CN116173931A - Polypyrrole-polyaniline modified xonotlite as well as preparation method and application thereof - Google Patents
Polypyrrole-polyaniline modified xonotlite as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN116173931A CN116173931A CN202310050124.XA CN202310050124A CN116173931A CN 116173931 A CN116173931 A CN 116173931A CN 202310050124 A CN202310050124 A CN 202310050124A CN 116173931 A CN116173931 A CN 116173931A
- Authority
- CN
- China
- Prior art keywords
- xonotlite
- polypyrrole
- modified
- polyaniline
- polyaniline modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical class O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000004088 foaming agent Substances 0.000 claims abstract description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 21
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 29
- 150000002500 ions Chemical class 0.000 claims description 27
- 239000002351 wastewater Substances 0.000 claims description 27
- 239000004202 carbamide Substances 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 35
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 abstract description 24
- 239000008367 deionised water Substances 0.000 abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 abstract description 17
- 238000003795 desorption Methods 0.000 abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 239000002131 composite material Substances 0.000 description 22
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 9
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FIMJSWFMQJGVAM-UHFFFAOYSA-N chloroform;hydrate Chemical compound O.ClC(Cl)Cl FIMJSWFMQJGVAM-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 210000003278 egg shell Anatomy 0.000 description 2
- 238000009297 electrocoagulation Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- -1 urea modified xonotlite Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001669696 Butis Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- JLDKGEDPBONMDR-UHFFFAOYSA-N calcium;dioxido(oxo)silane;hydrate Chemical class O.[Ca+2].[O-][Si]([O-])=O JLDKGEDPBONMDR-UHFFFAOYSA-N 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical group O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- 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
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses polypyrrole-polyaniline modified xonotlite and a preparation method and application thereof, and belongs to the technical field of material synthesis. The preparation method comprises the following steps: (1) Stirring and dissolving a calcium source with deionized water, adding a silicon source and a foaming agent, adding potassium hydroxide to obtain a mixture, reacting at 230 ℃ for 12 hours, cooling, washing, drying, grinding and sieving to obtain xonotlite; (2) Mixing xonotlite with chloroform, cooling to below 8 ℃ to obtain a suspension, adding polypyrrole and polyaniline into the suspension, adding ferric chloride solution, filtering, washing, drying and sieving after reaction to obtain the polypyrrole-polyaniline modified xonotlite. The polypyrrole-polyaniline modified xonotlite prepared by the invention has excellent desorption and lead ion adsorption properties, and in lead-containing wastewater treatment, the lead ion removal rate can reach more than 98%, and the adsorption capacity can reach more than 980 mg/g.
Description
Technical Field
The invention relates to polypyrrole-polyaniline modified xonotlite and a preparation method and application thereof, and belongs to the technical field of material synthesis.
Background
Water is an indispensable resource in human life and production activities, but with the development of industry, the discharge amount of production and domestic sewage is increasing, and the types and kinds of pollutants are also increasing. The wastewater is discharged in large quantity, and a severe water environment is gradually formed, so that the pollution of aquatic organisms, soil and crops is caused, and even the human health is endangered. The wastewater has different properties and components due to different production processes, raw materials and products, and one wastewater often contains various pollutants, and contains a large amount of heavy metal lead ions. Lead ions are accumulated in the liver and the kidney, so that anemia is caused by dyshemoglobin synthesis, biochemical and physiological activities of organisms are interfered, and healthy life of human beings is seriously endangered.
The existing lead-containing wastewater treatment methods mainly comprise a chemical precipitation method, an ion exchange method, a membrane separation method, a biological method, an electrocoagulation method, an adsorption method and the like. The chemical precipitation method has lower cost and is easy to cause two pollutions to the environment; ion exchange processes are multi-selective but costly to operate; membrane separation techniques, biological methods and electrocoagulation methods, while being efficient, are not efficient but are complex to operate and costly. The adsorption method is attractive because of the easy availability of materials, simple operation, flexible design, low price, good removal effect and strong reproducibility, and the environment-friendly concept is embodied in the field of wastewater treatment.
Xonotlite chemical formula is 6CaO.6SiO 2 ·H 2 O, which is one of the materials of the calcium silicate hydrate (C-S-H) class, is widely used for materials for light weight and heat preservation of buildings due to its excellent heat insulation. Meanwhile, because the xonotlite molecules have rough surfaces, the internal porous structure has good development, and the particle surfaces have exchangeable ions and charged points and are characterized by containing a large number of active sites such as silicon, calcium, hydroxyl and the like, the xonotlite molecules are widely applied to the adsorption treatment of heavy metals in a water system, and meanwhile, because the xonotlite has good coordination with the environment, secondary pollution is not easy to cause, the xonotlite becomes a novel environment functional material, and the xonotlite has strong attention.
The former research finds that the xonotlite is monoclinic system, which is formed by a calcium polyhedral layer, and both sides of the calcium polyhedral layer are aggregated by metasilicic acid chains to form fibrous or needle-shaped crystals, so that active groups in the interior of the crystals are difficult to replace, combine and exchange with metal ions, the adsorption performance is limited, and the popularization and application of the xonotlite in environmental treatment are limited. Therefore, the tobermorite needs to be modified, the agglomeration phenomenon of the tobermorite is reduced, and the specific surface area, the number of adsorbable groups in molecules and the exchange degree with heavy metals are improved.
In recent years, in order to improve the heavy metal removal capability of xonotlite, various scholars at home and abroad have actively explored a novel synthesis method, a modification method and application of xonotlite in pollution treatment. The patent with application number 201910240309.0 discloses a preparation method and application of a magnetic organic modified nano adsorption material, which uses ferrous chloride and ferric chloride to react in sodium citrate solution to prepare magnetic Fe 3 O 4 Then taking the calcined raw material of the waste eggshells as a calcium source, and adding SiO 2 Powder, NH 4 HCO 3 As a foaming agent, the magnetic nano-adsorption material xonotlite is prepared by a hydrothermal synthesis method, and then the amino-functionalized novel magnetic organic modified nano-adsorption material is prepared by using bridging molecules, butIs the adsorption material pair Cd 2+ The treatment efficiency of the lead-containing wastewater can only reach 90 percent, and 0.1g of adsorption material needs to be added into 100mL of lead-containing wastewater, so that the consumption is high; the patent with application number 201810791757.5 provides a method for preparing tobermorite and sodiumdiosite, and the application and regeneration thereof, which adopts waste eggshells as raw materials to prepare porous adsorption functional materials of tobermorite and sodiumdiosite, and the prepared tobermorite is used for Cd in wastewater 2+ The removal rate of (2) can only reach 81.68%. Therefore, there is a need to propose a new type of modified xonotlite for treating wastewater containing heavy metals.
Disclosure of Invention
In order to solve the technical problems, the invention provides polypyrrole-polyaniline modified xonotlite and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following solutions:
one of the technical schemes of the invention is as follows:
a preparation method of polypyrrole-polyaniline modified xonotlite (PPY-PANI modified xonotlite), comprising the following steps:
(1) Preparation of xonotlite
Stirring and dissolving a calcium source with deionized water at 25 ℃ for 30min to form pasty calcium hydroxide, adding a silicon source and a foaming agent, weighing potassium hydroxide to provide an alkali environment, continuously stirring to obtain a mixture, reacting the mixture at 230 ℃ for 12h, cooling, alternately washing with 0.1mol/L HCl solution and deionized water to be neutral, drying, grinding and sieving to obtain the tobermorite;
(2) Preparation of polypyrrole-polyaniline modified xonotlite
Magnetically stirring the xonotlite obtained in the step (1) and chloroform water bath for 30min, cooling to below 8 ℃ to obtain a suspension, adding polypyrrole (PPY) and Polyaniline (PANI) into the suspension, continuously stirring to obtain a mixture, adding ferric chloride solution into the mixture for reaction, filtering, alternately washing with ethanol and deionized water for 3-4 times, drying, and sieving to obtain the polypyrrole-polyaniline modified xonotlite (PPY-PANI modified xonotlite).
Further, the mass ratio of the calcium source to the silicon source to the foaming agent is 4:6:10, the calcium source is CaO, and the silicon source is SiO 2 The foaming agent is urea.
Further, the feed liquid ratio of the xonotlite to the polypyrrole to the polyaniline is 5g to 1.6mL to 1g.
Further, the ferric chloride solution is prepared by adding ferric chloride into chloroform and performing ultrasonic treatment for 15min, wherein the feed liquid ratio of the ferric chloride to the chloroform is 5g to 180mL.
Further, ferric chloride solution was added to the mixture to react at 8 ℃ for 10 hours.
Further, the temperature of the drying in the step (1) and the step (2) is 80 ℃, and the drying is sieved to pass through a 140-mesh sieve.
The second technical scheme of the invention is as follows:
polypyrrole-polyaniline modified xonotlite prepared by the preparation method.
The third technical scheme of the invention:
the application of polypyrrole-polyaniline modified xonotlite in treating lead wastewater comprises adding the polypyrrole-polyaniline modified xonotlite into wastewater to be treated, and adsorbing and removing lead in the wastewater.
Further, the addition amount of the polypyrrole-polyaniline modified xonotlite in the wastewater to be treated is more than or equal to 0.04g/100mL, and the adsorption time is more than or equal to 60min.
Further, the concentration of lead ions in the wastewater to be treated is less than or equal to 400mg/L, and the pH value is 5.5-8.
The invention discloses the following technical effects:
the conductive polymers polyaniline and polypyrrole have nitrogen-containing functional groups on the main chain, and heavy metal ions in water can be removed through complexation and electrostatic action, so that the adsorption selectivity of the polymer body is consistent, and the polymer is convenient to synthesize, low in cost and stable in property, and is considered to be an ideal adsorbent material. Therefore, the surface of the nitrogenous conductive polymer is modified with tobermorite, so that the aggregation of tobermorite can be reduced, the adsorption site and the surface area of the material are increased, and the removal of heavy metals is facilitated.
The PPY-PANI modified xonotlite prepared by the invention has excellent desorption and lead ion adsorption performance, and the dosage of the PPY-PANI modified xonotlite in the wastewater to be treated is 0.0400g and Pb 2+ When the initial concentration is 400mg/L, pH =5.5 and the adsorption time is 60min, the adsorption effect is optimal, the removal rate can reach more than 98%, and the adsorption capacity reaches more than 980 mg/g. And urea is added as a foaming agent, since urea provides CO 3 2- So that the negative charge on the surface of the xonotlite is increased, thereby being beneficial to adsorbing cations by electrostatic attraction and simultaneously CO 3 2- Can be combined with Pb 2+ Generating PbCO 3 And precipitating and removing part of lead ions, so that the adsorption performance of the xonotlite is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 is a flow chart of the preparation of PPY-PANI modified xonotlite in step (2) of example 1 of the present invention;
FIG. 2 is an infrared spectrum of the PPY-PANI modified xonotlite material prepared in the embodiment 1 of the invention;
FIG. 3 is an SEM image of a PPY-PANI modified xonotlite material prepared in example 1 of the present invention;
FIG. 4 is a flow chart of an experiment for exploring the effect of different factors on the adsorption of lead ions by a PPY-PANI modified xonotlite material as an adsorbent;
FIG. 5 shows the amount of PPY-PANI modified xonotlite adsorbent used versus Pb 2+ A removed influence result graph;
FIG. 6 shows the lead ion initial concentration versus Pb adsorption by the PPY-PANI modified xonotlite adsorbent 2+ Is a graph of the impact results;
FIG. 7 shows adsorption of Pb by a pH vs. PPY-PANI modified xonotlite adsorbent 2+ Is a graph of the impact results;
FIG. 8 shows adsorption time versus Pb by PPY-PANI modified xonotlite adsorbent 2+ Is a result of the influence of (1);
fig. 9 is a graph showing the results of adsorption of lead ions in filtrate by the non-foaming agent urea modified xonotlite, the xonotlite prepared in example 1, the PPY-PANI modified xonotlite (non-foaming agent urea modified), and the PPY-PANI modified xonotlite prepared in example 1, in this order from left to right.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The invention discloses a preparation method of polypyrrole-polyaniline modified xonotlite, which comprises the following steps:
(1) Preparation of xonotlite
Stirring and dissolving a calcium source with deionized water at 25 ℃ for 30min to form pasty calcium hydroxide, adding a silicon source and a foaming agent, weighing potassium hydroxide to provide an alkali environment, continuously stirring to obtain a mixture, reacting the mixture at 230 ℃ for 12h, cooling, alternately washing with 0.1mol/L HCl solution and deionized water to be neutral, drying, grinding and sieving to obtain the tobermorite;
(2) Preparation of polypyrrole-polyaniline modified xonotlite
Magnetically stirring the xonotlite obtained in the step (1) and chloroform water bath for 30min, cooling to below 8 ℃ to obtain a suspension, adding polypyrrole (PPY) and Polyaniline (PANI) into the suspension, continuously stirring to obtain a mixture, adding ferric chloride solution into the mixture for reaction, filtering, alternately washing with ethanol and deionized water for 3-4 times, drying, and sieving to obtain the polypyrrole-polyaniline modified xonotlite (PPY-PANI modified xonotlite).
In some preferred embodiments of the present invention, the mass ratio of the calcium source, the silicon source and the foaming agent is 4:6:10, the calcium source is CaO, and the silicon source is SiO 2 The foaming agent is urea. Urea can provide CO 3 2- So that the negative charge on the surface of the xonotlite is increased, thereby being beneficial to adsorbing cations by electrostatic attraction and simultaneously CO 3 2- Can be combined with Pb 2+ Generating PbCO 3 And precipitating and removing part of lead ions, so that the adsorption performance of the xonotlite is improved.
In some preferred embodiments of the invention, the feed ratio of xonotlite, polypyrrole, and polyaniline is 5g to 1.6mL to 1g.
In some preferred embodiments of the invention, the ferric chloride solution is prepared by adding ferric chloride into chloroform, and performing ultrasonic treatment for 15min, wherein the feed liquid ratio of the ferric chloride to the chloroform is 5g to 180mL.
In some preferred embodiments of the invention, ferric chloride solution is added to the mixture to react for 10 hours below 8 ℃.
In some preferred embodiments of the present invention, the temperature of the drying in step (1) and step (2) is 80 ℃, and the drying is sieved through a 140 mesh sieve.
The invention also provides polypyrrole-polyaniline modified xonotlite prepared by the preparation method.
The invention also provides application of the polypyrrole-polyaniline modified xonotlite in treating lead wastewater, wherein the polypyrrole-polyaniline modified xonotlite is added into the wastewater to be treated, and the lead in the wastewater is removed by adsorption.
In the embodiment of the invention, the addition amount of the polypyrrole-polyaniline modified xonotlite in the wastewater to be treated is more than or equal to 0.04g/100mL, and the adsorption time is more than or equal to 60min; in some preferred embodiments of the invention, the polypyrrole-polyaniline modified xonotlite is added to the wastewater to be treated in an amount of 0.04g/100mL, and the adsorption time is 60min.
In the embodiment of the invention, the concentration of lead ions in the wastewater to be treated is less than or equal to 400mg/L, and the pH value is 5.5-8.
In some preferred embodiments of the invention, the pH of the wastewater to be treated is 5.5. This is because the pH is too low, due to H + And Pb 2+ With the same electrical properties, so H + And Pb 2+ Competing with the PPY-PANI to modify the active site of the surface of the xonotlite composite material, thereby leading to the reduction of the adsorption performance of the adsorbent. Due to Pb 2+ Can form Pb (OH) with hydroxide ion 2 Precipitation affects the accuracy of the data, so the pH is chosen to be no more than 8.
In some preferred embodiments of the invention, the concentration of lead ions in the wastewater to be treated is 400mg/L, and the active adsorption sites on the surface of the PPY-PANI modified xonotlite composite material are rapidly adsorbed by Pb within 30min of starting adsorption 2+ Occupied, belonging to the rapid adsorption process; after 30min, the active adsorption sites on the surface of the PPY-PANI modified xonotlite composite material are basically occupied, and the rising is slowed downBelongs to a slow adsorption process; the dynamic equilibrium is already reached at 60min.
The instrument, model and manufacturer information used in the embodiment of the invention are shown in table 1.
Table 1 instrument and model and manufacturer information
The specific sources of purchase of the raw materials used in the examples of the present invention are shown in Table 2.
TABLE 2 sources of raw materials
The technical scheme of the invention is further described by the following examples.
In the embodiment of the invention, the room temperature is 25+/-2 ℃.
Example 1
(1) Preparation of xonotlite
Weighing 4.0g of powdery calcium oxide (CaO) as a calcium source, adding 40mL of deionized water at 90 ℃, magnetically stirring and dissolving for 30min under the condition of constant-temperature water bath at 25 ℃ to form pasty calcium hydroxide (Ca (OH) 2 ) 6.0g of powdered silicon dioxide (SiO 2 ) 10g of foaming agent urea (CH) 4 N 2 Adding 40mL of deionized water, continuously stirring, simultaneously weighing 2.0g of potassium hydroxide (KOH) and dissolving in 5mL of deionized water to obtain a potassium hydroxide solution, taking the potassium hydroxide solution as an alkaline environment, slowly dripping the potassium hydroxide solution into the deionized water within 30min to obtain a mixture, transferring the mixture into a high-pressure reaction kettle, reacting for 12h at 230 ℃, cooling to room temperature, alternately washing with 0.1mol/L of HCl solution and deionized water to neutrality, drying at 80 ℃, grinding and sieving with a 140-mesh sieve to obtain xonotlite;
(2) Preparation of polypyrrole-polyaniline modified xonotlite
Weighing 5.0g of powdery tobermorite prepared in the step (1), adding the powdery tobermorite into a 500mL three-necked flask, adding 100mL of chloroform as a reaction solution, magnetically stirring the mixture in a water bath for 30min, controlling the temperature below 8 ℃ by using an ice bag to obtain a suspension, adding 1.6mL of polypyrrole (PPY) and 1.0g of Polyaniline (PANI), continuously stirring the mixture for 30min to obtain a mixture, weighing 5.0g of ferric chloride, adding the ferric chloride into 180mL of chloroform solvent, carrying out ultrasonic treatment for 15min to obtain ferric chloride chloroform solution, slowly adding the ferric chloride chloroform solution into the mixture by using a constant-pressure dropping funnel, continuously reacting for 10h at the temperature below 8 ℃, filtering, alternately washing the mixture for 3-4 times by using ethanol and deionized water, drying the mixture at the temperature of 80 ℃, and sieving the mixture by a 140-mesh sieve to obtain the polypyrrole-polyaniline modified tobermorite (PPY-PANI modified tobermorite);
the preparation flow of the PPY-PANI modified xonotlite in the step (2) is shown in a figure 1.
1. Characterization of Performance
a. Fourier transform infrared analysis
The IR spectrum of the PPY-PANI modified xonotlite material prepared in example 1 was obtained by IRPrestinge-21/TIFTIR-8800S Fourier transform IR spectrometer (FIG. 2), as can be seen from FIG. 2, at 3403.24cm -1 The site has a polymolecular association O-H bond in the xonotlite structure, at 1446.46cm -1 And 871.18cm -1 The position has a stretching vibration peak of calcium carbonate ion at 708.86cm -1 At the peak of Si-O-Si absorption of bending vibration, and at 1145.69cm -1 The flexible vibration of C-N bond in polyaniline is 1000cm -1 To 600cm -1 There was a stretching vibration peak of Ar-H, and it was also observed at 1007.25cm -1 Is provided with deformation vibration of C-H in pyridine ring of 1587.29cm -1 The position is the telescopic vibration absorption peak of the pyridine ring, and the N-H bond of the pyridine is 3403.24cm -1 The positions are coincided with O-H, and the successful modification of xonotlite by polypyrrole and polyaniline in the embodiment 1 of the invention can be confirmed through the data analysis.
b. SEM analysis
SEM (scanning electron microscope) images of the PPY-PANI modified xonotlite material prepared in the embodiment 1 are shown in figure 3. As can be seen from fig. 3, the PPY-PANI modified xonotlite composite material is a stack of sheets, and has a large number of defects, and the surface of the sheets has a plurality of irregular fibers, which is beneficial to increasing the surface adsorption area of the composite material.
2. Application of polypyrrole-polyaniline modified xonotlite in treatment of lead wastewater
The PPY-PANI modified xonotlite material prepared in example 1 is taken as an adsorbent, and according to the experimental method of FIG. 4, the influence of the factors such as the amount of the adsorbent, the initial concentration of lead ions, pH, adsorption time and the like of the PPY-PANI modified xonotlite material on the effect of the composite material on lead ions is explored to obtain the effect of the PPY-PANI modified xonotlite composite material on Pb 2+ Is the optimal adsorption conditions of the (a) and the removal rate p% and the adsorption capacity Q e The calculation method of (a) is as shown in the formula I and the formula II:
p％＝(C 0 -C e )/C 0 *100％ (I)
Q e ＝(C 0 -C e )*V/m (II)
wherein C is 0 : lead ion (Pb) 2+ ) Is expressed in mg.L -1 ；
C e : lead ion (Pb) after being adsorbed by PPY-PANI modified xonotlite composite material 2+ ) Concentration in mg.L -1 ；
V: lead ion (Pb) 2+ ) The volume of the solution is L;
m: the mass of the added PPY-PANI modified tobermorite composite material is expressed in g.
Pb 2+ The drawing of the standard curve comprises the following steps:
(1) Lead ion (Pb) 2+ ) Preparing a stock solution: 3.1981g of lead nitrate (Pb (NO) 3 ) 2 ) Adding deionized water into 100mL beaker, dissolving, transferring into 1L volumetric flask, transferring liquid of beaker washed with deionized water into volumetric flask, washing for 3-4 times, diluting with water to 1/2-2/3 of volumetric flask, shaking, diluting with water to scale, fixing volume, shaking to obtain 2g/L lead ion (Pb) 2+ ) And (5) storing the stock solution. Taking outClean 1L reagent bottle, prepared lead ions (Pb 2+ ) The stock solution is moved into a reagent bottle, and a label is attached for standby.
(2) Preparation of an ammoniacal buffer solution (ph=10.5): 1.3373g of ammonium chloride (NH) was weighed out accurately by an analytical balance 4 Cl) in a 100mL beaker, adding deionized water for dissolution, transferring into a 250mL volumetric flask, adding 33.5mL ammonia water, adding water for dilution to the 1/2-2/3 position of the volumetric flask for shaking, adding water for dilution to a scale, fixing the volume, and shaking to obtain an ammonia buffer solution (pH=10.5). And transferring the prepared ammonia buffer solution into a reagent bottle, and labeling for later use.
(3) Lead ion (Pb) 2+ ) Preparation of color reagent (0.03% PF), namely accurately weighing 0.0750g of phenyl fluorescent copper by an analytical balance, dissolving the phenyl fluorescent copper in a mixed solution of 125mL of absolute ethyl alcohol and a sulfuric acid solution consisting of 12.5mL of sulfuric acid and water, wherein the volume ratio of the absolute ethyl alcohol to the total volume of sulfuric acid to water is 1:6, transferring the mixed solution into a 250mL volumetric flask, fixing the volume by absolute ethyl alcohol, and placing the mixed solution in a dark place for 24 hours, wherein a filtering method can be used.
(4) 10mg/L of lead ion (Pb) 2+ ) Preparing a standard solution: a100 mL volumetric flask was taken and 0.5mL of 2g/L lead ion (Pb) 2+ ) Diluting the stock solution with deionized water to scale to obtain 10mg/L lead ion (Pb) 2+ ) Standard solution.
Taking 8 clean 50mL volumetric flasks, and transferring 0mL, 1mL, 2mL, 3mL, 4mL, 5mL, 6mL, and 7mL of 10mg/L lead ion (Pb) 2+ ) Adding 2mL of ammonia buffer solution and 2mL of lead ion color developing agent into each volumetric flask, diluting to obtain lead ion solution with the concentration of 0mg/L, 0.2mg/L, 0.4mg/L, 0.6mg/L, 0.8mg/L, 1.0mg/L, 1.2mg/L and 1.4mg/L on a scale, shaking uniformly, preheating a visible light spectrophotometer for 20min in advance, measuring absorbance at the wavelength equal to 578nm, recording and processing data to obtain Pb 2+ A standard curve.
The amount of PPY-PANI modified xonotlite is used for adsorbing Pb 2+ Influence of (2)
0.0103g, 0.0201g, 0.0297g, 0.0400g, 0.0497g, 0.0698g, 0.1003g, 0.1300g and 0.1601g of the sample prepared in example 1 were accurately weighed by an analytical balancePPY-PANI modified xonotlite was added to a 250mL conical flask with 100mL Pb at 400mg/L, respectively 2+ And (3) setting the rotating speed of the water bath constant temperature vibrating box to 150r/min, taking out after 1h, and analyzing experimental data according to the method of FIG. 4 to determine the optimal adsorbent dosage.
The dosage of the PPY-PANI modified xonotlite adsorbent is equal to Pb 2+ The effect of removal is shown in fig. 5, and it can be seen from fig. 5 that as the amount of the adsorbent of the PPY-PANI modified tobermorite composite material increases, the removal rate generally increases from 79.69% to 98.68%, and then the adsorption capacity gradually decreases from 3007.48mg/g to 246.53mg/g as the amount of the adsorbent increases. When the dosage of the PPY-PANI modified xonotlite composite material reaches 0.0400g or more, the removal rate is almost unchanged and is maintained at about 98 percent. When the dosage of the PPY-PANI modified xonotlite composite material is 0.0400g, the removal rate reaches 98.26%, and the adsorption capacity is 982.59mg/g; when the amount of the adsorbent is 0.0297g, the removal rate is 84.62%, and the adsorption capacity is 1139.70mg/g; when the amount of the adsorbent used was 0.0497g, the removal rate was 98.33% and the adsorption capacity was 791.42mg/g. Through the data analysis, the influence of the removal rate and the adsorption capacity is comprehensively considered, the using amount of 0.0400g of the adsorbent is selected to be optimal, and the subsequent experiments all weigh 0.0400g of the adsorbent to explore the influence of other factors.
2. Pb is adsorbed by the initial concentration of lead ions on the PPY-PANI modified hard silicon calcium 2+ Influence of (2)
7 PPY-PANI modified xonotlite composite materials prepared in example 1, of which the concentration is 100mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L and 700mg/L are accurately weighed by an analytical balance, placed in a 250mL conical flask, and 100mL Pb with equal concentration gradients are prepared 2+ And (3) setting the rotating speed of the water bath constant temperature vibrating box to 150r/min, vibrating for 1h, taking out, and analyzing experimental data according to the method of FIG. 4 to determine the optimal initial concentration of lead ions.
The initial concentration of lead ions adsorbs Pb by the PPY-PANI modified xonotlite adsorbent 2+ As can be seen from FIG. 6, the effect of the PPY-PANI modified tobermorite composite material on the initial concentration of lead ions increases gradually as shown in FIG. 6The lead ion removal rate generally tends to decrease, and the adsorption capacity increases with the initial lead ion concentration. When the initial concentration of lead ions is 300mg/L, the removal rate reaches 97.59 percent, and the adsorption capacity is 730.11mg/L; when the initial concentration of lead ions is 400mg/L, the removal rate is 98.00%, and the adsorption capacity is increased to 984.96mg/L; when the initial concentration of lead ions is 500mg/L, the removal rate is 87.58%, and the adsorption capacity reaches 1092.08mg/L. Through the data analysis, the influence of the removal rate and the adsorption capacity is comprehensively considered, and the influence of other factors on the adsorption performance of the adsorbent is explored by selecting the initial concentration of 400mg/L lead ions.
pH vs. Pb adsorption 2+ Influence of (2)
7 parts of the PPY-PANI modified xonotlite composite material prepared in example 1, 0.0400g, was accurately weighed by an analytical balance into a 250mL conical flask, and 100mL of Pb at 400mg/L was added 2+ The solution is shaken up, the pH value of the system is respectively adjusted to 2, 3, 4, 5.5 (the acidity of the adsorbent is not adjusted by adding acid and alkali) and 6.5, 7.5 and 8 by using 1mol/L HCl and 1mol/L NaOH, the conical flask is placed in a water bath constant temperature shaking box, the rotating speed is adjusted to 150r/min, the solution is taken out after shaking for 1h, and experimental data are analyzed according to the method of FIG. 4 to determine the optimal adsorption pH value.
Adsorption pH to PPY-PANI modified xonotlite adsorbent to adsorb Pb 2+ As can be seen from fig. 7, the removal rate and adsorption capacity increased slowly with increasing pH at ph=2 to 4, and increased rapidly from 85% to 98% and from 858.59mg/g to 987.44mg/g at ph=4 to 5.5. The removal rate was lower at ph=2-4, probably due to H + And Pb 2+ With the same electrical properties, so H + And Pb 2+ Competing with the PPY-PANI to modify the active site of the surface of the xonotlite composite material, thereby leading to the reduction of the adsorption performance of the adsorbent. Due to Pb 2+ Can form Pb (OH) with hydroxide ion 2 Precipitation affects the accuracy of the data, so the pH is chosen to be no more than 8. When ph=4, the removal rate was 85.47%, the adsorption capacity was 858.95mg/L; when the pH=5.5, the removal rate reaches 98.00%, the adsorption capacity reaches 987.44mg/g, whenAt ph=6.5, the removal rate was 98.42% and the adsorption capacity was 991.42mg/g. Therefore, the factors such as the removal rate and the adsorption capacity are comprehensively considered, and the initial pH (5.5) is adopted as the adsorption condition for carrying out the next experiment.
4. Adsorption time pair Pb adsorption 2+ Influence of (2)
7 parts of the PPY-PANI modified xonotlite composite material prepared in example 1, 0.0400g of the PPY-PANI modified xonotlite composite material, prepared in example 1, are accurately weighed by an analytical balance, and 100mL of Pb at 400mg/L is added into a 250mL conical flask 2+ Placing the conical flask into a water bath constant temperature shaking box, adjusting the rotating speed to 150r/min, taking out one conical flask when the rotating speed is respectively 10min, 20min, 30min, 40min, 60min, 90min and 120min, and analyzing experimental data according to the method of FIG. 4 to determine the optimal adsorption time.
Adsorption time is used for adsorbing Pb by PPY-PANI modified xonotlite adsorbent 2+ As can be seen from fig. 8, the removal rate and the adsorption capacity generally increase with increasing adsorption time as seen in fig. 8. The removal rate and the adsorption capacity rise rapidly within 0-30min, rise slowly after 30min, and basically have no change after 60min. This is because the active adsorption sites on the surface of the PPY-PANI modified xonotlite composite material are rapidly adsorbed by Pb within 30min from the start of adsorption 2+ Occupied, belonging to the rapid adsorption process; after 30min, the active adsorption sites on the surface of the PPY-PANI modified xonotlite composite material are basically occupied, the rising is slowed down, and the slow adsorption process is adopted; the dynamic equilibrium is already reached at 60min. The lead ion removal rate is 97.70% when the adsorption time is 40min, the adsorption capacity is 969.73mg/g, the lead ion removal rate reaches 98.45% when the adsorption time is 60min, and the adsorption capacity is increased to 987.05mg/g, and basically no change exists after 60min. Comprehensively considering factors such as lead ion removal rate, adsorbent adsorption capacity and the like, and adopting the adsorption time of 60min is optimal.
5. The foaming agent species adsorbs Pb to PPY-PANI modified xonotlite 2+ Influence of (2)
Accurately weighing 0.0400g of the xonotlite prepared in the step (1) of the example 1 and the xonotlite modified by urea without a foaming agent respectively by using an analytical balance (the preparation method is the same as the step (1) of the example 1, except that the addition of urea as the foaming agent is omitted), and the corresponding modified materials (the PPY-PANI modified xonotlite prepared by using the xonotlite modified by urea without the foaming agent, the preparation method is the same as the step (2) of the example 1 and the PPY-PANI modified xonotlite prepared in the example 1), respectively placing the xonotlite into 4 conical flasks of 250mL, respectively adding 400mg/L of lead ion solution, placing the conical flasks in a water bath constant temperature shaking box, setting the rotating speed to 150r/min, taking out after shaking for 1h, recording and processing data, and analyzing experimental data according to the method of FIG. 4, and the results are shown in Table 3.
TABLE 3 different Material pairs Pb 2+ Adsorption performance influence of (2)
| Adsorbent and process for producing the same | Adsorption capacity (mg/g) |
| Tobermorite modified by urea without foaming agent | 439.12 |
| Tobermorite prepared in example 1 | 556.32 |
| PPY-PANI modified xonotlite (urea without foaming agent) | 798.50 |
| PPY-PANI modified xonotlite prepared in example 1 | 985.27 |
FIG. 9 shows, from left to right, a non-foaming agent urea modified xonotlite, a xonotlite prepared in example 1, a PPY-PANI modified xonotlite (non-foaming)The urea modification agent), and the result graph of the adsorption of lead ions in the filtrate by the PPY-PANI modified xonotlite prepared in the example 1, it can be clearly observed that the color gradually becomes lighter from left to right, namely the concentration of lead ions is from large to small from left to right. As can be seen from Table 3, the adsorption capacity of xonotlite increased from 439.12mg/L to 556.32mg/L, and the adsorption capacity of the modified material increased from 798.50mg/L to 985.27mg/L, and the adsorption capacity increased by 186.87mg/L. Therefore, it can be judged that adding urea as the foaming agent can promote the tobermorite material to Pb 2+ The adsorption performance of (2) may be improved due to the CO provided by urea 3 2- So that the negative charge on the surface of the xonotlite is increased, thereby being beneficial to adsorbing cations by electrostatic attraction and simultaneously CO 3 2- Can be combined with Pb 2+ Generating PbCO 3 And precipitating to remove part of lead ions, so that the adsorption performance of the xonotlite is improved.
In conclusion, by using the amount of Pb as the adsorbent 2+ The initial concentration, pH and adsorption time are used for adsorbing Pb by the PPY-PANI modified tobermorite composite material 2+ The influence of the adsorption effect can obtain the PPY-PANI modified xonotlite composite material with the dosage of 0.0400g and Pb 2+ When the initial concentration is 400mg/L, pH =5.5 and the adsorption time is 60min, the adsorption effect is optimal, the removal rate can reach more than 98%, the adsorption capacity reaches more than 980mg/g, and the adsorption effect of the material added with urea serving as the foaming agent on lead ions is obviously improved.
3. Desorption performance of PPY-PANI modified xonotlite
The lead ion desorption research is carried out on the PPY-PANI modified xonotlite by adopting HCl as an acidic desorber and EDTA-2Na as a salt desorber, and the specific method comprises the following steps:
2 parts of the PPY-PANI modified xonotlite prepared in example 1 is accurately weighed by an analytical balance, placed in a 250mL conical flask, 400mg/L of lead ion solution is added, then placed in a water bath constant temperature shaking box, the rotating speed is set to 150r/min, the mixture is taken out after shaking for 1 hour, filtered, residues are left, dried and placed in the conical flask, and 100mL, 0.01mol/L of hydrochloric acid and 0.01mol are respectively addedPlacing the EDTA-2Na solution of L in a water bath constant temperature shaking box, setting the rotating speed at 150r/min, shaking for 2h, taking out, filtering, reserving filter residues, drying the filter residues, grinding and sieving again to obtain an HCl desorption material and an EDTA-2Na desorption material, weighing 0.0400g PPY-PANI modified xonotlite, 0.01mol/L HCl desorption material and 0.01mol/LEDTA-2Na desorption material respectively, adding 400mg/L Pb 2+ The solution was re-adsorbed, and experimental data were recorded and processed, with the results shown in table 4.
TABLE 4 PPY-PANI modified xonotlite vs. Pb 2+ Is the desorption result of (2)
| Adsorbent and process for producing the same | Removal rate (%) | Adsorption capacity (mg/L) |
| PPY-PANI modified xonotlite | 99.06 | 983.26 |
| 0.01mol/L HCl desorbing material | 75.64 | 750.06 |
| 0.01mol/L EDTA-2Na desorption material | 86.72 | 860.74 |
As can be seen from the data in Table 4, the removal rate was reduced to 75.64% by desorption with 0.01mol/L HCl, 76.36% of the starting material, and the adsorption capacity was reduced from 983.26mg/L to 750.06mg/L, with a breakage of 23.72%. After desorption with 0.01mol/L EDTA-2Na solution, the removal rate was reduced from 99.06% to 86.72%, by 12.34%, the adsorption capacity was reduced to 87.54% of the starting material, and was 860.74mg/L. In general, the desorption effect of EDTA-2Na solution of 0.01mol/L is better than that of hydrochloric acid of 0.01mol/L, and the concentration of the EDTA-2Na solution should be paid attention to when the EDTA-2Na solution is desorbed by an acid desorber, and when the concentration is too high, the xonotlite is dissolved to cause material loss, but the PPY-PANI modified xonotlite prepared in the embodiment 1 of the invention has excellent desorption performance.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the polypyrrole-polyaniline modified xonotlite is characterized by comprising the following steps of:
(1) Preparation of xonotlite
Dissolving a calcium source in water, adding a silicon source and a foaming agent, continuously stirring under an alkali environment to obtain a mixture, reacting under a heating condition, cooling, washing to be neutral, drying, grinding and sieving to obtain the xonotlite;
(2) Preparation of polypyrrole-polyaniline modified xonotlite
Stirring the xonotlite obtained in the step (1) and chloroform in a water bath, cooling to below 8 ℃ to obtain a suspension, adding polypyrrole and polyaniline into the suspension, continuously stirring to obtain a mixture, adding ferric chloride solution into the mixture for reaction, filtering, washing, drying and sieving to obtain the polypyrrole-polyaniline modified xonotlite.
2. The method for preparing polypyrrole-polyaniline modified xonotlite according to claim 1, wherein the calcium source, the silicon source andthe mass ratio of the foaming agent is 4:6:10, the calcium source is CaO, and the silicon source is SiO 2 The foaming agent is urea.
3. The method for preparing polypyrrole-polyaniline modified xonotlite according to claim 1, wherein the feed liquid ratio of the xonotlite, the polypyrrole and the polyaniline is 5 g:1.6 ml:1 g.
4. The preparation method of polypyrrole-polyaniline modified xonotlite according to claim 1, wherein the ferric chloride solution is prepared by adding ferric chloride into chloroform, and performing ultrasonic treatment for 15min, wherein the feed liquid ratio of the ferric chloride to the chloroform is 5g to 180mL.
5. The method for preparing polypyrrole-polyaniline modified xonotlite according to claim 1, wherein the ferric chloride solution is added into the mixture to react for 10 hours at 8 ℃.
6. The method for preparing polypyrrole-polyaniline modified xonotlite according to claim 1, wherein the temperature of the drying in step (1) and step (2) is 80 ℃, and the drying is performed by sieving through a 140-mesh sieve.
7. A polypyrrole-polyaniline modified xonotlite prepared by the preparation method of any one of claims 1 to 6.
8. Use of polypyrrole-polyaniline modified xonotlite according to claim 7 in the treatment of lead wastewater, wherein the polypyrrole-polyaniline modified xonotlite is added to the wastewater to be treated to adsorb lead in the wastewater.
9. The use according to claim 8, wherein the addition of polypyrrole-polyaniline modified xonotlite in the wastewater to be treated is not less than 0.04g/100mL, and the adsorption time is not less than 60min.
10. The use according to claim 8, wherein the concentration of lead ions in the wastewater to be treated is 400mg/L or less and the pH is 5.5-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310050124.XA CN116173931B (en) | 2023-02-01 | Polypyrrole-polyaniline modified xonotlite as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310050124.XA CN116173931B (en) | 2023-02-01 | Polypyrrole-polyaniline modified xonotlite as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116173931A true CN116173931A (en) | 2023-05-30 |
| CN116173931B CN116173931B (en) | 2024-07-09 |
Family
ID=
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110269920A1 (en) * | 2010-04-28 | 2011-11-03 | Nanomaterial Innovation Ltd. | Functional polymers and novel composites for co2 sequestration and releasing of fertilizer conversion, co2 foaming, and their applications |
| JP2012240017A (en) * | 2011-05-23 | 2012-12-10 | Nittetsu Kankyo Engineering Kk | Treating material of harmful substance, and treating method of harmful substance |
| KR20150011302A (en) * | 2013-07-22 | 2015-01-30 | 광주과학기술원 | Heavy metal absorbent, method for absorbing heavy metal using the same, manufacturing method and recyling methood thereof |
| CN110090617A (en) * | 2019-04-30 | 2019-08-06 | 广州大学 | A kind of aluminium oxide/calcium silicates graduation laminated film and its preparation method and application |
| CN110385116A (en) * | 2019-06-28 | 2019-10-29 | 沈阳信达泰康医药科技有限公司 | A kind of magnetic nanometer composite material and its preparation and application |
| CN110449114A (en) * | 2019-07-23 | 2019-11-15 | 衡阳师范学院 | A kind of preparation method and application for mixing aluminium eakleite material |
| CN110605101A (en) * | 2019-10-08 | 2019-12-24 | 西安交通大学 | Adsorbent for adsorbing lead ions, and membrane protective agent and water treatment agent containing same |
| US11332389B1 (en) * | 2021-03-15 | 2022-05-17 | King Abdulaziz University | Recylable multifunctional composites for metal ion removal from water |
| WO2022193674A1 (en) * | 2021-03-16 | 2022-09-22 | 华南理工大学 | Magadiite/polypyrrole adsorption material for treating rhodamine b wastewater and preparation method and application of magadiite/polypyrrole adsorption material |
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110269920A1 (en) * | 2010-04-28 | 2011-11-03 | Nanomaterial Innovation Ltd. | Functional polymers and novel composites for co2 sequestration and releasing of fertilizer conversion, co2 foaming, and their applications |
| JP2012240017A (en) * | 2011-05-23 | 2012-12-10 | Nittetsu Kankyo Engineering Kk | Treating material of harmful substance, and treating method of harmful substance |
| KR20150011302A (en) * | 2013-07-22 | 2015-01-30 | 광주과학기술원 | Heavy metal absorbent, method for absorbing heavy metal using the same, manufacturing method and recyling methood thereof |
| CN110090617A (en) * | 2019-04-30 | 2019-08-06 | 广州大学 | A kind of aluminium oxide/calcium silicates graduation laminated film and its preparation method and application |
| CN110385116A (en) * | 2019-06-28 | 2019-10-29 | 沈阳信达泰康医药科技有限公司 | A kind of magnetic nanometer composite material and its preparation and application |
| CN110449114A (en) * | 2019-07-23 | 2019-11-15 | 衡阳师范学院 | A kind of preparation method and application for mixing aluminium eakleite material |
| CN110605101A (en) * | 2019-10-08 | 2019-12-24 | 西安交通大学 | Adsorbent for adsorbing lead ions, and membrane protective agent and water treatment agent containing same |
| US11332389B1 (en) * | 2021-03-15 | 2022-05-17 | King Abdulaziz University | Recylable multifunctional composites for metal ion removal from water |
| WO2022193674A1 (en) * | 2021-03-16 | 2022-09-22 | 华南理工大学 | Magadiite/polypyrrole adsorption material for treating rhodamine b wastewater and preparation method and application of magadiite/polypyrrole adsorption material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | La (OH) 3-modified magnetic pineapple biochar as novel adsorbents for efficient phosphate removal | |
| Lv et al. | Application of EDTA-functionalized bamboo activated carbon (BAC) for Pb (II) and Cu (II) removal from aqueous solutions | |
| Shang et al. | Preferable uptake of phosphate by hydrous zirconium oxide nanoparticles embedded in quaternary-ammonium Chinese reed | |
| Wang et al. | Fast removal of copper ions from aqueous solution by chitosan-g-poly (acrylic acid)/attapulgite composites | |
| Mousavi et al. | Synthesis of Fe3O4 nanoparticles modified by oak shell for treatment of wastewater containing Ni (II) | |
| CN105879841B (en) | A kind of SiO2@PDA@ZIF-8 compound adsorbent and preparation method thereof for selective absorption Pb In Exhausted Water ion | |
| Yao et al. | Defluoridation of water using neodymium-modified chitosan | |
| Pehlivan et al. | Removal of As (V) from aqueous solutions by iron coated rice husk | |
| Tao et al. | Simultaneous removal of acid green 25 and mercury ions from aqueous solutions using glutamine modified chitosan magnetic composite microspheres | |
| Qiu et al. | Fabrication and evaluation of a regenerable HFO-doped agricultural waste for enhanced adsorption affinity towards phosphate | |
| CN106824113B (en) | Preparation and application of imidazole ionic liquid modified chitosan adsorbent | |
| Tan et al. | Efficient removal of arsenate from water by lanthanum immobilized electrospun chitosan nanofiber | |
| Li et al. | Simultaneous speciation of inorganic rhenium and molybdenum in the industrial wastewater by amino-functionalized nano-SiO2 | |
| Guo et al. | Synthesis and application of 8-hydroxyquinoline modified magnetic mesoporous carbon for adsorption of multivariate metal ions from aqueous solutions | |
| Duan et al. | Characterization and adsorption properties of cross-linked yeast/β-cyclodextrin polymers for Pb (II) and Cd (II) adsorption | |
| CN109012586A (en) | Uranium absorption agent and preparation method thereof | |
| CN110801815A (en) | Modified cyclodextrin/mesoporous silicon for adsorbing Pb and Cd and application thereof | |
| Sun et al. | Recovering rare earth elements via immobilized red algae from ammonium-rich wastewater | |
| JP2003334542A (en) | Anion adsorbent, method for removing anion using the adsorbent, method for regenerating anion adsorbent, and method for recovering element | |
| Yin et al. | Facile synthesis of triazole and carboxyl-functionalized cellulose-based adsorbent via click chemistry strategy for efficient Gd (III) removal | |
| Liao et al. | Efficiency and mechanism of amidoxime-modified X-type zeolite (AO-XZ) for Cs+ adsorption | |
| Khoshraftar et al. | On the performance of perlite as a mineral adsorbent for heavy metals ions and dye removal from industrial wastewater: A review of the state of the art | |
| Li et al. | Magnetic polymer–supported adsorbent with two functional adsorption sites for phosphate removal | |
| Thirupathi et al. | Selective removal of copper (II) ions from aqueous solution using pyridyl-bridged mesoporous organosilica hybrid adsorbent | |
| Shao et al. | A pyrazine based metal-organic framework for selective removal of copper from strongly acidic solutions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |