, and control adsorption temp is 10 DEG C, water discharge speed 0.5Lm-2·h-1, step
(2) regenerative process is regenerated using 5% dilute sulfuric acid, and regeneration temperature is 30 DEG C, flow velocity 0.1Lm-2·h-1。
Embodiment 10
With embodiment 8, except that: the initial concentration of copper is 50mg/L in step (1), and the initial concentration of pyrophosphoric acid is
80mg/L, it is 8 that preprocessing process, which adjusts pH value, and control adsorption temp is 30 DEG C, water discharge speed 2.0Lm-2·h-1, step
(2) regenerative process is regenerated using 10% dilute sulfuric acid, and regeneration temperature is 25 DEG C, flow velocity 0.5Lm-2·h-1。
Embodiment 11
With embodiment 1 the difference is that composite membrane used is the pvdf membrane that not oxidised graphene and dopamine are modified,
Preparation method are as follows:
The PVDF powder that mass fraction is the DMAC N,N' dimethyl acetamide of 62 parts by weight, 18 parts by weight is added in the reactor
With the PEG of 20 parts by weight, casting solution is obtained after mixing well, casting solution is stirred to react to reaction temperature control for 24 hours in the reactor
50 DEG C are made as, diaphragm is formed using thermotropic phase method after standing and defoaming, then diaphragm is put into distilled water and is impregnated for 24 hours, is made through dry
Obtain PVDF flat sheet membrane.
Embodiment 12
The composite membrane of embodiment 1-11 is set as heavy metal aqueous concentration to the adsorption penetration point of heavy metal and reaches " plating dirt
Contaminate object discharge standard " (GB21900-2008) table 3 discharge limitation when, be effectively treated volume be out penetration by water when per membrane area
Wastewater treatment volume (L/m2).Treatment effect is shown in Fig. 1, it is seen that the present invention is to the weight in heavy metal and organic and inorganic complexing waste water
Metal has good treatment effect.
The regeneration effect of composite membrane counterweight metal complex heavy metal in waste water can be indicated with rate of recovery R, specific to calculate public affairs
Formula is as follows:
Wherein C0Indicate the concentration (mg/L) of heavy metal in initial soln, CeThe concentration of pollutant when representing penetration by water
(mg/L), CRIndicate the concentration (mg/L) of heavy metal in actified solution, VBWastewater volume (L) is handled when representing penetration by water, VRTable
Show desorption volume (L).To normalize composite membrane processing capacity, definition reaches " plating pollutant emission when heavy metal aqueous concentration
Standard " (GB21900-2008) table 3 discharge limitation when be breakthrough point, volume V is effectively treatedEPer membrane area when to go out penetration by water
Wastewater treatment volume (L/m2), it may be assumed that
Wherein, A is the effective membrane area (m of adsorption filtration system2)。
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of composite membrane, which is characterized in that the composite membrane is that flat sheet membrane is made with graphene oxide doped matrix, in institute
Plain film film surface deposition poly-dopamine is stated to be made.
2. a kind of preparation method of composite membrane, which comprises the following steps:
A, after the graphene oxide powder of the solvent of 57~91.9 mass parts and 0.1~5 mass parts being mixed dispersion, addition 7~
The film matrix powder of 18 mass parts and the pore-foaming agent of 1~20 mass parts obtain casting solution, casting solution are stirred to react 5~48h, instead
Answering temperature control is 50~100 DEG C, forms diaphragm using thermotropic phase method after standing and defoaming, then diaphragm is put into distilled water and is soaked
Bubble, the flat sheet membrane through dry obtained graphene oxide doped；
B, flat sheet membrane made from step A is placed in ultrafiltration cup, the dopamine solution of 0.5~5g/L of 50~500mL is added, sunk
Dry obtained composite membrane after the completion of product.
3. the preparation method of composite membrane as claimed in claim 2, which is characterized in that the film matrix is Kynoar, gathers
It is any one or several in ether sulfone, polyacrylonitrile and polysulfones.
4. the preparation method of composite membrane as claimed in claim 2, which is characterized in that the solvent is N, N- dimethyl formyl
Amine, triethyl phosphate, DMAC N,N' dimethyl acetamide, dimethyphthalate, any one or a few in trimethylolpropane.
5. the preparation method of composite membrane as claimed in claim 2, which is characterized in that the pore-foaming agent is polyvinylpyrrolidine
Any one in ketone, polyethylene glycol.
6. the preparation method of composite membrane as claimed in claim 2, which is characterized in that effective depositional area of the ultrafiltration cup film
For 30cm2, water discharge speed is 1~50.0Lm-2·h-1。
7. composite membrane as claimed in any one of claims 1 to 6 is applied in processing heavy metal complexing waste water.
8. the use as claimed in claim 7, which is characterized in that concrete application method are as follows:
Heavy metal complexing wastewater pH to be processed is adjusted to 2~10 by step 1, is pumped into the filtration system equipped with the composite membrane, will
Adsorption temp control is 5~45 DEG C, flow control is 0.1~20.0Lm-2·h-1, until adsorption penetration；
After step 2, adsorption penetration, diluted acid is pumped into the filtration system in step 1 and is regenerated, the composite membrane after regeneration is repeatable
It uses.
9. application as claimed in claim 8, which is characterized in that the heavy metal complexing waste water include heavy metal and it is organic or
Inorganic complex, the heavy metal are heavy metal cation, are Cu2+、Ni2+、Zn2+、Cd2+、Pb2+In it is any one or several；
The organic complex is organic acid, dyestuff or antibiotic；The inorganic complex is ammonia, pyrophosphoric acid.
10. application as claimed in claim 8, which is characterized in that in step 2, the diluted acid is that mass fraction is 1%~10%
Hydrochloric acid, nitric acid or sulfuric acid solution, regeneration temperature be 5~50 DEG C, flow velocity be 0.1~30Lm-2·h-1。
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