CN115382521B - Halloysite-based hydrotalcite-like composite material and preparation method and application thereof - Google Patents
Halloysite-based hydrotalcite-like composite material and preparation method and application thereof Download PDFInfo
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- CN115382521B CN115382521B CN202210938426.6A CN202210938426A CN115382521B CN 115382521 B CN115382521 B CN 115382521B CN 202210938426 A CN202210938426 A CN 202210938426A CN 115382521 B CN115382521 B CN 115382521B
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- halloysite
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 139
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 111
- 239000008367 deionised water Substances 0.000 claims description 58
- 229910021641 deionized water Inorganic materials 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 47
- 239000011259 mixed solution Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000725 suspension Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000007790 solid phase Substances 0.000 claims description 28
- 239000002957 persistent organic pollutant Substances 0.000 claims description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 14
- 229960001180 norfloxacin Drugs 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011229 interlayer Substances 0.000 claims description 9
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 claims description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 19
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 239000002734 clay mineral Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 35
- 238000005303 weighing Methods 0.000 description 23
- 238000001291 vacuum drying Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical group [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012799 strong cation exchange Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940099373 sudan iii Drugs 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
According to the invention, halloysite is used as a raw material or a carrier, the hydrotalcite-like compound is further assembled to construct a composite material, the synergistic effect of the two layered materials is exerted, the synthesis method of the hydrotalcite-like compound is improved, the functionality of the natural clay mineral halloysite is further improved, and the capability of purifying the water environment is fully exerted. The halloysite-based hydrotalcite-like composite material prepared by the method has good adsorption performance, the adsorption performance of the composite material can be improved by adding halloysite, and the adopted halloysite serving as a raw material is common and easy to obtain, low in cost, low in equipment requirement of the preparation method and convenient for mass production.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a halloysite-based hydrotalcite-like compound composite material, a preparation method and application thereof in treating organic wastewater.
Background
Layered Double Hydroxides (LDHs), also known as hydrotalcite-like compounds, are metal hydroxides composed of two or more metal elements, belonging to ionic layered clay compounds. LDHs are compounds formed by stacking interlayer anions and positively charged laminates. The chemical composition of LDHs has the following general formula [ M ] 2+ 1-x M 3+ x (OH) 2 ] x+ (A n- ) x/n ·mH 2 O, where M 2+ And M 3+ Respectively represent divalent metal cations (Ca) 2+ 、Mg 2+ 、Mn 2+ 、Ni 2+ 、Cu 2+ 、Co 2+ 、Zn 2+ ) And trivalent metal cations (Fe 3+ 、Al 3+ 、Mn 3+ 、Ni 3+ 、La 3+ )，A n– Is an interlayer anion, such as an inorganic anion CO 3 2- 、NO 3 - 、F - 、Cl - 、Br - 、I - 、CrO 4 2- 、PO 4 3- 、SO 4 2- Etc., which act to balance the charge. The layered double hydroxide is widely applied to high-efficiency adsorption materials and catalysts due to the characteristics of large surface area, high porosity, low and simple synthesis cost, unique redox activity, good adsorption performance, ecological friendliness and the like. At present, most hydrotalcite-like compounds are synthesized and prepared directly by adopting chemical reagents.
Besides the artificially synthesized layered clay compound, the natural clay mineral is a layered structure which is formed by connecting silicon oxygen tetrahedral sheets and aluminum oxygen octahedral sheets in different proportions through shared oxygen, has the characteristics of large specific surface area, strong cation exchange capacity, capability of adsorbing heavy metals and organic matters, and the like, and is an ideal pollutant adsorbing material. The halloysite monoclinic system water-containing layered silicate clay mineral is a tubular nanotube with hollow passage inside, and has the advantages of rich reserve, low cost, wide material source, etc. and is often used as carrier material.
Disclosure of Invention
The invention aims to further assemble hydrotalcite-like compound to construct a composite material by taking halloysite as a raw material or a carrier, simultaneously exert the synergistic effect of two layered materials, improve the synthesis method of the hydrotalcite-like compound-containing composite material, further promote the functionality of natural clay mineral halloysite and fully exert the capability of purifying the water environment.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a halloysite-based hydrotalcite-like composite material, which is prepared by the following method:
(1) Calcining halloysite powder in a muffle furnace at 500-800 ℃ for 1-4h (preferably at 600 ℃ for 2 h) in an air atmosphere to obtain calcined halloysite;
the calcined halloysite is subjected to the following treatment to obtain a suspension A: evenly dispersed into deionized water A (the temperature and time are unified for convenience of comparison in the example, and the only standard for practical operation is even dispersion); or stirring at 30-80deg.C in dilute acid water solution for 1-3 hr (preferably 60 deg.C for 2 hr), adding deionized water B, and dispersing; (preferably acid treatment)
The dosage ratio of calcined halloysite to deionized water A is 1g:30-50mL (preferably 1g:40 mL); the dosage ratio of the calcined halloysite to the dilute acid aqueous solution is 1g:10-20mL (preferably 1g:10 mL); the dilute acid aqueous solution is hydrochloric acid, sulfuric acid aqueous solution or nitric acid aqueous solution, and the concentration is 1-5mol/L (preferably 2-3 mol/L); the dosage ratio of calcined halloysite to the total volume of the dilute acid aqueous solution and deionized water B is 1g to 30-50mL (preferably 1g to 40 mL);
(2) Adding Co (NO) to the suspension A obtained in the step (1) 3 ) 2 ·6H 2 O and NiCl 2 ·6H 2 O, disperse allHomogenizing to obtain a mixed solution B; the Co (NO) 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 The mass ratio of O to the calcined halloysite in the step (1) is 1.58-2.2:0.85-1.2:1 (preferably 1.58:0.85:1);
(3) Adding NaOH solution into the mixed solution B obtained in the step (2), and stirring to obtain mixed solution C; the volume ratio of the NaOH solution to the mixed solution B is 1:3-4 (preferably 1:4); the NaOH solution is obtained by dissolving NaOH in deionized water C, and the dosage ratio of NaOH to deionized water C is 1g:5-20mL (preferably 1:12.5);
(4) Adding the raw materials for providing interlayer anions into the mixed solution C obtained in the step (3), and uniformly stirring to obtain a mixed solution D; the mass ratio of the raw material amount for providing interlayer anions to the calcined halloysite in the step (1) is 1-5:1, a step of;
(5) Transferring the mixed solution D obtained in the step (4) into an autoclave for hydrothermal reaction, and performing post-treatment on the obtained reaction mixture to obtain the halloysite-based hydrotalcite-like composite material; the hydrothermal reaction condition is that the reaction is carried out for 6-24 hours at 70-150 ℃.
Deionized water A, B, C is deionized water, and different letters are marked only for distinguishing the deionized water added in different stages, so that the description is convenient, and no other special meaning is provided. The other letters are also only used to distinguish between materials in different stages.
Further, the raw materials for providing interlayer anions in the step (4) are urea and Na 2 CO 3 、NaH 2 PO 4 、Na 2 C 2 O 4 One or a mixture of two or more of these, preferably urea.
Further, the post-treatment in the step (5) is as follows: and cooling the reaction mixture to room temperature, filtering and separating the mixed solution to obtain a solid phase E, washing the solid phase E with deionized water, drying in vacuum, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
The invention also provides the halloysite-based hydrotalcite-like composite material obtained by the preparation method of the halloysite-based hydrotalcite-like composite material, which can fully utilize the structural characteristics of the halloysite with high specific surface area and has obvious stacking generation of a hydrotalcite-like sheet structure.
When the halloysite-based hydrotalcite-like composite material is used for treating organic wastewater, an adsorption method can be adopted for treating organic pollutants in the water, and an advanced oxidation method represented by activated persulfate can also be adopted for treating the organic pollutants in the water.
In addition, the invention also provides application of the halloysite-based hydrotalcite-like composite material in treating organic pollutant wastewater, wherein the organic pollutant contained in the organic pollutant wastewater is one or a mixture of more than two of methylene blue, methyl orange, sudan red III, norfloxacin or tetracycline.
Specifically, the application is as follows: dispersing the halloysite-based hydrotalcite-like composite material and persulfate into organic pollutant wastewater to degrade organic pollutants; the concentration of the organic pollutant is 5-120mg/L; the proportion of the halloysite-based hydrotalcite composite material, the persulfate and the organic pollutant wastewater is 0.5-20g:0.2-1g:1L (preferably 0.2-2g:0.2-1 g:1L).
Further, the persulfate is potassium hydrogen persulfate, potassium persulfate, or sodium persulfate (preferably potassium hydrogen persulfate).
Compared with the prior art, the invention has the following beneficial effects:
(1) The halloysite-based hydrotalcite-like composite material prepared by the method has good adsorption performance, the adsorption performance of the composite material can be improved by adding halloysite, and the adopted halloysite serving as a raw material is common and easy to obtain, low in cost, low in equipment requirement of the preparation method and convenient for mass production.
(2) In the halloysite-based hydrotalcite-like composite material provided by the invention, hydrotalcite-like compounds are uniformly stacked in a sheet structure.
(3) According to the preparation method of the halloysite-based hydrotalcite-like composite material, the absorption performance of the halloysite-based hydrotalcite-like composite material can be remarkably improved through calcination treatment of the halloysite.
(4) According to the preparation method of the halloysite-based hydrotalcite-like composite material, the crystallization degree and the microscopic morphology of the halloysite-based hydrotalcite-like composite material can be improved by carrying out acid leaching treatment on the halloysite, and the halloysite-based hydrotalcite-like composite material is facilitated to be generated.
(5) In the preparation method of the halloysite hydrotalcite-like composite material, urea is adopted as an anion complex, so that the adsorption performance of the prepared halloysite hydrotalcite-like composite material can be remarkably improved.
(6) In the preparation method of the halloysite hydrotalcite-like composite material provided by the invention, the halloysite hydrotalcite-like composite material has an adsorption effect and a catalytic degradation effect on organic pollutants in sewage, and has good adsorption and catalytic degradation performances on dye sudan III and antibiotics.
Drawings
FIG. 1 is an XRD pattern of a halloysite-based hydrotalcite-like composite material prepared in example 1.
Fig. 2 is an SEM image of the halloysite-based hydrotalcite-like composite material prepared in example 1.
FIG. 3 is an XRD pattern of the halloysite-based hydrotalcite-like composite material prepared in example 2.
Fig. 4 is an SEM image of the halloysite-based hydrotalcite-like composite material prepared in example 2.
FIG. 5 is an XRD pattern of the halloysite-based hydrotalcite-like composite material prepared in comparative example 7.
Fig. 6 is an SEM image of the halloysite-based hydrotalcite-like composite material prepared in comparative example 7.
Detailed Description
Example 1
(1) Weighing 10g of halloysite powder, calcining at 600 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite. 1g of calcined halloysite calcined at 600 ℃ is taken and placed in 10mL of HCl solution with the concentration of 2mol/L, and the mixture is magnetically stirred in a water bath kettle at 60 ℃ for 2 hours to obtain a mixed solution containing acid-leached halloysite.
(2) Adding 30mL deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 0.85g NiCl into the mixture 2 ·6H 2 O and 1.58g Co (NO) 3 ) 2 ·6H 2 And stirring by O ultrasonic for 30min.
(3) Weighing 0.8g of NaOH, dissolving in 10mL of deionized water to obtain NaOH solution, slowly pouring into the solution obtained in the step (2), adding 2g of urea, and stirring for 20min by ultrasonic to obtain mixed suspension
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 120 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
The XRD pattern of the halloysite-based hydrotalcite-like composite material is shown in figure 1, and the result of figure 1 shows that the crystal phase component of the sample has a hydrotalcite-like (NiCoAl-LDH) phase;
the SEM image of the halloysite-based hydrotalcite-like composite material is shown in fig. 2, and the sample has obvious lamellar nano structure, uniform distribution, smooth surface and uniform shape.
Example 2
(1) Weighing 12g of halloysite powder, calcining at 600 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite. 1g of calcined halloysite calcined at 600 ℃ is taken and placed in 10mL of deionized water, and the halloysite is magnetically stirred in a water bath at 60 ℃ for 2 hours to uniformly disperse.
(2) Adding 30mL deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 0.85g NiCl into the mixture 2 ·6H 2 O and 1.58g Co (NO) 3 ) 2 ·6H 2 And stirring by O ultrasonic for 30min. .
(3) Weighing 0.8g of NaOH, dissolving in 10ml of deionized water to obtain NaOH solution, slowly pouring into the solution obtained in the step (2), adding 2g of urea, and stirring for 20min by ultrasonic to obtain mixed suspension
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 120 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
The XRD pattern of the halloysite-based hydrotalcite-like composite material is shown in figure 3, and the XRD result shows that the sample has a hydrotalcite-like (NiCoAl-LDH) phase.
The SEM image of the halloysite-based hydrotalcite-like composite material is shown in fig. 4, and the sample has obvious agglomeration and stacking phenomena and lamellar structure distribution.
Example 3
(1) Weighing 10g of halloysite powder, calcining at 600 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite. 1g of halloysite calcined at 600 ℃ is taken and placed in 10mL of HCl solution with the concentration of 2mol/L, and the mixture is magnetically stirred in a water bath kettle at 60 ℃ for 2 hours to obtain a mixed solution containing acid-leached halloysite.
(2) Adding 30mL deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 1.2g NiCl into the mixture 2 ·6H 2 O and 2.1g Co (NO) 3 ) 2 ·6H 2 And stirring by O ultrasonic for 30min.
(3) Weighing 0.8g of NaOH, dissolving in 10ml of deionized water to obtain a NaOH solution, slowly pouring the NaOH solution into the solution obtained in the step (2), adding 2g of urea, and stirring for 20min by ultrasonic waves to obtain a mixed suspension.
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 12 hours at 110 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
Example 4
(1) Weighing 5g of halloysite powder, calcining at 550 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a rate of 5 ℃/min to obtain calcined halloysite. 1g of halloysite calcined at 550 ℃ is taken and placed in 15mL of HCl solution with the concentration of 2mol/L, and the mixture is magnetically stirred in a water bath kettle at 80 ℃ for 2 hours to obtain a mixed solution containing acid-leached halloysite.
(2) Adding 30mL deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 0.95g NiCl into the mixture 2 ·6H 2 O and 1.63g Co (NO) 3 ) 2 ·6H 2 And stirring by O ultrasonic for 30min.
(3) Weighing 1g of NaOH, dissolving in 10ml of deionized water to obtain NaOH solution, slowly pouring into the solution obtained in the step (2), adding 3g of urea, and stirring for 20min by ultrasonic to obtain mixed suspension
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 120 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
Example 5
(1) Weighing a proper amount of halloysite powder, calcining at 700 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite. 1g of calcined halloysite at 700 ℃ is taken and placed in 10mL of HCl solution with the concentration of 3mol/L, and the mixture is magnetically stirred for 3 hours in a water bath kettle at 80 ℃ to obtain a mixed solution containing acid-leached halloysite.
(2) Adding 40mL deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 0.85g NiCl into the mixture 2 ·6H 2 O and 1.58g Co (NO) 3 ) 2 ·6H 2 And stirring by O ultrasonic for 30min.
(3) Weighing 0.5g of NaOH, dissolving in 10ml of deionized water to obtain NaOH solution, slowly pouring into the solution obtained in the step (2), adding 3g of urea, and stirring for 20min by ultrasonic to obtain mixed suspension
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 6 hours at 140 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
Example 6
(1) Weighing a proper amount of halloysite powder, calcining at 600 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite. 1g of halloysite calcined at 600 ℃ is taken and placed in 10mL of H with the concentration of 3mol/L 2 SO 4 And magnetically stirring the solution in a water bath kettle at 40 ℃ for 4 hours to obtain a mixed solution containing the acid-dipped halloysite.
(2) Adding 30ml deionized water into the mixture, and stirring with ultrasonic wave to disperse uniformlyThen 1.2g NiCl is added into the mixed solution at the same time 2 ·6H 2 O and 2.1g Co (NO) 3 ) 2 ·6H 2 And stirring by O ultrasonic for 30min.
(3) Weighing 1g of NaOH, dissolving in 10mL of deionized water to obtain NaOH solution, slowly pouring into the solution obtained in the step (2), adding 2.5g of urea, and stirring for 20min by ultrasonic to obtain mixed suspension
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 110 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
Comparative example 1
Halloysite was used as the sample of comparative example 1.
Comparative example 2
(1) 40mL of deionized water was measured in a beaker, while 0.85g of NiCl was added 2 ·6H 2 O and 1.58g Co (NO) 3 ) 2 ·6H 2 Ultrasonic stirring for 30min to obtain mixed solution
(2) Weighing 0.8g of NaOH, dissolving in 10mL of deionized water to obtain a NaOH solution, slowly pouring the NaOH solution into the mixed solution obtained in the step (1), adding 2g of urea, and stirring for 20min by ultrasonic waves to obtain a final mixed suspension. (3) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 120 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the hydrotalcite-like (NiCo-LDH) material.
Comparative example 2 in comparison with examples 1 and 2, the hydrotalcite-like NiCo-LDH composite material was directly hydrothermally synthesized without halloysite added in the synthesis of comparative example 2.
Comparative example 3
(1) Taking 1g of halloysite powder, placing the halloysite powder into 10mL of HCl solution with the concentration of 2mol/L, and magnetically stirring the solution in a water bath kettle at the temperature of 60 ℃ for 2 hours to obtain a mixed solution containing the acid-dipped halloysite.
(2) Adding 30ml deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 0.85g NiCl into the mixture 2 ·6H 2 O and 1.58g Co (NO) 3 ) 2 ·6H 2 And stirring by O ultrasonic for 30min.
(3) Weighing 0.8g of NaOH, dissolving in 10mL of deionized water to obtain a NaOH solution, slowly pouring the NaOH solution into the solution obtained in the step (2), adding 2g of urea, and stirring for 20min by ultrasonic waves to obtain a final mixed suspension.
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 120 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
Comparative example 3 the halloysite in comparative example 3 was not subjected to the calcination step as compared with the example.
Comparative example 4
Weighing a proper amount of halloysite powder, calcining at 600 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite.
Comparative example 5
(1) Weighing a proper amount of halloysite powder, calcining at 600 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite. 1g of calcined halloysite at 600 ℃ is taken and placed in 10ml of deionized water, and the halloysite is magnetically stirred in a water bath at 60 ℃ for 2 hours to uniformly disperse.
(2) Adding 30mL deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 0.85g NiCl into the mixture 2 ·6H 2 And stirring by O ultrasonic for 30min.
(3) Weighing 0.8g of NaOH, dissolving in 10mL of deionized water to obtain a NaOH solution, slowly pouring the NaOH solution into the solution obtained in the step (2), adding 2g of urea, and stirring for 20min by ultrasonic waves to obtain a final mixed suspension.
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 120 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
Comparative example 5 As compared with examples 1 and 2, only NiCl was used in comparative example 5 2 ·6H 2 O-soluble metal salts.
Comparative example 6
(1) Weighing a proper amount of halloysite powder, calcining at 600 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite. 1g of calcined halloysite at 600 ℃ is taken and placed in 10ml of deionized water, and the halloysite is magnetically stirred in a water bath at 60 ℃ for 2 hours to uniformly disperse.
(2) Adding 30mL deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 1.58g Co (NO) into the mixture 3 ) 2 ·6H 2 And stirring by O ultrasonic for 30min.
(3) Weighing 0.8g of NaOH, dissolving in 10mL of deionized water to obtain a NaOH solution, slowly pouring the NaOH solution into the solution obtained in the step (2), adding 2g of urea, and stirring for 20min by ultrasonic waves to obtain a final mixed suspension.
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 120 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃,
grinding to obtain the halloysite-based hydrotalcite-like composite material.
Comparative example 6 in comparison with the example, co (NO) alone was added to comparative example 6 3 ) 2 ·6H 2 O is used as a soluble metal salt.
Comparative example 7
(1) Weighing a proper amount of halloysite powder, calcining at 600 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite. 1g of calcined halloysite at 600 ℃ is taken and placed in 10mL of deionized water, and the halloysite is magnetically stirred in a water bath at 60 ℃ for 2 hours to uniformly disperse.
(2) Adding 30mL deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 0.85g NiCl into the mixture 2 ·6H 2 O and 1.58g Co (NO) 3 ) 2 ·6H 2 And stirring by O ultrasonic for 30min.
(3) Weighing 0.8g of NaOH, dissolving in 10mL of deionized water to obtain NaOH solution, slowly pouring into the solution obtained in the step (2), and adding 1g of Na 2 CO 3 And (5) stirring for 20min by ultrasonic to obtain a final mixed suspension.
(4) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 120 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃,
grinding to obtain the halloysite-based hydrotalcite-like composite material.
Comparative example 7 compared with the example, the raw material added in comparative example 7 capable of providing interlayer anions was Na 2 CO 3 。
The XRD pattern of the halloysite-based hydrotalcite-like composite material prepared in comparative example 7 is shown in FIG. 5; SEM images of the halloysite-based hydrotalcite-like composite material prepared in comparative example 7 are shown in fig. 6.
Comparative example 8
(1) Weighing a proper amount of halloysite powder, calcining at 600 ℃ in the air atmosphere of a tube furnace, preserving heat for 2 hours, and heating at a speed of 10 ℃/min to obtain calcined halloysite. 1g of calcined halloysite at 600 ℃ is taken and placed in 10mL of deionized water, and the halloysite is magnetically stirred in a water bath at 60 ℃ for 2 hours to uniformly disperse.
(2) Adding 30mL deionized water into the mixture, stirring with ultrasonic wave to disperse uniformly, and adding 0.85g NiCl into the mixture 2 ·6H 2 O and 1.58g Co (NO) 3 ) 2 ·6H 2 Ultrasonic stirring for 30min, adding 0.18g urea, and ultrasonic stirring for 20min to obtain final mixed suspension
(3) Transferring the mixed suspension into a high-pressure reaction kettle for reaction for 8 hours at 120 ℃, cooling to room temperature, filtering and separating the mixed solution to obtain a solid phase, washing the solid phase with deionized water, vacuum drying for 6 hours at 80 ℃, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
Comparative example 8 the amount of the anionic complex urea added in comparative example 8 was reduced compared to example 1.
Application of comparative experiment 1
50mL of Norfloxacin (NFA) solution with initial concentration of 20mg/L is prepared to simulate organic pollutant wastewater, 25mg or 40mg of samples prepared in examples 1-4 and comparative examples 1-8 are respectively weighed and added into the NFA solution, ultrasonic stirring is carried out, after a period of reaction, a small amount of solution is taken for solid-liquid separation, then the concentration of residual NFA in the solution is tested by an ultraviolet spectrophotometer, and the adsorption rate of the sample to the NFA is calculated. The experimental results are shown in table 1.
Application of comparative experiment 2
Preparing 50mL of Sudan red III solution with initial concentration of 20mg/L to treat organic pollutant wastewater, respectively weighing 25mg of samples prepared in examples 1-4, adding the samples into the Sudan red III solution, carrying out ultrasonic stirring, carrying out solid-liquid separation on a small amount of solution after reacting for a period of time, testing the concentration of residual Sudan red III in the solution by using an ultraviolet spectrophotometer, and calculating the adsorption rate of the samples to the Sudan red III.
Application of comparative experiment 3
50mL of Norfloxacin (NFA) solution with initial concentration of 20mg/L is prepared to simulate organic pollutant wastewater, 25mg of samples prepared in examples 1-4 and comparative example 1 are respectively weighed and added into the NFA solution, ultrasonic stirring is carried out, adsorption reaction is carried out for 30min, 25mg of potassium hydrogen Persulfate (PMS) is added for 20min and 40min, a small amount of solution is taken for solid-liquid separation, then the concentration of residual NFA of the solution is tested by an ultraviolet spectrophotometer, and the adsorption rate and degradation rate of the sample on the NFA are calculated. The experimental results are shown in table 1.
Table 1 adsorption catalytic degradation effect of samples on organic pollutants
1. The application experimental results of examples 1-4 and comparative examples 1 and 4 in table 1 show that the halloysite-based hydrotalcite-like composite material prepared in examples 1-4 has good adsorptivity and degradability to norfloxacin organic pollutants and good adsorptivity to sudan red III organic pollutants.
2. It is demonstrated by examples 1-4 and comparative example 2 that the addition of halloysite can increase the adsorption rate of halloysite-based hydrotalcite-like composite materials to norfloxacin organic pollutants.
3. By the description of examples 1-4 and comparative example 3, the adsorption performance of halloysite-based hydrotalcite-like composite material can be improved by calcining and modifying halloysite
4. By the description of examples 1-4 and comparative examples 6-7, the adsorption performance of the halloysite-based hydrotalcite-like composite material prepared by adopting urea as an anion complex can be remarkably improved.
5. Examples 1-4 and comparative examples 5-6 demonstrate that the adsorption performance of halloysite-based hydrotalcite-like composite materials prepared by adding the soluble bimetallic salt is better than that of halloysite-based hydrotalcite-like composite materials prepared by adding the soluble monometal salt.
Claims (6)
1. The application of the halloysite-based hydrotalcite-like composite material in treating organic pollutant wastewater is characterized in that the halloysite-based hydrotalcite-like composite material is prepared by adopting the following method:
(1) Calcining halloysite powder in a muffle furnace at 500-800 ℃ in an air atmosphere for 1-4h to obtain calcined halloysite;
the calcined halloysite is subjected to the following treatment to obtain a suspension A: uniformly dispersing into deionized water A; or stirring in dilute acid water solution at 30-80deg.C for 1-3 hr, adding deionized water B, and dispersing;
the dosage ratio of the calcined halloysite to the deionized water A is 1g:30-50mL; the dosage ratio of the calcined halloysite to the dilute acid aqueous solution is 1g:10-20mL; the dilute acid aqueous solution is hydrochloric acid, sulfuric acid aqueous solution or nitric acid aqueous solution, and the concentration is 1-5mol/L; the dosage ratio of the calcined halloysite to the total volume of the dilute acid aqueous solution and the deionized water B is 1g to 30-50mL;
(2) Adding Co (NO) to the suspension A obtained in the step (1) 3 ) 2 ·6H 2 O and NiCl 2 ·6H 2 O, dispersing uniformly to obtain a mixed solution B; the Co (NO) 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 The mass ratio of O to the calcined halloysite in the step (1) is 1.58-2.2:0.85-1.2:1, a step of;
(3) Adding NaOH solution into the mixed solution B obtained in the step (2), and stirring to obtain mixed solution C; the volume ratio of the NaOH solution to the mixed solution B is 1:3-4; the NaOH solution is obtained by dissolving NaOH in deionized water C, and the dosage ratio of NaOH to deionized water C is 1g:5-20mL;
(4) Adding the raw materials for providing interlayer anions into the mixed solution C obtained in the step (3), and uniformly stirring to obtain a mixed solution D; the mass ratio of the raw material amount for providing interlayer anions to the calcined halloysite in the step (1) is 1-5:1, a step of; the raw material for providing interlayer anions is urea;
(5) Transferring the mixed solution D obtained in the step (4) into an autoclave for hydrothermal reaction, and performing post-treatment on the obtained reaction mixture to obtain the halloysite-based hydrotalcite-like composite material; the hydrothermal reaction condition is that the reaction is carried out for 6-24 hours at the temperature of 110-150 ℃;
the application is as follows: dispersing the halloysite-based hydrotalcite-like composite material and persulfate into organic pollutant wastewater to degrade organic pollutants; the concentration of the organic pollutant is 5-120mg/L; the proportion of the halloysite-based hydrotalcite-like composite material, the persulfate and the organic pollutant wastewater is 0.5-20g, and the proportion of the persulfate and the organic pollutant wastewater is 0.2-1g and 1L.
2. The use according to claim 1, wherein: the calcined halloysite in the step (1) is subjected to the following treatment to obtain a suspension A: stirring in dilute acid water solution at 30-80deg.C for 1-3 hr, adding deionized water B, and dispersing.
3. The use according to claim 1, wherein: co (NO) as described in step (2) 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 The mass ratio of O to the calcined halloysite described in step (1) was 1.58:0.85:1.
4. the use according to claim 1, wherein: the post-treatment in the step (5) is as follows: and cooling the reaction mixture to room temperature, filtering and separating the mixed solution to obtain a solid phase E, washing the solid phase E with deionized water, drying in vacuum, and grinding to obtain the halloysite-based hydrotalcite-like composite material.
5. The use according to claim 1, wherein: the organic pollutant contained in the organic pollutant wastewater is one or a mixture of more than two of methylene blue, methyl orange, sudan red III, norfloxacin or tetracycline.
6. Use according to claim 1, characterized in that the persulfate is potassium persulfate, potassium persulfate or sodium persulfate.
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| Construction of nickel cobalt-layered double hydroxide/ functionalized–halloysite nanotubes composite for electrochemical detection of organophosphate insecticide;Thangavelu Kokulnathana 等;《Chemical Engineering Journal》;第433卷;第2页第2.1-2.3节、第5页第3.1节 * |
| Effects of calcination and acid treatment on improving benzene adsorption performance of halloysite;Liangliang Deng 等;《Applied Clay Science》;第181卷;摘要、第2页第2.2节 * |
| Singlet oxygen-dominated transformation of oxytetracycline by peroxymonosulfate with CoAl-LDH modified hierarchical porous ceramics: Toxicity assessment;Qingcan Zhou 等;《Chemical Engineering Journal》;第436卷;全文 * |
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