CN115501852A - Preparation method and application of metal-doped alumina hydrate with high adsorption performance - Google Patents
Preparation method and application of metal-doped alumina hydrate with high adsorption performance Download PDFInfo
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- CN115501852A CN115501852A CN202211061495.XA CN202211061495A CN115501852A CN 115501852 A CN115501852 A CN 115501852A CN 202211061495 A CN202211061495 A CN 202211061495A CN 115501852 A CN115501852 A CN 115501852A
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- doped alumina
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 37
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 238000007865 diluting Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 229910052785 arsenic Inorganic materials 0.000 claims description 16
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 16
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 10
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 claims 2
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical compound OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 abstract description 9
- 229960003052 roxarsone Drugs 0.000 abstract description 8
- 239000011787 zinc oxide Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 11
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 229910001388 sodium aluminate Inorganic materials 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 7
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 7
- 229910002588 FeOOH Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 4
- 229910002706 AlOOH Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- -1 phenolic acid compounds Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical group O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GEVMESGZABCIMM-UHFFFAOYSA-M [OH-].[Cu+]=O Chemical compound [OH-].[Cu+]=O GEVMESGZABCIMM-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- XKNKHVGWJDPIRJ-UHFFFAOYSA-N arsanilic acid Chemical compound NC1=CC=C([As](O)(O)=O)C=C1 XKNKHVGWJDPIRJ-UHFFFAOYSA-N 0.000 description 1
- 229950002705 arsanilic acid Drugs 0.000 description 1
- 150000001495 arsenic compounds Chemical class 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
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- IQGILBZPWWYYSR-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe].[Fe] IQGILBZPWWYYSR-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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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 & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method and application of metal-doped alumina hydrate with high adsorption performance, wherein the method comprises the following steps: s1, preparing a metal salt solution: mixing metal salt with deionized water to form a uniform metal salt solution; s2, preparing a sodium metaaluminate solution: taking NaAlO 2 Mixing with deionized water, stirring until the mixture is completely dissolved, adding ethylene glycol, and stirring uniformly again to form a sodium metaaluminate solution; s3, preparing a metal-doped alumina hydrate material: and (2) diluting the metal salt solution, mixing the diluted metal salt solution with a sodium metaaluminate solution, and then sequentially stirring and mixing, carrying out hydrothermal reaction, centrifuging, washing and drying to obtain the metal-doped alumina hydrate material. Andcompared with a single alumina hydrate material, the prepared metal-doped alumina hydrate material has the advantages that the adsorption performance of the material on Roxarsone (ROX) solution is obviously improved, and the adsorption capacity of the material on ROX is obviously improved.
Description
Technical Field
The invention belongs to the technical field of synthesis of composite materials, and particularly relates to a preparation method and application of a metal-doped alumina hydrate with high adsorption performance.
Background
The 3-nitro-4-hydroxyphenylarsonic acid (roxarsone, ROX) belongs to one of aromatic organic arsenic and is a novel organic-inorganic composite arsenic pollutant. With the development of industry, ROX is used in large quantities as livestock feed additive and pesticide additive, and this organic arsenic compound enters into the environment along with livestock feces and soil, and is converted into inorganic arsenic with stronger toxicity under the action of microorganism or light degradation, which brings safety hazard to ecological environment and human health [ Chen W R, huang C h. Along with the development of industrialization, arsenic pollution in groundwater becomes a global crisis, and global arsenic concentration standards in water are becoming stricter, such as the emission standard of arsenic wastewater is 0.5mg/g, and the arsenic content standard of drinking water is 10 mug/L. Therefore, finding suitable means to treat the pollution of the organic arsenic, a new pollutant, has become the focus of the related field.
For the preparation of the rock sand arsenic adsorbent, the metal coordination, complexation and hydrogen bond and oxygen vacancy formation mechanisms are mainly utilized, and the adsorption materials commonly used in the related research fields at present for removing organic arsenic in water bodies include activated carbon, agricultural wastes, metal oxides, mineral clay, nano materials, molecular sieves and the like [ XieX, cheng H.Adsorption and desorption of phenolic acid compounds on metal oxides and hydroxides, and clay minerals [ J.].Science ofthe Total Environment,2021,757:143765.]. Wentao Fu et al [ FuW, lu D L, yao H, et al, simultaneous roxarsone photocatalytic degradation and inductive addition removal by TiO 2 /FeOOH hybrid[J].Environmental Science and Pollution Research,2020,27(15):18434-18442.]Adopts a hydrothermal method to synthesize the difunctional titanium dioxide/iron hydrate (TiO) 2 FeOOH) hybrid, simultaneously photocatalytically degrading roxaseone and releasing arsenic adsorption, and an adsorption strip with 0.1g/L adsorbent and 10mg/L ROX concentrationUnder the condition, 96% arsenic adsorption removal rate is obtained. The main adsorption mechanism is that the ROX is catalyzed and degraded by abundant hydroxyl on the surface of the adsorbent to release As (V), and the released As (V) is degraded by TiO 2 FeOOH added into the/FeOOH hybrid is quickly absorbed and removed, and the released inorganic arsenic ions are adsorbed. TiO of interest 2 the/FeOOH hybrid has good stability and reliability, and provides possible mechanisms of degrading the roxarsone and releasing the inorganic arsenic by the hybrid, and the defects of the hybrid are that the preparation temperature of the adsorbent is high, the preparation period is long, the preparation process is complex (180 ℃,12 hours), and the removal research of a high-concentration ROX solution is not carried out. Further, paola Santander et al [ alpha ], [
K,
J,Ranganathan S,et al.Photocatalytic degradation of roxarsone by using synthesized ZnO nanoplates[J].Solar Energy,2017,157:335-341.]Synthesizing a ZnO nano-plate by adopting a wet chemical method, realizing effective photodegradation of ROX under the irradiation of ultraviolet light, and realizing 70% of degradation efficiency under the conditions that the concentration of ZnO is 2.5g/L and the concentration of ROX is 15 mg/L; a possible photocatalytic mechanism is the photocatalytic degradation of ROX leading to mineralization into CO 2 And As (V). Wan-Ru Chen et al [ Chen W R, huang C H. Surface adaptation of organic roxarsone and arsanilic acid on and aluminum oxides [ J].Journal ofHazardous Materials,2012,227:378-385]Surface adsorption of ROX and ASA to iron and aluminum oxides was studied and it was found that various inorganic arsenates adsorb rapidly and abundantly to various iron and aluminum oxides, while for ROX aromatic arsenic might adsorb strongly to iron and aluminum oxides due to its arsenate groups. However, the final adsorption capacity of the pure metal oxides herein is not satisfactory.
In conclusion, because the existing ROX adsorbing material often has the problems of complex preparation process, high energy consumption, low adsorption capacity and the like, the method for cleanly preparing the adsorbing material with high adsorption performance by using cheap raw materials under mild conditions is an urgent problem to be solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a metal-doped modified alumina hydrate adsorbent material which is easy to prepare, easily available in raw materials, environment-friendly and excellent in ROX adsorption performance, and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a method for preparing a metal-doped alumina hydrate with high adsorbability, which adopts a one-step hydrothermal method to prepare the metal-doped alumina hydrate with high adsorbability, and comprises the following steps:
step S1, preparing a metal salt solution:
mixing metal salt with deionized water to form a uniform metal salt solution;
step S2, preparing a sodium metaaluminate solution:
taking NaAlO 2 Mixing with deionized water, stirring until the mixture is completely dissolved, adding ethylene glycol, and stirring uniformly again to form a sodium metaaluminate solution;
step S3, preparing a metal-doped alumina hydrate material:
and (2) diluting the metal salt solution, mixing the diluted metal salt solution with a sodium metaaluminate solution, and then sequentially stirring and mixing, carrying out hydrothermal reaction, centrifuging, washing and drying to obtain the metal-doped alumina hydrate material.
Preferably, the metal salt solution in step S1 includes Na 2 ZnO 2 Solution, feCl 3 Solution and CuCl 2 One of the solutions.
Preferably, the Na 2 ZnO 2 The preparation process of the solution is as follows:
dissolving NaOH in deionized water, stirring until the NaOH is completely dissolved, gradually adding ZnO while heating, and heating the solution to boiling after the ZnO is completely added; then keeping the temperature and continuously stirring until the solution becomes clear, stopping heating, naturally cooling, cooling to room temperature, diluting to obtain Na 2 ZnO 2 And (3) solution.
Preferably, the Na 2 ZnO 2 In the preparation process of the solution, the mass ratio of ZnO, naOH and deionized water is 10.
Preferably, the FeCl 3 The preparation process of the solution is as follows:
taking FeCl 3 Dissolving in deionized water, stirring to obtain FeCl 3 And (3) solution.
Preferably, the FeCl 3 In the preparation of the solution, feCl 3 The mass ratio to deionized water was 5.95.
Preferably, the CuCl 2 The preparation process of the solution is as follows:
taking CuCl 2 ·2H 2 Dissolving O in deionized water, stirring to completely dissolve to obtain CuCl 2 And (3) solution.
Preferably, the CuCl 2 In the preparation of the solution, cuCl 2 ·2H 2 The mass ratio of O to deionized water was 6.2.
Preferably, in the step S2, naAlO 2 The mass ratio of the deionized water to the ethylene glycol is 1.2.
Preferably, in the step S3, the dilution process of the metal salt solution is as follows: the metal salt solution was mixed with deionized water in a volume ratio of 4.
Preferably, in the step S3, the diluted metal salt solution and the sodium metaaluminate solution are mixed according to a volume ratio of 10.
Preferably, in step S3, the temperature of the hydrothermal reaction is 60 ℃, the washing is performed 3 times by using deionized water and then 1 time by using absolute ethyl alcohol, and the drying is performed in a drying oven at 60 ℃ for 24 hours.
In a second aspect, the invention provides a metal-doped alumina hydrate with high adsorption performance prepared by the method, which is used as an adsorption material of roxazone ROX.
The preparation method and the application of the metal-doped alumina hydrate with high adsorption performance provided by the invention have the beneficial effects that:
(1) The preparation environment of the metal-doped alumina hydrate composite material is mild, the operation is simple, and the prepared composite material is preparedEnvironment friendly, aluminum source NaAlO 2 Is cheap and easy to obtain.
(2) The prepared metal-doped alumina hydrate material has obviously improved ROX solution adsorption performance, and compared with a single alumina hydrate material, the metal-doped alumina hydrate material has obviously improved ROX adsorption capacity.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is an XRD pattern of metal doped alumina hydrate prepared in examples 1-6;
FIG. 2 is an enlarged XRD pattern of the metal doped alumina hydrate prepared in examples 1-4;
FIG. 3 is a graph showing adsorption kinetics of metal-doped alumina hydrates prepared in examples 1 to 6 when the initial ROX concentration is 100 mg/g;
FIG. 4 is an adsorption isotherm of the metal-doped alumina hydrate prepared in example 5.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but the present invention should not be construed as being limited to the implementable scope of the present invention.
The starting materials, reagents or apparatuses used in the following examples are, unless otherwise specified, either commercially available from conventional sources or can be obtained by known methods. The starting materials referred to in the following examples are commercially available. Experimental procedures according to the invention the examples refer to room temperature of 25 ℃.
Self-made sodium aluminate solution: 1.2g of sodium aluminate is dissolved in 15mL of deionized water at room temperature, and a solution is formed after magnetic stirring, wherein the concentration of the sodium aluminate solution is 0.97mol/L.
Self-made sodium zincate solution: 23.2g of NaOH was dissolved in 20mL of deionized water at room temperature and stirred until completely dissolved. Heating the solution, adding 10g of ZnO in 5 times in batches, and heating the solution to slightly boil after all ZnO is added; and continuously heating until the solution is gradually clarified, cooling, stirring to room temperature, diluting the solution to 40mL to obtain the sodium zincate with the concentration of 1.83mol/L, and diluting to different concentrations as required when preparing samples of the examples.
The invention is further described with reference to the following figures and examples.
Example 1:
the preparation method of the metal-doped alumina hydrate with high adsorption performance provided by the embodiment of the invention adopts a one-step hydrothermal method to prepare the metal-doped alumina hydrate with high adsorption performance, and specifically comprises the following steps:
step S1, preparing a metal salt solution:
mixing metal salt with deionized water to form a uniform metal salt solution;
step S2, preparing a sodium metaaluminate solution:
taking NaAlO 2 Mixing with deionized water, stirring until the mixture is completely dissolved, adding ethylene glycol, and stirring uniformly again to form a sodium metaaluminate solution;
step S3, preparing a metal-doped alumina hydrate material:
and (2) diluting the metal salt solution, mixing the diluted metal salt solution with a sodium metaaluminate solution, and then sequentially stirring and mixing, carrying out hydrothermal reaction, centrifuging, washing and drying to obtain the metal-doped alumina hydrate material.
Specifically, the method comprises the following steps:
s1: taking 15mL of self-made sodium aluminate solution into a beaker at room temperature, quickly adding 25mL of ethylene glycol, magnetically stirring for 1min to form a uniform clear solution, adding 10mL of deionized water into the system, and violently stirring for 2min;
s2: and (3) putting the reaction system in a 60 ℃ oven for hydrothermal treatment for 4h, centrifuging the reacted mixture, washing with deionized water for 3 times, then washing with ethanol for 1 time, and drying in a 60 ℃ drying oven for 24h to obtain an undoped hydrated alumina sample, wherein the sample is marked as AlOOH.
S3: the sample was adsorbed with 50mL of an initial concentration of 100mg/L of ROX solution. 50mL of ROX solution with the initial concentration of 100mg/L is prepared, 20mg of the sample is added, the sample is placed in a shaking box for adsorption for 12 hours, and the equilibrium adsorption capacity of the sample under the condition is measured to be 142.3mg/g.
Example 2:
the preparation method and application of the metal-doped alumina hydrate with high adsorption performance provided by the embodiment are basically the same as those of the embodiment 1, and the difference is that the preparation method comprises the following steps:
s1: dispersing 6.20g of copper chloride dihydrate into 20mL of deionized water at room temperature;
s2: taking 15mL of self-made sodium aluminate solution into a beaker at room temperature, quickly adding 25mL of glycol, and magnetically stirring for 1min to form a uniform clear solution;
s3: taking 4.0mL of the copper chloride solution obtained in the step (1), diluting to 10mL, and dropwise adding into the reaction system in the step (2); violently stirring for 2min, and then putting the reaction system in a 60 ℃ oven for hydrothermal treatment for 4h; washed 3 times with deionized water, then 1 time with ethanol, and subsequently dried in a 60 ℃ drying cabinet for 24h to yield Cu-doped samples. XRD analysis showed that copper was present as copper oxide-hydroxide and aluminum was present as amorphous hydrated alumina in this sample; marking the metal-doped alumina hydrate sample as CuO/AlOOH;
s4: 50mL of ROX solution with an initial concentration of 100mg/L was adsorbed by the sample. 50mL of ROX solution with the initial concentration of 100mg/L is prepared, 20mg of the sample is added, the sample is placed in a shaking box for adsorption for 12 hours, and the equilibrium adsorption quantity of the sample under the condition is determined to be 183.3mg/g.
Example 3:
the preparation method and the application of the metal-doped alumina hydrate with high adsorption performance provided by the embodiment are basically the same as those of the embodiments 1 and 2, and the difference is that the method comprises the following steps:
s1: dispersing 5.95g of ferric chloride in 20mL of deionized water at room temperature;
s2: taking 15mL of self-made sodium aluminate solution into a beaker at room temperature, quickly adding 25mL of glycol, and magnetically stirring for 1min to form a uniform clear solution;
s3: taking 4.0mL of ferric chloride solution obtained in the step (1), firstly diluting to 10mL, and then dropwise adding into the reaction system in the step (2); after being stirred vigorously for 2min, the reaction system is placed in a 60 ℃ oven and is subjected to hydrothermal treatment for 4h; washing with deionized water for 3 times, then washing with ethanol for 1 time, and drying in a drying oven at 60 ℃ for 24h to obtain the Fe-doped sample. XRD analysis shows that the sample is a composite material of amorphous hydrated ferric oxide and amorphous hydrated alumina; the metal doped alumina hydrate sample was labeled as FeOOH/AlOOH.
S4: the sample was adsorbed with 50mL of ROX solution at an initial concentration of 100 mg/L. 50mL of ROX solution with the initial concentration of 100mg/L is prepared, 20mg of the sample is added, the sample is placed in a shaking box for adsorption for 12 hours, and the equilibrium adsorption capacity of the sample under the condition is determined to be 198.1mg/g.
Example 4:
the preparation method and the application of the metal-doped alumina hydrate with high adsorption performance provided by the embodiment are basically the same as those of the embodiments 1 to 3, and the difference is that the method comprises the following steps:
(1) Taking 15mL of self-made sodium aluminate solution into a beaker at room temperature, quickly adding 30mL of ethylene glycol, and magnetically stirring for 1min to form uniform clear liquid;
(2) Taking 0.5mL of self-made sodium zincate solution, firstly diluting to 10mL, and then dropwise adding the solution into the reaction solution in the step (1); after being stirred vigorously for 2min, the reaction system is placed in an oven with the temperature of 70 ℃ to be heated by water for 2h; washing with deionized water for 3 times, then washing with ethanol for 1 time, and drying in a drying oven at 60 ℃ for 24h to obtain a Zn-doped sample. XRD analysis shows that the sample is a composite material of zinc oxide and amorphous hydrated alumina; the metal doped alumina hydrate sample was labeled ZnO/AlOOH-1.
(3) 50mL of ROX solution with an initial concentration of 100mg/L was adsorbed by the sample. 50mL of ROX solution with the initial concentration of 100mg/L is prepared, 20mg of the sample is added, the sample is placed in a shaking box for adsorption for 12 hours, and the equilibrium adsorption capacity of the sample under the condition is measured to be 166.3mg/g.
Example 5:
the preparation method and the application of the metal-doped alumina hydrate with high adsorption performance provided by the embodiment are basically the same as those of the embodiments 1 to 4, and the difference is that the method comprises the following steps:
(1) Taking 15mL of self-made sodium aluminate solution into a beaker at room temperature, quickly adding 30mL of glycol, and magnetically stirring for 1min to form a uniform clear solution;
(2) Taking 2mL of self-made sodium zincate solution, diluting to 10mL, and dropwise adding the self-made sodium zincate solution into the reaction solution in the step (1); after being stirred vigorously for 2min, the reaction system is placed in a drying oven with the temperature of 60 ℃ to be heated by water for 4h; washing with deionized water for 3 times, washing with ethanol for 1 time, and drying in a drying oven at 60 deg.C for 24h to obtain Zn-doped sample. The sample is a composite of zinc oxide and amorphous hydrated alumina; the metal doped alumina hydrate sample was labeled as ZnO/AlOOH-2.
(3) The sample was adsorbed with 50mL of an initial concentration of 100mg/L of ROX solution. 50mL of ROX solution with the initial concentration of 50mg/L is prepared, 20mg of the sample is added, the sample is placed in a shaking box for adsorption for 12 hours, and the equilibrium adsorption quantity of the sample under the condition is measured to be 237.7mg/g.
Example 6:
the preparation method and the application of the metal-doped alumina hydrate with high adsorption performance provided by the embodiment are basically the same as those of the embodiments 1 to 5, and the difference is that the method comprises the following steps:
(1) Taking 15mL of self-made sodium aluminate solution into a beaker at room temperature, quickly adding 20mL of ethylene glycol, and magnetically stirring for 1min to form uniform clear liquid;
(2) Taking 4mL of self-made sodium zincate solution, diluting to 10mL, and dropwise adding the self-made sodium zincate solution into the reaction solution in the step (1); after being stirred vigorously for 2min, the reaction system is placed in an oven with the temperature of 50 ℃ to be heated by water for 8h; washing with deionized water for 3 times, washing with ethanol for 1 time, and drying in a drying oven at 60 deg.C for 24h to obtain Zn-doped sample. The sample is a composite of zinc oxide and amorphous hydrated alumina; the metal doped alumina hydrate sample was labeled as ZnO/AlOOH-3.
(3) The sample was adsorbed with 50mL of an initial concentration of 100mg/L of ROX solution. 50mL of ROX solution with the initial concentration of 100mg/L is prepared, 20mg of the sample is added, the sample is placed in a shaking box for adsorption for 12 hours, and the equilibrium adsorption capacity of the sample under the condition is measured to be 236.5mg/g.
Application example 7:
in order to examine the adsorption capacity of the metal-doped boehmite for different concentrations of ROX solution, the adsorbent ZnO/AlOOH-2 prepared in example 5 is taken as an example, and the adsorption performance of the adsorbent ZnO/AlOOH-2 for different initial concentrations of ROX solution is tested. The adsorption process is as follows: 50mL of ROX solutions with the concentrations of 20mg/L, 100mg/L, 300mg/L, 500mg/L and 1000mg/L are prepared respectively, 0.02g of ZnO/AlOOH-2 is added respectively, the mixture is placed in an oscillation box to be adsorbed for 12 hours, then an ultraviolet spectrophotometer is used for measuring the adsorption effect, the parameters of the constant-temperature oscillation box are set to be 25 ℃ and 150r/min, the adsorption isotherm of the sample ZnO/AlOOH-2 prepared in example 5 is shown in figure 3, and the preferred adsorption capacity is 1110.8mg/g.
In order to illustrate the present invention more clearly, the present invention also provides the following table, table 1 shows the preparation of the precursor solutions of examples 1-6 and the comparison of the samples; table 2 is a comparison of the equilibrium adsorption amount and adsorption removal rate of ROX for the metal-doped alumina hydrate samples prepared in examples 1 to 6; table 3 is a comparison of the adsorption of example 2 for different initial ROX concentrations.
Table 1 examples 1-6 precursor solution formulations and sample comparisons
TABLE 2 comparison of equilibrium adsorption amount and adsorption removal rate of ROX in examples 1 to 6
Table 3 comparison of equilibrium adsorption amounts for example 2 for different initial ROX concentrations
| C 0 (mg/L) | 20 | 100 | 300 | 500 | 1000 |
| Equilibrium adsorption capacity (mg/g) | 42.9 | 237.7 | 712.5 | 1110.8 | 1091.1 |
According to the preparation method and the application of the metal-doped alumina hydrate with high adsorption performance provided by the embodiment of the invention, the preparation environment of the metal-doped alumina hydrate composite material is mild, the operation is simple, the preparation process is environment-friendly, and the aluminum source NaAlO 2 The price is low and the product is easy to obtain; the prepared metal-doped alumina hydrate material has obviously improved ROX solution adsorption performance, and compared with a single alumina hydrate material, the metal-doped alumina hydrate material has obviously improved ROX adsorption capacity.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of metal-doped alumina hydrate with high adsorbability is characterized in that the metal-doped alumina hydrate with high adsorbability is prepared by a one-step hydrothermal method, and comprises the following steps:
s1, preparing a metal salt solution:
mixing metal salt with deionized water to form a uniform metal salt solution;
s2, preparing a sodium metaaluminate solution:
taking NaAlO 2 Mixing with deionized water, stirring until the mixture is completely dissolved, adding ethylene glycol, and stirring uniformly again to form a sodium metaaluminate solution;
s3, preparing a metal-doped alumina hydrate material:
and (2) diluting the metal salt solution, mixing the diluted metal salt solution with a sodium metaaluminate solution, and then sequentially stirring and mixing, carrying out hydrothermal reaction, centrifuging, washing and drying to obtain the metal-doped alumina hydrate material.
2. The method for preparing a metal-doped aluminum oxide hydrate with high adsorbability according to claim 1, wherein the metal salt solution in the step S1 includes Na 2 ZnO 2 Solution, feCl 3 Solution and CuCl 2 One of the solutions.
3. The method for preparing metal-doped alumina hydrate with high adsorbability according to claim 2, wherein the Na is 2 ZnO 2 The preparation process of the solution is as follows:
dissolving NaOH in deionized water, stirring until the NaOH is completely dissolved, gradually adding ZnO while heating, and heating the solution to boiling after the ZnO is completely added; then keeping the temperature and continuously stirring until the solution becomes clear, stopping heating, naturally cooling, cooling to room temperature, diluting to obtain Na 2 ZnO 2 A solution; wherein, the Na 2 ZnO 2 During the preparation of the solution, the mass ratio of ZnO, naOH and deionized water is 10.
4. The method of claim 2, wherein the FeCl is the source of the high adsorptive capacity metal-doped alumina hydrate 3 The preparation process of the solution is as follows:
taking FeCl 3 Dissolving in deionized water, stirring to completely dissolve to obtain FeCl 3 A solution;
wherein the FeCl 3 In the preparation of the solution, feCl 3 The mass ratio to deionized water was 5.95.
5. The method of claim 1, wherein the CuCl is added to the metal-doped alumina hydrate 2 The preparation process of the solution is as follows:
taking CuCl 2 ·2H 2 Dissolving O in deionized water, stirring to completely dissolve to obtain CuCl 2 A solution;
wherein, the CuCl 2 In the preparation of the solution, cuCl 2 ·2H 2 The mass ratio of O to deionized water was 6.2.
6. The method for preparing metal-doped aluminum oxide hydrate with high adsorbability according to claim 1, wherein in the step S2, naAlO is added 2 The mass ratio of the deionized water to the ethylene glycol is 1.2.
7. The method for preparing metal-doped alumina hydrate with high adsorbability according to claim 1, wherein the dilution treatment process of the metal salt solution in the step S3 is as follows: the metal salt solution was mixed with deionized water at a volume ratio of 4.
8. The method for preparing a metal-doped alumina hydrate with high adsorbability according to claim 1, wherein in the step S3, the diluted metal salt solution and the sodium metaaluminate solution are mixed in a volume ratio of 10.
9. The method for preparing the metal-doped alumina hydrate with high adsorbability according to claim 1, wherein the temperature of the hydrothermal reaction in step S3 is 60 ℃, the washing is performed by washing 3 times with deionized water and then washing 1 time with absolute ethanol, and the drying is performed in a drying oven at 60 ℃ for 24 hours.
10. Use of a metal-doped alumina hydrate with high adsorption performance as a rocky arsenic (ROX) adsorption material, wherein the metal-doped alumina hydrate prepared by the preparation method of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102689727B1 (en) * | 2023-06-20 | 2024-07-31 | 케이에이치에코텍 주식회사 | Recycling method of nickel sludge |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060096891A1 (en) * | 1999-08-11 | 2006-05-11 | Dennis Stamires | Quasi-crystalline boehmites containing additives |
| CN101049972A (en) * | 2007-05-10 | 2007-10-10 | 桂林工学院 | Method for synthesizing composite hydroxide of iron and aluminum, and application |
| CN101422720A (en) * | 2008-11-24 | 2009-05-06 | 中国科学院生态环境研究中心 | Absorption filtration dearsenication method based on in-situ composite metal oxides generation |
| CN107551986A (en) * | 2017-09-28 | 2018-01-09 | 福州大学 | Zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent and preparation method thereof |
| CN107913665A (en) * | 2017-11-29 | 2018-04-17 | 中南大学 | A kind of metal-doped boehmite and its preparation method and application |
| CN108034818A (en) * | 2017-11-29 | 2018-05-15 | 中国科学院过程工程研究所 | Method for synchronously removing impurity elements in manganese sulfate leaching solution through in-situ neutralization and synergistic adsorption |
| CN111530459A (en) * | 2020-05-19 | 2020-08-14 | 福州大学 | Preparation method and application of 0D/2D composite material based on AlOOH nanosheets |
-
2022
- 2022-09-01 CN CN202211061495.XA patent/CN115501852A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060096891A1 (en) * | 1999-08-11 | 2006-05-11 | Dennis Stamires | Quasi-crystalline boehmites containing additives |
| CN101049972A (en) * | 2007-05-10 | 2007-10-10 | 桂林工学院 | Method for synthesizing composite hydroxide of iron and aluminum, and application |
| CN101422720A (en) * | 2008-11-24 | 2009-05-06 | 中国科学院生态环境研究中心 | Absorption filtration dearsenication method based on in-situ composite metal oxides generation |
| CN107551986A (en) * | 2017-09-28 | 2018-01-09 | 福州大学 | Zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent and preparation method thereof |
| CN107913665A (en) * | 2017-11-29 | 2018-04-17 | 中南大学 | A kind of metal-doped boehmite and its preparation method and application |
| CN108034818A (en) * | 2017-11-29 | 2018-05-15 | 中国科学院过程工程研究所 | Method for synchronously removing impurity elements in manganese sulfate leaching solution through in-situ neutralization and synergistic adsorption |
| CN111530459A (en) * | 2020-05-19 | 2020-08-14 | 福州大学 | Preparation method and application of 0D/2D composite material based on AlOOH nanosheets |
Non-Patent Citations (2)
| Title |
|---|
| CHUNSHENG LEI ET AL.: ""Synthesis of hierarchical porous flower-like ZnO-AlOOH structures and their applications in adsorption of Congo Red"", 《CHEMICAL PHYSICS LETTERS》, vol. 687, pages 143 - 151, XP085208454, DOI: 10.1016/j.cplett.2017.09.018 * |
| KATHERINE ACUÑA ET AL.: ""Photocatalytic degradation of roxarsone by using synthesized ZnO nanoplates"", 《SOLAR ENERGY》, vol. 157, pages 335 - 341, XP085268556, DOI: 10.1016/j.solener.2017.07.054 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102689727B1 (en) * | 2023-06-20 | 2024-07-31 | 케이에이치에코텍 주식회사 | Recycling method of nickel sludge |
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