CN115582102B - Porous sponge adsorbent and preparation method and application thereof - Google Patents
Porous sponge adsorbent and preparation method and application thereof Download PDFInfo
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- CN115582102B CN115582102B CN202211220539.9A CN202211220539A CN115582102B CN 115582102 B CN115582102 B CN 115582102B CN 202211220539 A CN202211220539 A CN 202211220539A CN 115582102 B CN115582102 B CN 115582102B
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- sponge
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 68
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 48
- 239000010457 zeolite Substances 0.000 claims abstract description 48
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 34
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000002033 PVDF binder Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 55
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 6
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 62
- 229910001431 copper ion Inorganic materials 0.000 abstract description 62
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000011521 glass Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 11
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000012528 membrane Substances 0.000 description 9
- 238000005070 sampling Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002145 thermally induced phase separation Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
- 206010010356 Congenital anomaly Diseases 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007698 birth defect Effects 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000008383 multiple organ dysfunction Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a porous sponge adsorbent, a preparation method and application thereof, wherein the preparation method of the porous sponge adsorbent comprises the following steps: s1, preparing a zeolite imidazole skeleton ZIF-L; s2, dissolving the zeolite imidazole skeleton ZIF-L in the S1 in N, N dimethylformamide to prepare zeolite imidazole skeleton solution; s3, uniformly dispersing the zeolite imidazole skeleton solution in the S2; s4, heating the solution after the reaction in the S3, and adding polyvinylidene fluoride and stirring; s5, immersing the melamine sponge into the solution prepared in the S4, taking out the melamine sponge from the solution, and drying to obtain the melamine sponge. The electron microscope result shows that the adsorbent maintains the original three-dimensional network structure of the melamine sponge, and the zeolite imidazole skeleton loaded on the sponge presents a hollow annular shape. The adsorbent disclosed by the invention has excellent adsorption performance on lead and copper ions, and is mainly characterized by higher adsorption capacity, faster adsorption rate, better anti-interference capability and regeneration and recycling property.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a porous sponge adsorbent for adsorbing heavy metal wastewater and a preparation method thereof; the invention also relates to application of the porous adsorbent.
Background
Along with the acceleration of industrialization progress, industries such as mining industry, smelting industry, electroplating industry, battery industry and the like develop rapidly, so that the discharge amount of heavy metal wastewater is increased rapidly, and serious pollution to water environment is caused. Lead (Pb) and copper (Cu) are one of the two most widely used heavy metals, with high toxicity and non-biodegradability. The lead and copper in the water body can be enriched in fish and other aquatic organisms, enter the human body through a food chain, and also can directly enter the human body through a drinking water system, so that serious damage to the human body, such as multiple organ dysfunction, birth defects and the like, is caused.
Currently, a series of methods for removing heavy metals from water have been developed, including flocculation, chemical precipitation, ion exchange, adsorption, electrolysis and membrane filtration. Among them, the adsorption method is considered as a very attractive heavy metal removal technology because of its advantages of simple design and operation, low cost, good removal effect, no secondary pollution, etc. However, the conventional adsorbent is generally poor in adsorption performance, so that it is highly desirable to design a novel adsorbent with high performance and high selectivity, and meanwhile, the requirement of industrial application, i.e., easy separation, recoverability, strong anti-interference capability, etc., should be met.
The invention discloses an iron ion adsorption sponge, a preparation method and application thereof, wherein the adsorption sponge is prepared by firstly carrying out amination modification on melamine sponge by using a silane coupling agent, then carrying out hydroformylation modification on the melamine sponge by using glyoxal alcohol solution, and finally carrying out reflux modification on the melamine sponge and rhodamine hydrazide, the prepared adsorption sponge can be used for selectively enriching and recycling iron ions and can be reused after being regenerated by simple alkaline washing.
Chinese patent publication No. CN106279033a discloses a flaky cross ZIF-L and a method for preparing the same. The appearance of the ZIF-L is in a sheet cross shape, wherein the sheets forming the sheet cross shape ZIF-L are in a salix leaf shape, the sheet length is 4.5-8.5 mu m, the sheet thickness is 0.2-0.4 mu m, the sheet center width is 1-3 mu m, the sheet cross shape is in a cross sheet cross shape or more than three sheets of multi-sheet cross shapes, and the specific surface area of the sheet cross shape ZIF-L is more than or equal to 303m 2/g; the method comprises the steps of preparing a zinc nitrate hexahydrate aqueous solution and a 2-methylimidazole aqueous solution respectively, uniformly mixing the zinc nitrate hexahydrate aqueous solution and the 2-methylimidazole aqueous solution to obtain a mixed solution, placing the mixed solution in a closed state to react at 115-135 ℃ to obtain a reaction solution, and sequentially carrying out solid-liquid separation, washing, solvent activation and drying on the reaction solution to obtain a target product. Because the particle size of ZIF-L is small, when it is used for adsorbing heavy metal ions in aqueous solutions, ZIF-L is extremely difficult to recover and the effect of adsorbing heavy metal ions is poor, so that improvement of the above-mentioned technology is needed.
Disclosure of Invention
The invention aims to provide a porous sponge adsorbent and a preparation method thereof, and the prepared porous sponge adsorbent has the advantages of higher adsorption rate, higher adsorption capacity, better anti-interference capability and regeneration cycle capability on lead and copper ions, and is easy to recycle.
It is another object of the present invention to provide the use of a porous sponge adsorbent for removing lead and copper from wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for preparing a porous sponge adsorbent, comprising the following steps:
s1, preparing a zeolite imidazole skeleton ZIF-L;
s2, dissolving the zeolite imidazole skeleton ZIF-L in the S1 in N, N dimethylformamide to prepare zeolite imidazole skeleton solution;
s3, uniformly dispersing the zeolite imidazole skeleton solution in the S2;
s4, heating the solution after the reaction in the S3, and adding polyvinylidene fluoride and uniformly stirring;
S5, immersing the melamine sponge into the solution prepared in the S4, taking out the melamine sponge from the solution, and drying to obtain the multi Kong Haimian adsorbent.
According to the invention, the zeolite imidazole skeleton ZIF-L is selected and dissolved in N, N dimethylformamide, so that the zeolite imidazole skeleton ZIF-L is uniformly dispersed, polyvinylidene fluoride is added, and then melamine sponge is immersed in the solution, and the porous sponge adsorbent is prepared through a thermally induced phase separation process, so that the original three-dimensional network structure of the melamine sponge is maintained, the zeolite imidazole skeleton can be stably adsorbed on the melamine sponge, and the loading rate of the zeolite imidazole skeleton on the melamine sponge is 35% -45%. The above steps are indispensable, and none of them can stably adsorb the zeolite imidazole skeleton in the melamine sponge, so that the effect that the porous sponge adsorbent is easily separated from the aqueous phase cannot be achieved.
The zeolite imidazole skeleton loaded on the sponge presents a hollow annular shape, and the zeolite imidazole skeleton with the shape has selective adsorptivity to lead and copper in wastewater and has good adsorption effect to lead and copper in wastewater.
The zeolite imidazole skeleton ZIF-L is selected by the invention, so that the zeolite imidazole skeleton ZIF-L can be synthesized in a water phase, is more environment-friendly, and has higher synthesis rate and yield compared with the traditional zeolite imidazole skeleton ZIF-8.
The reason why polyvinylidene fluoride is a typical crosslinking adhesive is selected in the invention is that polyvinylidene fluoride has good chemical stability and thermal stability and can generate a porous structure in a thermally induced phase separation process, and N, N-dimethylformamide is selected in the invention is that N, N-dimethylformamide is mutually soluble with most organic solvents and is commonly used as a solvent with low volatility.
In a preferred embodiment of the invention, the mass-to-volume ratio of the zeolite imidazole framework ZIF-L to the melamine sponge is 1-3g:10-15cm 3.
In a preferred embodiment of the invention, ultrasonic cell disruption is used in S3 to uniformly disperse the zeolitic imidazolate framework solution in S2.
In a preferred embodiment of the invention, the ultrasonic cytoclasis instrument in S3 has a power of 800-1200W, and the high power makes the zeolite imidazole skeleton dispersed more uniformly in the N, N-dimethylformamide solution.
In a preferred embodiment of the invention, the time of ultrasound in S3 is 5-15min. Further preferably, the time of the ultrasonic treatment in the step S3 is 7-13min, and the porous functionalized sponge adsorbent prepared in the ultrasonic treatment time of 7-13min has the best adsorption performance on lead and copper ions, because the porous functionalized sponge adsorbent has a unique hollow annular morphology, and the morphology is beneficial to promoting mass transfer and accessibility of active sites.
In a preferred embodiment of the invention, the mass to volume ratio of the zeolite imidazole framework ZIF-L, N, N dimethylformamide and polyvinylidene fluoride is 1-3g:80-120mL:1-3g.
In a preferred embodiment of the invention, the temperature of the heating in S4 is 40-60 ℃.
In a preferred embodiment of the invention, the melamine sponge is immersed in the solution prepared in S3 in S4 and repeatedly pressed two to four times to ensure that the melamine sponge is in sufficient contact with the solution.
In a preferred embodiment of the invention, the temperature of the drying in S5 is 130-170 ℃ and the drying time is 0.5-1.5h.
In a preferred embodiment of the present invention, the preparation method of the zeolite imidazole framework ZIF-L in S1 comprises the following steps:
1) Zn (NO 3)2·6H2 O and dimethyl imidazole are respectively dissolved in deionized water to obtain solution A and solution B, and the solution A and the solution B are mixed to prepare a mixed solution;
2) Stirring the mixed solution obtained in the step 1) for 1-3h at the temperature of 20-30 ℃;
3) And (3) filtering the mixed solution after the reaction in the step (2) after stirring is completed to obtain a solid filter material, washing the solid filter material by adopting methanol and deionized water, and then freeze-drying the solid filter material to obtain the zeolite imidazole skeleton ZIF-L.
In a preferred embodiment of the present invention, in step 1), the ratio of the amounts of zinc ions, dimethylimidazole and deionized water in the mixture is 1:8-10:1000-1200 to ensure that the zeolite imidazole framework ZIF-L is synthesized.
In a preferred embodiment of the invention, in step 1), zn (NO 3)2·6H2 O and dimethylimidazole are dissolved in 150-250mL deionized water, respectively, to give solution A, B.
In a preferred embodiment of the invention, in step 1), zn (NO 3)2·6H2 O to dimethylimidazole mass ratio is 5-7:14.
In a preferred embodiment of the invention, in step 2), the stirring rate is 15-40rpm.
In a preferred embodiment of the invention, in step 3), the lyophilization time is 20-30 hours.
The invention also discloses a porous sponge adsorbent prepared by the method.
In a preferred embodiment of the invention, the loading rate of the zeolite imidazole framework on the melamine sponge is 35% -45%; preferably, the loading rate of the zeolite imidazole framework on the melamine sponge is 39.82% to 40.72%.
The invention also discloses application of the porous sponge adsorbent in adsorbing lead and copper in wastewater.
In a preferred embodiment of the invention, the porous sponge adsorbent has higher lead and copper ion removal rate when the pH value of the wastewater is 4-6.
In some specific embodiments, the adsorbent has an adsorption capacity of 624.8mg/g for lead ions in a body of water.
In some specific embodiments, the adsorbent has an adsorption capacity of 588.6mg/g for copper ions in a body of water.
In some specific embodiments, the adsorbent maintains the original three-dimensional network structure of the melamine sponge, and the zeolite imidazole skeleton loaded on the sponge presents a hollow annular morphology.
In some embodiments, the adsorption effect of the adsorbent on lead and copper ions is mainly derived from nitrogen-containing functional groups contained on the surface of the adsorbent.
Compared with the existing adsorbent and preparation method, the invention has the advantages that:
1) The porous functional sponge adsorbent prepared by the invention has the advantages of higher adsorption rate, higher adsorption capacity, better anti-interference capability and regeneration cycle capability on lead and copper ions, is easy to recycle, and is suitable for large-scale industrial application;
2) The preparation method of the porous functional sponge adsorbent provided by the invention is simple and low in cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention.
Fig. 1 is an SEM image of the adsorbent obtained in example 1.
Fig. 2 is an XRD pattern of the adsorbent obtained in example 1.
FIG. 3 is a nitrogen-adsorption desorption isotherm plot of the adsorbent obtained in example 1.
FIG. 4 is a graph showing the kinetics of the lead copper ion by the adsorbent obtained in example 1.
FIG. 5 is an isothermal adsorption curve of lead copper ions by the adsorbent obtained in example 1.
FIG. 6 is a graph showing the influence of pH on the adsorption capacity of the adsorbent obtained in example 1 on lead copper ions.
FIG. 7 is a graph showing the influence of coexisting ions on the adsorption capacity of lead ions by the adsorbent obtained in example 1.
FIG. 8 is a graph showing the influence of coexisting ions on the adsorption capacity of copper ions by the adsorbent obtained in example 1.
FIG. 9 is a graph showing the effect of natural organic matters on the adsorption capacity of the adsorbent obtained in example 1 on lead and copper ions.
FIG. 10 is a graph showing the selectivity of the adsorbent obtained in example 1 to lead copper ions.
FIG. 11 shows the results of the recycling property test of the adsorbent obtained in example 1.
FIG. 12 is a continuous flow test result of the adsorbent obtained in example 1.
FIG. 13 is a Fourier infrared spectrum of the adsorbent obtained in example 1 after adsorbing lead copper ions.
FIG. 14 is a total X-ray photoelectron spectrum of the adsorbent obtained in example 1 after adsorbing lead copper ions.
FIG. 15 is a high-resolution X-ray photoelectron spectrum of N1s after lead copper ions are adsorbed by the adsorbent obtained in example 1.
Fig. 16 shows the thermal mechanical properties of different materials for lead ion adsorption.
Fig. 17 shows the thermal mechanical properties of different materials for copper ion adsorption.
Fig. 18 is an effect of ultrasound duration on lead ion adsorption thermodynamic properties.
Fig. 19 is an effect of ultrasonic duration on copper ion adsorption thermodynamic properties.
Detailed Description
The following detailed description of embodiments of the present invention will be given with reference to the accompanying drawings and examples, by which the implementation process of how the present invention can be applied to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the starting materials and reagents in the examples of the invention were all purchased commercially.
The analysis method in the embodiment of the invention is as follows:
A Scanning Electron Microscope (SEM) of the material is characterized by adopting a TESCAN MIRA model field emission scanning electron microscope;
The X-ray diffraction (XRD) spectrum of the material is characterized by adopting an X-ray diffractometer model Bruker D8, the scanning speed is 10 degrees/min, and the scanning range of a 2 theta angle is 5-85 degrees;
The specific surface area and pore size distribution (BET) of the material is characterized by adopting an automatic specific surface area and pore size analyzer of ASAP 2460 model;
the concentration of metal ions in the solution was measured on an inductively coupled plasma mass spectrometer (ICP-MS).
Example 1: porous functional sponge adsorbent and preparation method thereof
The embodiment provides a porous functional sponge adsorbent, which is obtained by taking melamine sponge as a structural support body and fixing a zeolite imidazole skeleton on the surface of the melamine sponge structure by adopting an impregnation method.
The embodiment also provides a preparation method of the porous functionalized sponge adsorbent
Dissolving 6gZn (NO 3)2·6H2 O and 14g of dimethyl imidazole in 200mL of deionized water respectively to obtain a solution A, B, mixing A, B solutions, placing the mixed solution into a constant-temperature water bath kettle at 25 ℃ for stirring for 2 hours, filtering the mixed solution to obtain a solid filtrate, washing the solid filtrate with methanol once and then with deionized water for two times, placing the solid filtrate into a vacuum freeze dryer for drying to obtain a zeolite imidazole skeleton (ZIF-L), dissolving 2g of zeolite imidazole skeleton into 100mL of pure N, N-dimethylformamide, placing the solution into an ultrasonic cell disrupter for ultrasonic treatment, placing the solution obtained after ultrasonic treatment into a constant-temperature water bath kettle at 50 ℃, slowly adding 2g of polyvinylidene fluoride into the solution, stirring for 1 hour to obtain a uniform mixed solution, cutting melamine sponge with the size of 1.5X1.5X 3 into the uniform mixed solution, repeatedly extruding the melamine sponge three times, and placing the sponge into an oven for drying to obtain the porous adsorbent (MS 10).
Wherein the stirring speed of the constant-temperature water bath kettle is 25rpm, the freeze drying time is 24 hours, the ultrasonic time is 10 minutes, the temperature of the oven is set to 150 ℃, and the baking time is 1 hour; the working temperature of the vacuum freeze dryer is-55 ℃ and the vacuum degree is 30Pa.
Example 2: characterization of porous functionalized sponge adsorbent
The morphology of the porous functionalized sponge adsorbent prepared in example 1 was observed using a scanning electron microscope, and the results are shown in fig. 1. The detection result shows that the adsorbent maintains the original three-dimensional network structure of the melamine sponge, and the zeolite imidazole skeleton loaded on the sponge presents a hollow annular shape.
The porous functionalized sponge adsorbent prepared in example 1 was analyzed for crystal structure using an X-ray diffractometer, and the results are shown in fig. 2. The detection result shows that diffraction peaks of ZIF-L and ZIF-8 appear in the spectrum at the same time, which indicates that the adsorbent is a mixed phase composed of ZIF-L and ZIF-8 and takes the ZIF-8 phase as the main phase.
The porous functionalized sponge adsorbent prepared in example 1 was characterized for specific surface area and pore size distribution using an automatic specific surface area and pore size analyzer, and the nitrogen adsorption-desorption isotherm results are shown in fig. 3. The detection result shows that the isotherm of the adsorbent belongs to an IV-type isotherm and is provided with a hysteresis loop, which indicates that the material is of a mesoporous structure.
Example 3: adsorption kinetics performance test of porous functional sponge adsorbent on lead and copper ions
80Mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into a glass bottle containing 80mL of lead nitrate or copper nitrate solution having an initial concentration of about 10mg/L, and the glass bottle was placed in a constant temperature shaker, and was subjected to constant temperature shaking at 25℃and 180r/min, sampling was performed by a syringe at shaking times of 0,1, 2, 5, 10, 20, 30, 45, 60, 120 minutes, each time 2mL was taken, the sampled liquid was subjected to a 0.22 μm filter membrane, and the residual concentration of lead and copper ions therein was measured by ICP-MS, and all groups of experiments were repeated twice in this process, and the results were shown in FIG. 4.
As can be seen from fig. 4, the adsorption of the lead and copper ions by the adsorbent shows a process of 'fast before slow and then tending to balance', the adsorption of the lead ions tends to balance at 10min, and the adsorption of the copper ions tends to balance at 10min, which shows that the adsorption rate of the lead ions by the adsorbent is faster than the adsorption rate of the copper ions, meanwhile, the kinetic data is fitted by adopting a mass transfer model, and the mass transfer coefficient of the lead is calculated to be 7.79×10 -6 m/s, and the mass transfer coefficient of the copper is calculated to be 2.54×10 -6 m/s.
Example 4: adsorption thermodynamic property test of porous functional sponge adsorbent on lead and copper ions
20Mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into a glass bottle containing 20mL of lead nitrate or copper nitrate solution of initial concentration of 20mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 350mg/L, 400mg/L, 500mg/L, pH=5 was adjusted with 0.1mol/L NaOH or 0.1mol/L HCL before the addition, and then the glass bottle was placed in a constant temperature shaker and shaken at a constant temperature of 25℃at 180r/min, after shaking for 24 hours, sampling was performed by a syringe, the residual concentration of lead copper ions therein was measured by ICP-MS after passing through a 0.22 μm filter, and all groups of experiments were repeated twice according to the procedure and then the average was drawn with Freundlich model and Langmuir model, and the results are shown in FIG. 5.
From fig. 5, it can be seen that the adsorption amount of the adsorbent to the lead and copper ions increases with the increase of the initial lead and copper concentration, then tends to be balanced, and the fitting coefficients of the Freundlich model and the Langmuir model are compared, so that the adsorption of the adsorbent to the lead and copper ions is more in accordance with the Langmuir model, and the single-layer adsorption process is shown. In addition, the theoretical maximum adsorption capacity (q m) of the adsorbent to lead and copper ions is 624.8mg/g and 588.6mg/g respectively.
Example 5: influence of pH on the adsorption Property of a porous functionalized sponge adsorbent
20Mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into glass bottles containing 20mL of lead nitrate or copper nitrate solution having an initial concentration of about 25mg/L, the pH of the initial solution was adjusted to 1, 2, 3,4, 5, 6 with 0.1mol/L NaOH or 0.1mol/L HCL, and then these glass bottles were placed in a constant temperature shaker, and were shaken at 25℃for 24 hours at 180r/min, after the shaking was completed, the sample was taken by a syringe, the sampled liquid was filtered with a 0.22 μm filter membrane, the residual concentration of lead copper ions therein was measured by ICP-MS, and the results were averaged after repeating the procedure twice for all groups of experiments, as shown in FIG. 6.
As can be seen from fig. 6, the adsorption effect of the adsorbent on lead and copper ions is negligible in the polar acid environment with the pH value of 1-2, the removal rate of the adsorbent on lead and copper ions is greater than 94% when the pH value is increased to 3, and the removal rate of the adsorbent on lead and copper ions is as high as 99% in the pH range of 4-6. The pH of natural water is often between 4 and 7, so the adsorbent has better applicability in the pH range of natural water.
Example 6: influence of coexisting ions on the adsorption performance of a porous functionalized sponge adsorbent
20Mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into a glass bottle containing 20mL of lead nitrate or copper nitrate solution with an initial concentration of about 25mg/L, pH=5 of the initial solution was adjusted with 0.1mol/L NaOH or 0.1mol/L HCL, and a certain amount of sodium salt, potassium salt, calcium salt and magnesium salt were added respectively to make the coexisting ion concentrations 0mol/L, 0.01mol/L and 0.1mol/L, and then the glass bottles were placed in a constant temperature shaker and shaken at 25℃for 24 hours at 180r/min, after the shaking was completed, sampling was performed by a syringe, the sampled liquid was filtered with a 0.22 μm filter membrane, and the residual concentration of lead copper ions therein was measured by ICP-MS, and the results were averaged after repeating the procedure twice, as shown in FIG. 7 and FIG. 8.
As is clear from fig. 7 and 8, the removal rate of the lead copper ions by the adsorbent was reduced with the increase of the concentration of the coexisting ions, but the removal rate was still greater than 96%, indicating that the influence of the coexisting ions on the adsorption performance of the adsorbent was small.
Example 7: influence of natural organic matters on adsorption performance of porous functionalized sponge adsorbent
20Mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into a glass bottle containing 20mL of lead nitrate or copper nitrate solution having an initial concentration of about 25mg/L, pH=5 of the initial solution was adjusted with 0.1mol/L NaOH or 0.1mol/L HCL, and a certain amount of humic acid was added to make the humic acid concentration 0mg/L, 5mg/L, 10mg/L, 25mg/L, 50mg/L, 100mg/L and 200mg/L, respectively, and then the glass bottles were placed in a constant temperature shaker, and were shaken at 25℃for 24 hours at 180r/min, after the shaking was completed, sampling was performed by a syringe, the sampled liquid was filtered with a 0.22 μm filter membrane, the residual concentration of lead copper ions therein was measured by ICP-MS, and the results were averaged after repeating the procedure twice, as shown in FIG. 9.
As can be seen from fig. 9, the removal rate of lead and copper ions by the adsorbent was reduced with the increase of the humic acid concentration, but the removal rate was still more than 96%, indicating that the influence of natural organic substances on the adsorption performance of the adsorbent was small. Therefore, the adsorbent has better anti-interference capability.
Example 8: selectivity of porous functional sponge adsorbent to lead and copper ions
Preparing lead nitrate, copper nitrate, sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, zinc nitrate, cadmium nitrate, nickel nitrate and mixed solutions of all the ions with the concentration of 25mg/L respectively, pouring 20mg of the porous functionalized sponge adsorbent prepared in example 1 into the various solutions filled with 20mL and 25mg/L respectively, adjusting the pH=5 of the initial solution by 0.1mol/L NaOH or 0.1mol/L HCL, placing the glass bottles in a constant-temperature oscillator, oscillating for 24 hours at 25 ℃ and 180r/min, sampling by using a syringe after the oscillation is finished, filtering the sampled liquid by using a 0.22 mu m filter membrane, measuring the residual concentration of the lead copper ions in the liquid by using ICP-MS, repeating the process twice, and taking an average value, wherein the result is shown in figure 10.
As can be seen from fig. 10, the removal rate of the adsorbent for lead and copper ions is far higher than that of other ions, both when multiple divalent ions coexist and when only one metal ion exists in the solution, which indicates that the adsorbent has better selectivity for lead and copper ions, and meanwhile, the selectivity of the adsorbent for various metal ions is ranked as follows: pb (II) > Cu (II) > Zn (II) > Ni (II) > Na (I) > Ca (II) > Cd (II) > K (I) > Mg (II).
Example 9: cyclic utilization performance test result of porous functional sponge adsorbent
20Mg of the porous functionalized sponge adsorbent prepared in example 1 was poured into a glass bottle containing 20mL of lead nitrate or copper nitrate solution having an initial concentration of about 25mg/L, the glass bottle was then placed in a constant temperature shaker, the shaking was carried out at a constant temperature of 25℃for 24 hours, the sampled liquid was filtered with a 0.22 μm filter membrane, the residual concentration of lead and copper ions therein was measured by ICP-MS, the porous functionalized sponge adsorbent after adsorbing lead and copper ions was separated from the mixed solution, the adsorbent after adsorption was placed in 0.1mol/L HCl, the desorption solution concentration was measured at 25℃for 4 hours, then the desorbed adsorbent was immersed in deionized water for 4 hours, after the completion of the immersing, the adsorbent was dried at 60℃for 12 hours, and after the drying treatment, it was used for the next adsorption-desorption cycle test, and the results thereof were shown in FIG. 11.
As can be seen from fig. 11, the adsorbent has good regeneration cycle performance, and although the removal rate of lead and copper ions of the adsorbent is reduced with the increase of the regeneration times, the removal rate of lead and copper ions after 10 cycles is still more than 90%, which proves that the adsorbent is a sustainable efficient adsorbent.
Example 10: continuous flow test results for porous functionalized sponge adsorbents.
A lead nitrate solution with the concentration of 3mg/L and a copper nitrate solution with the concentration of 5mg/L are respectively prepared as simulated wastewater, the porous functionalized sponge adsorbent prepared in the embodiment 1 is cut into sizes of 1.5X1.5X1.5mm 3, then an organic glass column with the diameter of 12mm and the length of 100mm is filled with the porous functionalized sponge adsorbent, quartz cotton with the thickness of 10mm is filled at two ends of the glass column for filtration and split flow, the effective bed volume is 9.04mL, the Empty Bed Contact Time (EBCT) is set to 7.5min, a peristaltic pump is adopted to enable the simulated wastewater to flow through the filled glass column, the inlet liquid maintains an upstream flow with the flow rate of 1.2mL/min, sampling is carried out at intervals of 12h, the sampled solution is filtered by a 0.22 mu m filter membrane, and the outlet water concentration of lead copper ions is measured by ICP-MS, and the result is shown in FIG. 12.
As can be seen from fig. 12, when the effluent concentration exceeds the value (MCL) specified by the standard for domestic drinking water, the packed column now treated 16.5L (1821 BV) of lead-simulated wastewater and 14.8L (1630 BV) of copper-simulated wastewater, indicating that the adsorbent is expected to be applied to a small-sized lead-copper wastewater treatment system.
The beneficial effects of the invention are as follows: the porous functional sponge adsorbent provided by the invention is simple to prepare, can be used for removing lead and copper ions in wastewater, has a high adsorption rate and a high adsorption capacity, has high anti-interference capability on environmental factors, has good recycling property, and is suitable for industrial application.
Example 11: the adsorption mechanism of the porous functional sponge adsorbent is explored.
The surface functional groups after adsorption of lead copper ions by the porous functionalized sponge adsorbent prepared in example 1 were analyzed by fourier transform infrared spectroscopy (FTIR), and the results are shown in fig. 13. The test results showed that after the zeolitic imidazolate framework was supported on melamine sponge, -CF 2 bond at 840cm -l and c=o bond at 1638cm -l, which were derived from polyvinylidene fluoride and N, N dimethylformamide, respectively, were added. After adsorption of the lead copper ions, the peak intensities of the C-N bond of 1148cm -l and the c=n bond of 1584cm -l were significantly reduced or disappeared, indicating that a chemical interaction was created between the metal ions and the nitrogen-containing functional groups on the surface of the porous functionalized sponge adsorbent.
The chemical composition of the porous functionalized sponge adsorbent prepared in example 1 after adsorbing lead and copper ions was analyzed by an X-ray photoelectron spectrometer (XPS), and the results are shown in fig. 14 and 15. The results in the total spectrogram 14 show that lead and copper elements respectively appear in the XPS spectrogram of the adsorbent after adsorption, and successful adsorption of lead and copper ions is confirmed. The result of the high-resolution N1s spectrogram 15 shows that both the C-N peak at 398.6eV and the C=N peak at 400.1eV are shifted after adsorption, and new Pb-N peak and Cu-N peak respectively appear, which proves that the nitrogen-containing functional group on the surface of the porous functionalized sponge adsorbent is a main adsorption active site.
Comparative example 1: adsorption thermodynamic property test of pure melamine sponge on lead and copper ions
20Mg of commercially purchased pure melamine sponge was poured into a glass bottle containing 20mL of lead nitrate or copper nitrate solution with initial concentration of 20mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 350mg/L, 400mg/L, 500mg/L respectively, pH=5 was adjusted with 0.1mol/L NaOH or 0.1mol/L HCL before the addition, then the glass bottle was placed in a constant temperature shaker, and was oscillated at a constant temperature of 25℃at 180r/min, after the oscillation was completed, sampling was performed by a syringe, the residual concentration of lead copper ions therein was measured by ICP-MS after the sampled liquid was filtered with a 0.22 μm filter, and all groups of experiments were repeated twice according to the procedure, and the results were plotted using a Freundlich model and a Langmuir model for data fitting, as shown in FIGS. 16 and 17.
From FIGS. 16 and 17, the adsorption capacity of the adsorbent to lead and copper ions is negligible, and the maximum adsorption capacities of the adsorbent to lead and copper ions are respectively 5.9mg/g and 12.4mg/g, which indicates that the adsorption performance of the sponge is poor, and the loaded zeolite imidazole skeleton plays a main role in the porous functionalized sponge adsorbent.
Comparative example 2: adsorption thermodynamic property test of zeolite imidazole skeleton (ZIF-L) on lead and copper ions
20Mg of the zeolite imidazole skeleton (ZIF-L) prepared in example 1 was poured into a glass bottle containing 20mL of lead nitrate or copper nitrate solution of initial concentration of 20mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 350mg/L, 400mg/L, 500mg/L, pH=5 of the solution was adjusted with 0.1mol/L NaOH or 0.1mol/L HCL before the addition, and then the glass bottle was placed in a constant temperature shaker, and was oscillated at 25℃at 180r/min for 24 hours, after the oscillation was completed, the syringe was used for sampling, after the sampled liquid was passed through a 0.22 μm filter membrane, the residual concentration of lead copper ions therein was measured with ICP-MS, and after the whole set of experiments was repeated twice as described above, the average was taken, and the data were fitted using the Freundlich model and Langmuir model, as shown in FIG. 16, 17.
From fig. 16 and 17, it can be seen that the adsorption capacity of the adsorbent for lead and copper ions increases with the increase of the initial lead and copper concentration, and the maximum adsorption capacity of the adsorbent for lead and copper ions obtained by fitting is 101.2mg/g and 543.4mg/g respectively, and the adsorption capacity of the adsorbent is inferior to that of a porous functionalized sponge adsorbent, because the zeolite imidazole skeleton distributed on the sponge is reduced in particle agglomeration after ultrasonic treatment, the contact area with metal ions is increased, and the adsorption performance is improved.
Comparative example 3: influence of ultrasonic duration on adsorption performance of porous functionalized sponge adsorbent
The ultrasonic time of the porous functionalized sponge adsorbent in the example 1 is changed, the rest preparation conditions are unchanged, the ultrasonic time is respectively changed to 5min and 15min, and the porous functionalized sponge adsorbents with different ultrasonic time are respectively marked as MS-ZIF 5 (namely, the ultrasonic time is 5 min) and MS-ZIF 15 (namely, the ultrasonic time is 15 min). 20mg of the prepared MS-ZIF 5 and MS-ZIF 15 were poured into glass bottles containing 20mL of lead nitrate or copper nitrate solution with initial concentration of 20mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 350mg/L, 400mg/L and 500mg/L respectively, pH=5 of the solution was adjusted by 0.1mol/L NaOH or 0.1mol/L HCL before the addition, the glass bottles were placed in a constant temperature oscillator, and were oscillated at 25 ℃ at 180r/min for constant temperature, after the oscillation was completed for 24 hours, the samples were taken by using a syringe, the residual concentration of lead copper ions therein was measured by ICP-MS after the sampled liquid was filtered through a 0.22 μm filter membrane, the average value was taken after the whole set of experiments was repeated twice, and the data were fitted by using a Freundlich model and Langmuir model, as shown in FIG. 18 and FIG. 19.
As can be seen from fig. 18 and 19, the maximum adsorption capacities of the porous functionalized sponge adsorbent for lead and copper ions obtained when the ultrasonic duration is 5min are 398.3mg/g and 422.0mg/g, respectively, and the maximum adsorption capacities of the porous functionalized sponge adsorbent for lead and copper ions obtained when the ultrasonic duration is 15min are 326.2mg/g and 342.3mg/g, respectively. The result shows that the porous functionalized sponge adsorbent prepared when the ultrasonic duration is 10min has the best adsorption performance on lead and copper ions, and the reason is that the porous functionalized sponge adsorbent has a unique hollow annular shape, and the shape is beneficial to promoting mass transfer and accessibility of active sites.
The foregoing is illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (9)
1. The application of the porous sponge adsorbent in adsorbing lead and copper in wastewater is characterized in that:
the porous sponge adsorbent is a mixed phase formed by ZIF-L and ZIF-8, and takes ZIF-8 as a main material, and the loading rate of the zeolite imidazole skeleton on the melamine sponge is 35% -45%;
The adsorbent maintains the original three-dimensional network structure of the melamine sponge, and the zeolite imidazole skeleton loaded on the sponge presents a hollow annular shape;
the surface of the porous functional sponge adsorbent comprises a nitrogen-containing functional group, and the nitrogen-containing functional group is a main adsorption active site.
2. The use according to claim 1, wherein: the loading rate of the zeolite imidazole skeleton on the melamine sponge is 39.82 to 40.72 percent.
3. The use according to claim 1, wherein: the preparation method of the porous sponge adsorbent comprises the following steps:
s1, preparing a zeolite imidazole skeleton ZIF-L;
s2, dissolving the zeolite imidazole skeleton ZIF-L in the S1 in N, N dimethylformamide to prepare zeolite imidazole skeleton solution;
s3, uniformly dispersing the zeolite imidazole skeleton solution in the S2;
s4, heating the solution after the reaction in the S3, and adding polyvinylidene fluoride and uniformly stirring;
S5, immersing the melamine sponge into the solution prepared in the S4, taking out the melamine sponge from the solution, and drying to obtain the multi Kong Haimian adsorbent.
4. Use of a porous sponge adsorbent according to claim 3, wherein: the mass volume ratio of the zeolite imidazole skeleton ZIF-L to the melamine sponge is 1-3g:10-15cm 3.
5. Use of a porous sponge adsorbent according to claim 3, wherein: and S3, uniformly dispersing the zeolite imidazole skeleton solution in S2 by adopting ultrasonic cell disruption.
6. Use of a porous sponge adsorbent according to claim 3, wherein: the mass volume ratio of the zeolite imidazole framework ZIF-L, N, N dimethylformamide and polyvinylidene fluoride is 1-3g:80-120mL:1-3g.
7. Use of a porous sponge adsorbent according to claim 3, wherein: and S5, drying at 130-170 ℃ for 0.5-1.5h.
8. Use of a porous sponge adsorbent according to claim 3, wherein: the heating temperature in S4 is 40-60 ℃.
9. The use of the porous sponge adsorbent as claimed in claim 3, wherein the preparation method of the zeolite imidazole framework ZIF-L in S1 comprises the following steps:
1) Zn (NO 3)2·6H2 O and dimethyl imidazole are respectively dissolved in deionized water to obtain solution A and solution B, and the solution A and the solution B are mixed to prepare a mixed solution;
2) Stirring the mixed solution obtained in the step 1) for 1-3h at the temperature of 20-30 ℃;
3) And (3) filtering the mixed solution after the reaction in the step (2) after stirring is completed to obtain a solid filter material, washing the solid filter material by adopting methanol and deionized water, and then freeze-drying the solid filter material to obtain the zeolite imidazole skeleton ZIF-L.
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