CN109603746A - Loading structure for adsorption of heavy metal pollutants, preparation method and application thereof - Google Patents
Loading structure for adsorption of heavy metal pollutants, preparation method and application thereof Download PDFInfo
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- CN109603746A CN109603746A CN201811514394.7A CN201811514394A CN109603746A CN 109603746 A CN109603746 A CN 109603746A CN 201811514394 A CN201811514394 A CN 201811514394A CN 109603746 A CN109603746 A CN 109603746A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 75
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 6
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 6
- 238000011068 loading method Methods 0.000 title description 2
- 238000010146 3D printing Methods 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000002086 nanomaterial Substances 0.000 claims abstract description 37
- 239000002114 nanocomposite Substances 0.000 claims abstract description 21
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 238000013461 design Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000356 contaminant Substances 0.000 claims description 20
- 229910052785 arsenic Inorganic materials 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011133 lead Substances 0.000 claims description 11
- 238000007639 printing Methods 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000110 selective laser sintering Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 25
- 230000000694 effects Effects 0.000 description 22
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 11
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 241000894007 species Species 0.000 description 5
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- 229910052770 Uranium Inorganic materials 0.000 description 4
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- 238000001514 detection method Methods 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
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- 230000010355 oscillation Effects 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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Classifications
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- 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
-
- 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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/314—Preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
一种用于重金属污染物吸附的负载结构及其制备方法与应用，该负载结构为利用3D打印纳米复合材料通过3D打印得到的镂空结构，3D打印纳米复合材料由重金属吸附纳米材料和3D打印材料混合而成。具体使用三维画图软件设计特定形状和尺寸的装置或部件，将重金属吸附纳米材料均匀地掺杂到3D打印材料中，并使用3D打印技术利用合成的3D打印纳米复合材料对三维画图软件设计的装置或部件进行加工制造，随后利用打印的装置或部件对含有目标重金属污染物的污水进行吸附处理。本发明避免了重金属吸附材料发生团聚，提高吸附选择性和吸附效率，且使用简便，使用后不会造成吸附剂的残留，避免了潜在的二次污染，易于回收和重复使用，降低了成本。
A load structure for the adsorption of heavy metal pollutants, a preparation method and application thereof, the load structure is a hollow structure obtained by 3D printing a nanocomposite material, and the 3D printing nanocomposite material is composed of heavy metal adsorption nanomaterials and 3D printing materials. mixed. Specifically, 3D drawing software is used to design devices or components of specific shapes and sizes, and heavy metal adsorption nanomaterials are uniformly doped into 3D printing materials, and 3D printing technology is used to use synthetic 3D printing nanocomposite materials to design devices designed by 3D drawing software. Or parts are processed and manufactured, and then the printed devices or parts are used for adsorption treatment of sewage containing target heavy metal pollutants. The invention avoids the agglomeration of heavy metal adsorption materials, improves adsorption selectivity and adsorption efficiency, and is easy to use, does not cause residues of adsorbents after use, avoids potential secondary pollution, is easy to recover and reuse, and reduces costs.
Description
Technical field
The invention belongs to heavy metal-polluted water-treatment technology field more particularly to a kind of bearing for heavy metal contaminants absorption
Carry structure and the preparation method and application thereof.
Background technique
With economic fast development, causes a large amount of metals such as copper, arsenic, lead, mercury, cadmium, cobalt etc. with mining, smelts
The discharge of wastewater of the generations such as industry, chemical company, agricultural irrigation not only causes serious dirt to aquatic environment into natural water
Dye, also seriously threatens the health of the mankind.Existing heavy metal containing wastewater treatment technology include precipitating, redox, ion exchange,
Absorption, reverse osmosis, electrolysis analysis, UF membrane and biological treatment etc..Wherein, absorption method is utilized with high-specific surface area, insoluble
The solid material of property makees adsorbent, by reaction mechanisms such as physics, chemisorption and ion exchanges by the heavy metal in water
Pollutant adsorbs on the surface thereof, is a kind of technology for removing heavy metal in water removal being simple and efficient to achieve the purpose that removal.
But there are adsorption treatment effects for traditional adsorbent material such as active carbon, metal oxide, functional resin and various natural minerals etc.
Rate is low, at high cost, and is easy to cause secondary pollution problems, so that the application of the technology is subject to certain restrictions.
Nano material is due to unique surface property, macro quanta tunnel effect, quantum size effect and small size
The characteristics such as effect can significantly improve the specific surface area and reactivity of material, therefore as to organic compound and heavy metal
The pollutants such as ion have the Ideal adsorption agent of larger adsorption capacity and affinity, are gradually applied to water pollutant at present
Adsorption.Such as nano-TiO2It is widely used in the absorption and removal of arsenic in water, nano zero valence iron is used for chlorine in water
The absorption and removal of the heavy metals such as generation, bromo organic matter, disinfection by-products and As, Co and a variety of carbon nanomaterials be used to inhale
Attached organic pollutants, antibiotic and heavy metal contaminants etc..However, nano material in terms of water process application there is also
More problem to be solved, some nano materials it is more difficult as adsorbent practical operation, it is difficult to recycled from water, inhale
Attached selectivity is low, and regeneration effect is poor, and the nano material of high-purity is at high price, easily occurs when use to reunite to reduce absorption effect
Rate, there are different degrees of residuals after use, are easy migration in the environment, become the potential pollution of the secondary release of heavy metal instead
Source etc..
To solve the above-mentioned problems, being modified and research and develop different carriers to nano material for loading nano material is
Current main research tendency, but often cost is higher for modified Nano material, and synthesis is more complex, and the load of nanocomposite
Process is usually that carrier material is immersed in the solution containing nano material, and some relies solely on the physics of carrier material itself
Suction-operated is loaded, and storeroom conjugation is not high, and load stability is poor, it is not easy to stablized and a large amount of finished product,
And the composite material that those are loaded by chemisorption, in practical applications often due to the influence of environmental condition causes to take off
It falls, limits adsorption efficiency.Therefore fast and convenient, the economically viable novel load technology of one kind is urgently developed to be used to prepare more
Efficiently, more stable nanocomposite and support structures are to remove heavy metal contaminants in water removal.
Summary of the invention
In view of this, the main purpose of the present invention is to provide it is a kind of for heavy metal contaminants absorption support structures and
Preparation method and application, at least be partially solved at least one of above-mentioned the technical issues of referring to.
To achieve the goals above, technical scheme is as follows:
As one aspect of the present invention, a kind of support structures for heavy metal contaminants absorption are provided, for benefit
The engraved structure obtained with 3D printing nanocomposite by 3D printing, the 3D printing nanocomposite are inhaled by heavy metal
Attached nano material and 3D printing material mix.
As another aspect of the present invention, a kind of preparation method of support structures as described above is provided comprising
The following steps:
Step 1 uses the support structures of three-dimensional picture software design specific shape and size；
Step 2, by heavy metal adsorption nano material Uniform Doped into 3D printing material；
Step 3 is printed as step 1 by the 3D printing nanocomposite that 3D printing technique obtains step 2 and sets
The support structures of meter；
Step 4, the support structures for printing step 3 are cleaned repeatedly to remove the 3D printing material for remaining in surface,
And it is dried.
As another aspect of the invention, a kind of support structures as described above are provided in absorption heavy metal contaminants
In application.
Based on the above-mentioned technical proposal, the present invention is used for support structures of heavy metal contaminants absorption and preparation method thereof and answers
With having the advantages that
1,3D printing nanocomposite provided by the invention can according to the actual situation, for different heavy metal-polluted in water
Object is contaminated, the adsorbent material of doping variety classes, size and concentration is into 3D printing material, to reach optimal adsorption effect, because
This adsorptive selectivity is higher, and adsorption efficiency is high；
2, the support structures for adsorbing heavy metal in water pollutant are fabricated using 3D printing technique, therefore
Entire manufacturing process is fast and convenient, and processing cost is low, can also be according to actual Demand Design and processing and manufacturing specific shape and ruler
Very little support structures, to be applicable in different occasions；
3, in the preparation process of support structures, heavy metal adsorption nano material is doped in advance in 3D printing material,
And it is distributed on entire support structures as the process of 3D printing is uniform and stable, therefore avoid heavy metal adsorption nanometer material
Material is reunited, and adsorption efficiency is improved, and using simplicity, is easily recycled, not will cause heavy metal adsorption nanometer after use
The residual of material avoids potential secondary pollution, can also be repeatedly used, be reduced costs.
4, have not provided by the present invention for the support structures and the preparation method and application thereof of heavy metal contaminants absorption
The possibility of disconnected optimization.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 is prepared using the 3D printing nanocomposite containing 2% mass fraction nano zero valence iron
Cell structure schematic diagram；
Fig. 2 is that cell structure prepared by the embodiment of the present invention 1 carries out adsorption treatment to the aqueous solution of the arsenic ion containing trivalent
As a result；
Fig. 3 is that cell structure prepared by the embodiment of the present invention 1 carries out adsorption treatment to the aqueous solution of the ion containing various metals
Result；
Fig. 4 is that the embodiment of the present invention 2 is beaten using the 3D containing 2% mass fraction hydrophilic and oleophilic type anatase nano-titanium dioxide
Print the cell structure schematic diagram of nanocomposite preparation；
Fig. 5 is that cell structure prepared by the embodiment of the present invention 2 carries out adsorption treatment to the aqueous solution of the arsenic ion containing trivalent
As a result；
Fig. 6 is that cell structure prepared by the embodiment of the present invention 2 carries out adsorption treatment to the aqueous solution of the ion containing various metals
Result.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The support structures and the preparation method and application thereof that the invention discloses a kind of to adsorb for heavy metal contaminants, for
The target heavy metal contaminants for needing Adsorption adulterate different heavy metal adsorption nano materials in 3D printing material, lead to
It crosses 3D printing heavy metal adsorption nano material is uniformly and stably distributed on entire support structures, avoids adsorbent material hair
It is raw to reunite, improve adsorptive selectivity and adsorption efficiency, and using it is easy, be easily recycled and reuse, avoid potential
Secondary pollution is with a wide range of applications.
Specifically, the present invention provides a kind of support structures for heavy metal contaminants absorption, which is benefit
The engraved structure obtained with 3D printing nanocomposite by 3D printing, the 3D printing nanocomposite is by heavy metal adsorption
Nano material and 3D printing material mix.
Wherein, which includes but is not limited to grid, filter membrane, filter ball or pipeline type structure etc., theoretically can
Fabricate various geometries, size.
Wherein, heavy metal adsorption nano material includes but is not limited to active carbon, carbon nanotube, graphene, nanometer titanium dioxide
The nano materials such as titanium, nano zero valence iron or nano ferriferrous oxide are theoretically adapted to that the institute of heavy metal contaminants can be adsorbed
There is nano material.
Wherein, 3D printing material includes but is not limited to acrylonitrile-butadiene-styrene (ABS), polylactic acid, nylon, polyether-ether-ketone
Equal thermoplastics, various light-cured resins or ceramic powders etc..Specifically solid can be selected respectively according to the material type of selection
The 3D printing techniques such as offset printing, fusion sediment, selective laser sintering, digital light processing.
Wherein, in 3D printing nanocomposite, the mass concentration of heavy metal adsorption nano material is 0~10%, weight
The mass concentration of metal adsorption nano material is excessively high to will lead to 3D printing failure.
The present invention also provides a kind of preparation methods of support structures as described above, comprise the following steps:
Step 1 uses the support structures of three-dimensional picture software design specific shape and size；
Step 2, by heavy metal adsorption nano material Uniform Doped into 3D printing material；
Step 3 is printed as step 1 by the 3D printing nanocomposite that 3D printing technique obtains step 2 and sets
The support structures of meter；
Step 4, the support structures for printing step 3 are cleaned repeatedly to remove the 3D printing material for remaining in surface,
And it is dried.
Wherein, in step 1, which includes grid, filter membrane, filter ball or pipeline type structure；In step 2, one
In a little embodiments, heavy metal adsorption nano material can be doped into 3D printing material by the way of stirring, in other realities
It applies in example, other suitable doping way can be selected according to actual needs；In step 3, which includes three-dimensional plate
Printing, fusion sediment, selective laser sintering or digital optical processing technique；In step 4, the support structures are carried out using solvent
Cleaning, the solvent includes clear water, alcohol, dehydrated alcohol or isopropanol etc..
The present invention also provides a kind of application of support structures as described above in absorption heavy metal contaminants.
Wherein the heavy metal contaminants include but is not limited in mercury, chromium, cadmium, arsenic, lead, molybdenum, nickel, gold, silver, copper, iron and lead
One or more heavy metal ion.
Specific embodiment is exemplified below to be described further to technical solution of the present invention.
Embodiment 1
Load has the preparation of the cell structure of heavy metal adsorption nano material:
As shown in Figure 1, the present embodiment has fabricated a kind of lattice for adsorbing trivalent arsenic ion in water using the method for the present invention
Grid.It in the present embodiment, is the grid of face-centerd cubic structure first with a kind of each single lattice of three-dimensional picture software design,
The space utilization rate of the structure is higher, and specific surface area is larger, and stable structure, and grid thickness is 0.3mm, and single lattice length, width and height are
2.5mm, the three-dimensional of entire grid are respectively 1.53cm, 1.53cm, 1.375cm.Then, for the trivalent arsenic in Adsorption water
Ion, we select the nano zero valence iron of 50nm partial size as heavy metal adsorption nano material, and by the nanometer of 50nm partial size zero
Valence iron powder is doped in 3D printing light-cured resin with 2% mass fraction, is stirred using magnetic stirring apparatus,
Obtain 3D printing nanocomposite.Later, processing system is carried out by 3D photocuring printing technique, that is, stereolithography technology
It makes to obtain grid.Finally after the completion of printing, remain in lattice using the cleaning that 75% alcohol carries out repeatedly grid to remove
The uncured light-cured resin in grid surface, and be placed at shady and cool ventilation and dry.To the grid weighed the results show that should
The average weight of grid is 0.829 ± 0.042g, average 16.581 ± 0.845mg of nano zero valence iron containing 50nm.
The adsorption effect of trivalent arsenic ion is tested:
In order to verify above-mentioned grid to the adsorption effect of trivalent arsenic ion in water, the present embodiment is initial using trivalent arsenic ion
The aqueous solution (pH=7) that concentration is 100ppb or so carries out the absorption test of different time.Specific step is as follows:
The trivalent arsenic solution that 45mL initial concentration is 100ppb or so is added in 50mL centrifuge tube, and in each centrifugation
Be put into the multiple groups adsorption experiment that an above-mentioned grid carries out different time in pipe, adsorption time is respectively 0.5,1,2,4,8,12,
24 hours.Sample is placed on constant-temperature table in adsorption process and be protected from light oscillation, hunting speed is 200 revs/min, temperature
It is set as 30 DEG C.After adsorption experiment, solution is sampled, and uses icp ms pair73As
With56Fe element is detected.
As shown in Fig. 2, inhaling the experimental results showed that the grid of the present embodiment has apparent adsorption effect to trivalent arsenic ion
After attached 8 hours, the concentration of trivalent arsenic ion is lower than 50ppb in solution, and adsorption rate is more than 50%.And do not have in detection process
It is found56Fe signal increases, and shows that the grid does not discharge nano zero valence iron into aqueous solution or release concentration is lower than instrument
Detection limit (5ppb).
Adsorption effect experiment to other heavy metal contaminants in water:
In order to verify the method for the present invention to the adsorption efficiency of other heavy metal contaminants in water, institute in the present embodiment 1 is used
The cell structure that the 50nm nano zero valence iron of 2% mass concentration must be adulterated, inhales the aqueous solution containing Determination of multiple metal elements
Attached test.Specific step is as follows:
Prepare be used to carry out absorption test the aqueous solution (pH=6) containing 25 metal ion species, wherein Na, Mg, K,
The initial concentration of Ca, Fe plasma in 1ppm or so, Be, Al, V, Cr, Mn, Co, Ni, Cu, Zn, Ge, As, Se, Mo, Ag, Cd,
The initial concentration of Sb, Ba, Tl, Pb, U plasma is in 80ppb or so.It is small that each grid carries out 12 to the above-mentioned aqueous solution of 45mL respectively
When adsorption treatment.Sample solution is rocked by shaking table in adsorption process, shaking speed is 200 revs/min, temperature control
It is made as 25 degree.After absorption, solution is sampled, and using icp ms to above-mentioned all members
Element is detected.
As shown in figure 3, the experimental results showed that containing nano zero valence iron used in the present embodiment after absorption 12 hours
Cell structure to the grid containing nano zero valence iron to Be, Al, V, Cr, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Sb, Ba,
17 metal ion species such as Pb, U have adsorption effect, wherein the absorption to 8 metal ion species such as V, As, Se, Mo, Ag, Sb, Pb, U
Efficiency is more than 50%, and particularly, the adsorption efficiency to Ag is more than 90%.
Embodiment 2
Load has the preparation of the cell structure of heavy metal adsorption nano material:
As shown in figure 4, the present embodiment has fabricated a kind of size in the same manner as in Example 1, shape using the method for the present invention
The grid of trivalent arsenic ion in the absorption water of shape.The grid is equally designed first with three-dimensional drawing software, grid thickness
For 0.3mm, single lattice length, width and height are 2.5mm, and the three-dimensional of entire grid is respectively 1.53cm, 1.53cm, 1.375cm.But it distinguishes
It is, in the present embodiment, we select the hydrophilic and oleophilic type anatase nano-titanium dioxide of 5~10nm as heavy metal adsorption
Nano material, and the hydrophilic and oleophilic type anatase nano titanium dioxide powder of 5~10nm is doped to 3D with 2% mass fraction and is beaten
It prints in light-cured resin, is then equally stirred using magnetic stirring apparatus, obtain 3D printing nanocomposite.
Later, it is fabricated to obtain grid by 3D photocuring printing technique.After the completion of finally printing, 75% alcohol pair is used
The cleaning that grid carries out repeatedly remains in the uncured light-cured resin of grid surface to remove, and is placed at shady and cool ventilation and dries in the air
It is dry.The average weight of the grid be 0.738 ± 0.073g, averagely containing 5~10nm nano-titanium dioxide 14.760 ±
1.470mg。
The adsorption effect experiment 1 of trivalent arsenic ion:
In order to verify above-mentioned grid to the adsorption effect of trivalent arsenic ion in water, the present embodiment is initial using trivalent arsenic ion
The aqueous solution (pH=7) that concentration is 100ppb or so carries out the absorption test of different time.Suction in specific steps and embodiment 1
Attached effect experiment 1 is similar, and difference is that adsorption time is respectively 0.17,0.33,0.5,1,2,4,8,12,24 hour, is adsorbing
After experiment, icp ms pair are used73As and48Ti element is detected.
As shown in figure 5, the experimental results showed that the cell structure of the present embodiment has apparent adsorption effect to trivalent arsenic ion,
After adsorbing 4 hours, the concentration of trivalent arsenic ion is lower than 3ppb in solution, and adsorption rate is more than 95%.And detection process
In do not find48Ti signal increases, and shows that the grid does not discharge nano-titanium dioxide into aqueous solution or release concentration is low
In instrument detection limit (1ppb).
The adsorption effect experiment 2 of trivalent arsenic ion:
Using above-mentioned grid and with original 5~10nm water of adsorbent material quality an order of magnitude contained by above-mentioned grid parent
Oil type anatase nano titanium dioxide powder (21.267 ± 2.042mg) is 500ppb's or so to trivalent arsenic ion initial concentration
Aqueous solution (pH=7) carries out the test of absorption in 24 hours, to compare the adsorption efficiency of the two.Suction in specific steps and embodiment 1
Attached effect experiment 2 is similar, after adsorption experiment, uses icp ms pair73As element is detected.
To the trivalent arsenic solution of 500ppb adsorbed the results show that grid of the present invention to the unit adsorbance of trivalent arsenic
For 1.117 ± 0.058mg arsenic/g adsorbent material.And original 5-10nm water lipophilic anatase nano titanium dioxide powder is to trivalent
The unit adsorbance of arsenic is 1.090 ± 0.113mg arsenic/g adsorbent material.Show that the arsenic removal efficiency outline of the method for the present invention is better than
It is adsorbed using original material.
Adsorption effect experiment to other heavy metal contaminants in water:
Use 5~10nm hydrophilic and oleophilic type anatase nanometer titanium dioxide of 2% mass concentration of gained doping in the present embodiment 1
The cell structure of titanium carries out absorption test to the aqueous solution containing Determination of multiple metal elements.To in water in specific steps and embodiment 1
The adsorption effect experiment of other heavy metal contaminants is similar.
As shown in fig. 6, the experimental results showed that the experimental results showed that absorption 12 hours after, used in the present embodiment
Cell structure containing nano-titanium dioxide is to V, Cr, Fe, Co, Ni, Cu, Ge, As, Se, Mo, Ag, Cd, Sb, Ba, Tl, Pb, U etc.
17 metal ion species have adsorption effect, wherein waiting the adsorption efficiency of 5 metal ion species to be above V, As, Se, Mo, Sb
90%.
Comparative example 1
Load has the preparation of the support structures of heavy metal adsorption nano material:
This comparative example has fabricated one kind and identical size, shape in embodiment 1 and embodiment 2 using the method for the present invention
Absorption water in trivalent arsenic ion grid.The grid is equally designed first with three-dimensional drawing software, and grid thickness is
0.3mm, single lattice length, width and height are 2.5mm, and the three-dimensional of entire grid is respectively 1.53cm, 1.53cm, 1.375cm.But difference exists
In in the present embodiment, we select the hydrophilic and oleophilic type anatase nano-titanium dioxide of 5~10nm to receive as heavy metal adsorption
Rice material, and the hydrophilic and oleophilic type anatase nano titanium dioxide powder of 5~10nm is doped to 3D with 12% mass fraction and is beaten
It prints in light-cured resin, is then equally stirred using magnetic stirring apparatus, in whipping process, due to doping
Powder quality score is excessive, causes nano material that can not be uniformly distributed, and initial resin becomes non-with nano material composite material
It often sticks together, discovery can not printing shaping after multiple trial printing.
Table 1
It is in table 1 the experimental results showed that, the present invention can be prepared successfully under specific doping concentration with molding 3D printing
Material is the carrier loaded support structures for having heavy metal adsorption nano material, all has adsorption effect to contents of many kinds of heavy metal ion.
Although above-described embodiment is to prepare cell structure based on 3D photocuring printing technique, those skilled in the art can
To understand, should also be as by the engraved structure that other 3D printing techniques obtain with phase using other heavy metal adsorption nano materials
Same or similar technical effect.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (9)
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