CN109499524B - A kind of preparation method of AlOOH/MnO2@diatomite composite material - Google Patents
A kind of preparation method of AlOOH/MnO2@diatomite composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 229910002706 AlOOH Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 14
- BOMINLBVYNPVIK-UHFFFAOYSA-N azane;manganese(2+) Chemical compound N.[Mn+2] BOMINLBVYNPVIK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- -1 arsenic ions Chemical class 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000005909 Kieselgur Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 3
- 241000195493 Cryptophyta Species 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000002057 nanoflower Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910017251 AsO4 Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 125000001870 arsonato group Chemical group O=[As]([O-])([O-])[*] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage 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
- 239000012086 standard solution Substances 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J20/06—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
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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
- B01J20/06—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
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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
- B01J20/14—Diatomaceous earth
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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Abstract
本发明公开了一种AlOOH/MnO2@硅藻土复合材料的制备方法，包括：将AlCl3加入到硅藻土悬浮液中，调节pH值后加入十二烷基苯磺酸钠；随后缓慢滴加由过硫酸铵和高锰酸钾溶于去离子水中制得的铵锰复合溶液，搅拌后加入尿素制得硅藻土复合溶液；将硅藻土复合溶液发生水热反应，即得。本发明所提供的在硅藻土藻盘上沉积纳米花、线状的AlOOH/MnO2@硅藻土复合材料，提高了硅藻土基体对重金属砷离子的吸附敏感性，在增加比表面积的同时，对砷离子的吸附容量显著增加；该方法设计巧妙合理，制备过程科学简单，工艺过程可控，对生产设备的要求较低，经济效益显著，具有重大的理论和实际意义。
The invention discloses a preparation method of AlOOH/MnO 2 @diatomite composite material. Add dropwise an ammonium-manganese composite solution prepared by dissolving ammonium persulfate and potassium permanganate in deionized water, and add urea after stirring to obtain a diatomite composite solution; the diatomite composite solution is subjected to a hydrothermal reaction to obtain it. The nano-flower and linear AlOOH/MnO 2 @diatomite composite material deposited on the diatomite algae disk provided by the invention improves the adsorption sensitivity of the diatomite matrix to heavy metal arsenic ions, and increases the specific surface area. At the same time, the adsorption capacity of arsenic ions is significantly increased; the method is ingenious and reasonable in design, scientific and simple in preparation process, controllable in process process, low in requirements for production equipment, and has significant economic benefits, which has great theoretical and practical significance.
Description
Technical Field
The invention belongs to the technical field of environmental materials, relates to a heavy metal ion adsorption purification and toxicity degradation material, and particularly relates to AlOOH/MnO2A preparation method of a @ diatomite composite material.
Background
As is internationally recognized as the most toxic heavy metal pollutant, the safety threshold of arsenic is low (0.01mg/g), and the arsenic is in the form of acid radical anion (H) in water2AsO3 -、HasO3 2-、AsO3 3-； H2AsO4 -、HAsO4 2-、AsO4 3-) The arsenic is easy to migrate, namely, the toxicity can be migrated and transformed along with water bodies and soil in biological chains of animals, plants and the like, and the standard treatment of the arsenic in the industrial sewage is very difficult.
The adsorption method is the method for treating and applying heavy metal arsenic most, mainly has the advantages of simple method, suitability for deep purification of low-concentration arsenic-containing wastewater and easy industrial application, but the adsorption method is usually limited by the adsorption efficiency (adsorption capacity, adsorption speed and removal rate) of an adsorbent, and how to improve the adsorption efficiency of the adsorption material is very critical.
Research shows that the porous adsorbent with large specific surface area and abundant surface functional groups is an excellent heavy metal ion adsorption material and can be used for deep purification of heavy metal wastewater containing arsenic and the like; however, the existing adsorbent capable of being applied in large scale mainly comprises molecular sieve and active carbon, and the industrial application is limited to a certain extent due to higher price. Therefore, the preparation method has low price and excellent adsorption performance, can be used for large-scale production, and can meet the requirements of industrial application.
The diatomite is a mineral material with a natural ordered microporous structure, the pore diameter of a small pore is 20-50nm, the pore diameter of a large pore is 100-300nm, the pore diameter distribution is reasonable, and the pore channel structure is ordered; the main chemical component of the material is amorphous SiO2The diatomite adsorbs heavy metal ions, and is an adsorption material which has the industrial application prospect of treating heavy metal wastewater containing arsenic and the like, and the preparation and industrial application cost of treating the heavy metal ion adsorption material can be greatly reduced due to the natural property of the pore structure; however, the diatomite raw ore has lower specific surface area (25-30 m)2And/g), the adsorption capacity is limited, and the adaptability to arsenate anions in the water body is poor. Therefore, studies on improvement of the adsorption capacity of heavy metal ions by surface treatment or modification of diatomaceous earth have been focused, and studies on modified diatomaceous earth such as iron salt, manganese salt, magnesium salt, and aluminum salt have been conducted most. However, most of the related studies at present are mechanical mixing (disordered compounding) of modifiers (iron salts, manganese salts, aluminum salts, organic matters, etc.) and diatomite, and the adsorption and removal efficiency of heavy metal ions is greatly influenced at the cost of destroying the natural microporous structure of the diatomite.
Therefore, the nano-structure metal oxide can be prepared on the diatom disc by deposition while the microporous structure of the kieselguhr is kept, and the quality of the adsorbent is expected to be greatly improved; and the nano-structure composite metal oxide is prepared on the diatomite matrix in a deposition manner, so that the adsorption capacity of the material can be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides AlOOH/MnO2A preparation method of a @ diatomite composite material.
According to one aspect of the invention, AlOOH/MnO is provided2The preparation method of the @ diatomite composite material comprises the following steps:
s1, adding diatomite into ionized water, stirring to obtain diatomite suspension, and adding AlCl3Stirring to dissolve, and adding dropwise ammonia waterAdjusting the pH value to 3.5-5.8, adding sodium dodecyl benzene sulfonate, and dispersing and dissolving to obtain a diatomite mixed solution;
s2, weighing ammonium persulfate and potassium permanganate according to a proportion, dissolving the ammonium persulfate and the potassium permanganate in deionized water to prepare an ammonium-manganese composite solution, then slowly dropwise adding the ammonium-manganese composite solution into the diatomite mixed solution prepared in the step S1, uniformly stirring, adding urea, and uniformly mixing to prepare a diatomite composite solution;
s3, carrying out hydrothermal reaction on the diatomite composite solution prepared in the step S2 to obtain AlOOH/MnO2@ diatomite composite material.
In the above technical solution, in step S1, the AlCl is added3The mass ratio of the added amount of the diatomite is 0.9-3.6: 1, preferably 1.8-2.4: 1.
in the technical scheme, in the step S1, the pH value is adjusted to 4-5 by dropwise adding the ammonia water.
In the above technical solution, in step S1, the ratio of the added amount of the sodium dodecylbenzenesulfonate to the mass of the diatomaceous earth is 0.03-0.12: 1, preferably 0.08-0.10: 1.
Further, in the above technical solution, in step S2, the mass ratio of the added amount of the potassium permanganate to the diatomaceous earth is 0.4-1.6: 1, preferably 0.8-1.2: 1.
Still further, in the above technical solution, in step S2, the molar ratio of the added amount of ammonium persulfate to the added amount of potassium permanganate is 0.8-1.2: 1, preferably 1: 1.
still further, in the above technical means, in the step S2, the dropping rate of the ammonium manganese complex solution is 45 to 55 drops/minute.
Still further, in the above technical solution, in step S2, a ratio of an amount of the urea added to the diatomaceous earth is 0.45 to 1.8: 1, preferably 0.8 to 1.5: 1.
still further, in the above technical solution, in the step S3, the reaction temperature of the hydrothermal reaction is 110-.
Preferably, in the above technical solution, in step S3, the reaction time of the hydrothermal reaction is 5-14h, preferably 6-10 h.
Further preferably, in the above technical solution, in step S3, the hydrothermal reaction is completed and is cooled, and then the filtration, the washing and the drying are further included.
Still further preferably, in the above technical solution, in step S3, the washing includes washing with deionized water and absolute ethyl alcohol in sequence three times.
According to another aspect of the invention, AlOOH/MnO prepared by the preparation method is provided2@ diatomite composite material.
According to still another aspect of the present invention, there is provided the above-mentioned preparation method or the above-mentioned AlOOH/MnO2The application of the @ diatomite composite material in adsorption treatment of heavy metal arsenic ions.
The invention has the advantages that:
(1) the AlOOH/MnO with the nanometer flower and nanometer linear structure can be deposited on the diatomite algae dish2The @ diatomite composite material greatly improves the adsorption sensitivity of the diatomite matrix to heavy metal arsenic ions, and obviously increases the adsorption capacity to the arsenic ions while increasing the specific surface area of the material;
(2) the preparation method provided by the invention has the advantages of ingenious and reasonable design, scientific and simple preparation process, controllable process, low requirement on production equipment, remarkable economic benefit and great theoretical and practical significance.
Drawings
FIG. 1 is an AlOOH/MnO residue prepared in example 2 of the present invention2@ XRD (X-ray diffraction) pattern of diatomite composite material (wherein the lower part is XRD pattern of diatomite and the upper part is AlOOH/MnO2@ XRD pattern of diatomite composite);
FIG. 2 is AlOOH/MnO prepared in example 2 of the present invention2@ SEM photographs of the diatomaceous earth composite material at different magnifications;
FIG. 3 is AlOOH/MnO prepared in example 2 of the present invention2@ EDS spectrum of diatomite composite material;
FIG. 4 is AlOOH/MnO prepared in example 2 of the present invention2@ siliconXPS spectra of an diatomite composite material (wherein A is an XPS full spectrum of AlOOH/MnO2@ diatomite composite material absorbing pentavalent As front < a > and rear < B >, B is an Mn 2p orbital diagram, C is an Al 2p orbital diagram, and D is an O1 s orbital diagram);
FIG. 5 is an adsorption isotherm of the AlOOH/MnO2@ diatomaceous earth composite prepared in example 2 of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples.
The following examples are intended to illustrate the present invention, but not to limit the scope of the invention, which is defined by the claims.
In the following examples and comparative examples, XRD (2 θ ═ 10 to 80 °) patterns were obtained using X-ray diffractometers of type D/MAX-ii; SEM photograph was obtained by using Hitachi model 570 scanning electron microscope; the XPS spectrum is obtained by a Thermo ESCALB 250XI type X-ray photoelectron spectrometer; the specific surface area test result is obtained by using an ASAP 2020 specific surface area tester.
In the following examples and comparative examples, the adsorption performance test procedure was as follows: 100ml of As (V) standard solution of known concentration is added to a 250ml conical flask, the pH value of the solution is adjusted by adding dilute HCl and NaOH solutions, 0.1g of test sample is added, the mixture is stirred for 10-30min with a PTFE plastic stirring rod under constant temperature conditions, and filtered with a 0.22 μm syringe filter to obtain a filtrate, and the concentration of As (V) in the solution is determined by ICP-AES.
Unless otherwise specified, experimental reagents and materials used in the examples of the present invention are commercially available, and unless otherwise specified, technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment 1 of the invention provides AlOOH/MnO2The preparation method of the @ diatomite composite material specifically comprises the following steps:
s1, weighing 1.0g of diatomite, adding into a 200mL beaker, adding 40mL of deionized water, magnetically stirring for 20min, and then adding 1.8g of AlCl3Stirring the mixture to dissolve the mixture,and ammonia water is dripped to adjust the pH value to 4.0, 0.06g of sodium dodecyl benzene sulfonate is added, and the diatomite mixed solution is prepared after dispersion and dissolution;
s2, respectively weighing 1.1g of ammonium persulfate and 0.8g of potassium permanganate, dissolving the ammonium persulfate and the potassium permanganate in 10mL of deionized water to prepare an ammonium-manganese composite solution, then dropwise adding the ammonium-manganese composite solution into the diatomite mixed solution prepared in the step S1 at a speed of 50 drops/min, stirring for 20min, uniformly mixing, then adding 0.9g of urea, stirring for 20min, and uniformly mixing to prepare the diatomite composite solution;
s3, placing the diatomite composite solution prepared in the step S2 into a reaction kettle, carrying out hydrothermal reaction at 120 ℃, and reacting for 8 hours to obtain AlOOH/MnO2@ diatomite composite material.
After the reaction is finished, cooling, filtering, washing and drying are carried out to obtain AlOOH/MnO2@ diatomite composite material.
And (3) detecting the appearance, structure and performance of the sample: AlOOH/MnO grown in situ on diatomite plate2@ diatomite composite material in which AlOOH is in the form of sheet, MnO2Is flower-shaped, and has a thickness of 5-8nm, a length of 40-50nm, and a width of 10-20 nm; specific surface area: 120m2(ii)/g; arsenic (v) adsorption capacity: 135 mg/g.
Example 2
The embodiment 2 of the invention provides AlOOH/MnO2The preparation method of the @ diatomite composite material specifically comprises the following steps:
s1, weighing 1.5g of diatomite, adding into a 200mL beaker, adding 40mL of deionized water, magnetically stirring for 20min, and then adding 2.7g of AlCl3Stirring for dissolving, adjusting the pH value to 4.5 by dripping ammonia water, adding 0.09g of sodium dodecyl benzene sulfonate, and dispersing and dissolving to obtain a diatomite mixed solution;
s2, respectively weighing 2.2g of ammonium persulfate and 1.6g of potassium permanganate, dissolving the ammonium persulfate and the potassium permanganate in 10mL of deionized water to prepare an ammonium-manganese composite solution, then dropwise adding the ammonium-manganese composite solution into the diatomite mixed solution prepared in the step S1 at a speed of 45 drops/min, stirring for 30min, uniformly mixing, then adding 1.5g of urea, stirring for 30min, and uniformly mixing to prepare the diatomite composite solution;
s3, placing the diatomite composite solution prepared in the step S2 into a reaction kettle, carrying out hydrothermal reaction at 120 ℃, and reacting for 12h to obtain AlOOH/MnO2@ diatomite composite material.
After the reaction is finished, cooling, filtering, washing and drying are carried out to obtain AlOOH/MnO2@ diatomite composite material.
And (3) detecting the appearance, structure and performance of the sample: FIG. 1 is an AlOOH/MnO residue prepared in example 2 of the present invention2The XRD pattern of the @ diatomite composite material is characterized in that the lower part is the XRD pattern of diatomite raw soil, and the upper part is AlOOH/MnO2@ XRD (X-ray diffraction) spectrum of the diatomite composite material; FIG. 2 is AlOOH/MnO prepared in example 2 of the present invention2SEM photographs of the @ diatomaceous earth composite at different magnifications, from which it can be seen that AlOOH/MnO grown in situ on the diatomaceous earth disk2In the @ diatomite composite material, AlOOH is in a sheet shape, MnO2Is flower-shaped, and has a thickness of 8-10nm, a length of 60-70nm and a width of 15-25 nm; FIG. 3 is AlOOH/MnO prepared in example 2 of the present invention2@ EDS spectrum of diatomite composite material; FIG. 4 is AlOOH/MnO prepared in example 2 of the present invention2The XPS spectrum of the @ diatomite composite material, wherein A is an XPS full spectrum of front < a > and back < B > of the AlOOH/MnO2@ diatomite composite material for adsorbing pentavalent As, B is an Mn 2p orbital diagram, C is an Al 2p orbital diagram, and D is an O1 s orbital diagram; FIG. 5 is an adsorption isotherm of an AlOOH/MnO2@ diatomaceous earth composite material prepared in example 2 of the present invention, and the calculated specific surface area thereof was 140m2(ii)/g; in addition, AlOOH/MnO prepared in example 2 of the present invention was measured2@ arsenic (v) adsorption capacity of diatomaceous earth composite material: 160 mg/g.
Example 3
s1, 2.0g of diatomite is weighed into a 200mL beaker, 40mL of deionized water is added, magnetic stirring is carried out for 20min, and then 3.6g of AlCl is added3Stirring for dissolving, adding dropwise ammonia water to adjust pH to 4.0, adding 0.12g sodium dodecylbenzenesulfonate, dispersing and dissolving to obtainObtaining diatomite mixed solution;
s2, respectively weighing 2.3g of ammonium persulfate and 1.6g of potassium permanganate, dissolving the ammonium persulfate and the potassium permanganate in 10mL of deionized water to prepare an ammonium-manganese composite solution, then dropwise adding the ammonium-manganese composite solution into the diatomite mixed solution prepared in the step S1 at a speed of 45 drops/min, stirring for 30min, uniformly mixing, then adding 1.8g of urea, stirring for 30min, and uniformly mixing to prepare the diatomite composite solution;
s3, placing the diatomite composite solution prepared in the step S2 into a reaction kettle, carrying out hydrothermal reaction at 120 ℃, and reacting for 16h to obtain AlOOH/MnO2@ diatomite composite material.
After the reaction is finished, cooling, filtering, washing and drying are carried out to obtain AlOOH/MnO2@ diatomite composite material.
And (3) detecting the appearance, structure and performance of the sample: AlOOH/MnO grown in situ on diatomite plate2@ diatomite composite material in which AlOOH is in the form of sheet, MnO2Is flower-shaped, and has a thickness of 8-12nm, a length of 60-80nm, and a width of 20-30 nm; specific surface area: 146m2(ii)/g; arsenic (v) adsorption capacity: 165 mg/g.
Finally, the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. AlOOH/MnO2The preparation method of the @ diatomite composite material is characterized by comprising the following steps of:
s1, adding diatomite into ionized water, stirring to obtain diatomite suspension, and adding AlCl3Stirring for dissolving, adding dropwise ammonia water to adjust pH to 4-5, adding sodium dodecylbenzenesulfonate, dispersing and dissolving to obtain diatomaceous earth mixture solution, wherein AlCl is3The mass ratio of the added amount of the diatomite is 1.8-2.4: 1, the mass ratio of the addition amount of the sodium dodecyl benzene sulfonate to the diatomite is 0.08-0.10: 1;
s2, weighing ammonium persulfate and potassium permanganate according to a proportion, dissolving the ammonium persulfate and the potassium permanganate in deionized water to prepare an ammonium-manganese composite solution, then slowly dropwise adding the ammonium-manganese composite solution into the diatomite mixed solution prepared in the step S1, uniformly stirring, adding urea, and uniformly mixing to prepare a diatomite composite solution, wherein the ratio of the addition amount of the potassium permanganate to the mass of the diatomite is 0.8-1.2: 1, the molar ratio of the added ammonium persulfate to the added potassium permanganate is 0.8-1.2: 1, the mass ratio of the added urea to the diatomite is 0.8-1.5: 1;
s3, carrying out hydrothermal reaction on the diatomite composite solution prepared in the step S2 to obtain AlOOH/MnO2The reaction temperature of the hydrothermal reaction is 120 ℃, and the reaction time of the hydrothermal reaction is 6-10 h.
2. The preparation method according to claim 1, wherein in step S2, the molar ratio of the added ammonium persulfate to the added potassium permanganate is 1: 1.
3. the production method according to claim 1 or 2, wherein, in step S2,
the dropping speed of the ammonium-manganese composite solution is 45-55 drops/min.
4. The method according to claim 1, wherein the step S3 further comprises filtering, washing and drying after the hydrothermal reaction is completed and cooled;
the washing comprises washing with deionized water and absolute ethyl alcohol for three times respectively.
5. AlOOH/MnO obtainable by the process according to any one of claims 1 to 42@ diatomite composite material.
6. AlOOH/MnO according to claim 52The application of the @ diatomite composite material in adsorption treatment of heavy metal arsenic ions.
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