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CN109499524A - A kind of AlOOH/MnO2The preparation method of@diatomite composite material - Google Patents

A kind of AlOOH/MnO2The preparation method of@diatomite composite material Download PDF

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CN109499524A
CN109499524A CN201811436039.2A CN201811436039A CN109499524A CN 109499524 A CN109499524 A CN 109499524A CN 201811436039 A CN201811436039 A CN 201811436039A CN 109499524 A CN109499524 A CN 109499524A
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diatomite
preparation
alooh
mno
composite material
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CN109499524B (en
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杜玉成
李强
江卓填
李杨
靳翠鑫
牛炎
李生辉
谷恒学
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Guangdong Ward Environmental Protection New Material Co Ltd
Beijing University of Technology
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Guangdong Ward Environmental Protection New Material Co Ltd
Beijing University of Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—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
    • 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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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

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

A kind of AlOOH/MnO2The preparation method of@diatomite composite material
Technical field
The invention belongs to environmentally conscious materials technical fields, are related to the adsorption cleaning and toxic decomposition material of heavy metal ion, tool Body is related to a kind of AlOOH/MnO2The preparation method of@diatomite composite material.
Background technique
Arsenic be by the maximum heavy metal contaminants of internationally recognized toxicity, because the safe threshold of arsenic is low (0.01mg/g), and With acid radical anion (H in water body2AsO3 -、HasO3 2-、AsO3 3-；H2AsO4 -、HAsO4 2-、AsO4 3-) form presence, meanwhile, Toxicity easily migrates, i.e., its toxicity can carry out Transport And Transformation in biological chains such as animals and plants with water body, soil, arsenic in trade effluent Processing up to standard is extremely difficult.
Absorption method is that most methods is applied in the processing containing heavy metal arsenic, essentially consists in method simplicity, contains suitable for low concentration The deep purifying of arsenic waste water, and industrial applications are easy, but absorption method is often limited to adsorption (the absorption appearance of adsorbent Amount, adsorption rate and removal rate), the adsorption for how improving adsorbent material is very crucial.
Studies have shown that the porosity adsorbent with bigger serface and abundant surface functional group, is excellent heavy metal Ion adsorbing material can be used for the deep purifying containing heavy metal wastewater therebies such as arsenic；But existing energy scale application adsorbent is with molecule Based on sieve, active carbon, because its price is higher, industrial application is limited to a certain extent.Therefore, cheap, absorption property is excellent It is different, can be mass-produced and be able to satisfy requirement on industrial application adsorbent material preparation research is concerned.
Diatomite is the mineral material with natural ordered micro-cellular structure, small aperture 20-50nm, and macropore diameter is 100-300nm, pore-size distribution is reasonable, cellular structure is orderly；Its main chemical is amorphous Si O2, by oxygen-octahedron Mutual bridging forms reticular structure, and there are coordination defects and oxygen bridge defect on surface, causes a large amount of Si-O- dangling bonds, is easy to combine H Si-OH, i.e. surface silanol group are formed, therefore, it is most to locate that kieselguhr adsorption heavy metal ion, which has natural structural advantage, The adsorbent material of the heavy metal wastewater therebies prospects for commercial application containing arsenic etc. is managed, and because of the natural sex of its pore structure, so that being greatly lowered The preparation of processing heavy metal ion adsorbing material is possibly realized with industrial application expense；However diatomite original ore specific surface area is lower (25-30m2/ g), adsorption capacity is limited and poor to arsenic in water body acid radical anion adaptability.Therefore, diatomite carries out surface Processing is modified, and the adsorption capacity correlative study of Lai Tigao heavy metal ion is concerned, and molysite, manganese salt, magnesium salts, aluminium salt etc. change Property diatomite most study.However, current correlative study, is mostly by modifying agent (molysite, manganese salt, aluminium salt, organic matter etc.) It is mixed with the mechanicalness of diatomite (unordered compound), and to destroy diatomite natural micropore structure as cost, heavy metal ion is inhaled Attached removal efficiency is influenced by very big.
Therefore, it is able to maintain diatomite microcellular structure simultaneously, deposition prepares nanostructured metal oxides on diatom disk, has Hope the quality that such adsorbent is substantially improved；And deposition prepares nanostructured composite metal oxide on diatomite matrix, it can Further increase the adsorption capacity of material.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of AlOOH/MnO2The preparation side of@diatomite composite material Method.
A kind of AlOOH/MnO is provided according to an aspect of the present invention2The preparation method of@diatomite composite material, including with Lower step:
S1, obtained diatomite suspension is stirred after diatomite is added in ionized water, AlCl is then added3Stirring and dissolving, And its pH value is adjusted by the way that ammonium hydroxide is added dropwise as neopelex after 3.5-5.8, is added, diatomite is made after dispersing and dissolving Mixed liquor；
S2, ammonium persulfate and potassium permanganate are weighed in proportion, be dissolved in deionized water and ammonium manganese composite solution is made, then will Ammonium manganese composite solution is slowly dropped in diatomite mixed liquor obtained in step S1, is stirred evenly, and urea mixing is added Uniformly obtained composite diatomite solution；
S3, hydro-thermal reaction is occurred into for composite diatomite solution obtained in step S2 to get AlOOH/MnO2@diatomite Composite material.
In the above-mentioned technical solutions, in step S1, the AlCl3Additional amount and the mass ratio of the diatomite be 0.9-3.6: 1, preferably 1.8-2.4:1.
It in the above-mentioned technical solutions, is 4-5 by the way that the ammonium hydroxide is added dropwise to adjust its pH value in step S1.
In the above-mentioned technical solutions, in step S1, the additional amount of the neopelex and the diatomite Mass ratio is 0.03-0.12:1, preferably 0.08-0.10: 1.
Further, in the above-mentioned technical solutions, in step S2, the additional amount of the potassium permanganate and the diatomite Mass ratio is 0.4-1.6: 1, preferably 0.8-1.2: 1.
Still further, in the above-mentioned technical solutions, in step S2, the addition of the ammonium persulfate and the potassium permanganate Amount molar ratio is 0.8-1.2:1, preferably 1:1.
Further, in the above-mentioned technical solutions, in step S2, the rate of addition of the ammonium manganese composite solution is 45- 55 drops/minute.
Further, in the above-mentioned technical solutions, in step S2, the matter of the additional amount of the urea and the diatomite The ratio between amount is 0.45-1.8:1, preferably 0.8-1.5:1.
Also further, in the above-mentioned technical solutions, in step S3, the reaction temperature of the hydro-thermal reaction is 110-130 DEG C, preferably 120 DEG C.
Preferably, in the above-mentioned technical solutions, in step S3, the reaction time of the hydro-thermal reaction is 5-14h, preferably 6-10h。
It is further preferred that in the above-mentioned technical solutions, in step S3, further including, hydro-thermal reaction completion is simultaneously after cooling It is filtered, washed and dried.
Further preferably, in the above-mentioned technical solutions, in step S3, the washing includes successively using deionized water It is respectively washed three times with dehydrated alcohol.
The AlOOH/MnO that above-mentioned preparation method is prepared is provided according to a further aspect of the invention2@composite diatomite material Material.
Above-mentioned preparation method or above-mentioned AlOOH/MnO are also on the one hand provided according to the present invention2@diatomite composite material exists Application in adsorption treatment heavy metal arsenic ion.
Advantages of the present invention:
(1) one kind provided by the present invention deposition can prepare nano flower, nanometer linear structure on the diatomite algae disk AlOOH/MnO2@diatomite composite material substantially increases diatomite matrix to the absorption sensibility of heavy metal arsenic ion, is increasing The specific surface area for adding material itself simultaneously, dramatically increases the adsorption capacity of arsenic ion；
(2) preparation method of the invention is ingenious in design rationally, and preparation process science is simple, and technical process is controllable, to production The requirement of equipment is lower, remarkable in economical benefits, has great theoretical and practical significance.
Detailed description of the invention
Fig. 1 is AlOOH/MnO prepared by the embodiment of the present invention 22The XRD spectrum of@diatomite composite material is (under wherein, Side is the XRD spectrum of diatomite original soil, top AlOOH/MnO2The XRD spectrum of@diatomite composite material)；
Fig. 2 is AlOOH/MnO prepared by the embodiment of the present invention 22@diatomite composite material under different enlargement ratios SEM photograph；
Fig. 3 is AlOOH/MnO prepared by the embodiment of the present invention 22The EDS map of@diatomite composite material；
Fig. 4 is AlOOH/MnO prepared by the embodiment of the present invention 22(wherein, A is the XPS map of@diatomite composite material AlOOH/MnO2@diatomite composite material adsorbs the full spectrogram of XPS of pentavalent As preceding < a > and rear < b >, and B is Mn 2p trajectory diagram, and C is Al 2p trajectory diagram, D are O 1s trajectory diagram)；
Fig. 5 is the adsorption isotherm of AlOOH/MnO2@diatomite composite material prepared by the embodiment of the present invention 2.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.
The following examples are intended to illustrate the invention, but is not limited to protection scope of the present invention, protection model of the invention It encloses and is subject to claims.
In the following Examples and Comparative Examples, XRD (2 θ=10-80 °) map is obtained using II type X-ray diffractometer of D/MAX- It arrives；SEM photograph is obtained using 570 type scanning electron microscope of Hitachi；XPS map uses Thermo ESCALAB 250XI type X X-ray photoelectron spectroscopy X instrument obtains；Specific surface area test result is obtained using 2020 specific-surface area detection instrument of ASAP.
In the following Examples and Comparative Examples, absorption property detection process is as follows: the As (V) of 100ml known concentration is marked Quasi- solution is added into 250ml Erlenmeyer flask, adjusts solution ph by the way that dilute HCl and NaOH solution is added, 0.1g test specimens are added Product stir 10-30min with PTFE plastic stir rod, are filtered with 0.22 μm of syringe filters, obtain filtrate under constant temperature conditions, The concentration of As (V) in solution is measured by ICP-AES.
Unless otherwise specified, experiment reagent used in the embodiment of the present invention and material etc. are commercially available, if not having Body indicates, the conventional means that technological means used in the embodiment of the present invention is well known to the skilled person.
Embodiment 1
The embodiment of the present invention 1 provides a kind of AlOOH/MnO2The preparation method of@diatomite composite material, specifically include with Lower step:
S1, it weighs 1.0g diatomite and is added in the beaker of 200mL, be added 40mL deionized water, magnetic agitation 20min, 1.8g AlCl is then added3Stirring and dissolving, and by be added dropwise ammonium hydroxide adjust its pH value be 4.0 after, be added 0.06g dodecyl Diatomite mixed liquor is made after dispersing and dissolving for benzene sulfonic acid sodium salt；
S2,1.1g ammonium persulfate and 0.8g potassium permanganate are weighed respectively, be dissolved in 10mL deionized water that be prepared into ammonium manganese multiple Solution is closed, ammonium manganese composite solution is then added drop-wise to diatomite mixed liquor obtained in step S1 with 50 drops/minute speed In, 20min is stirred, is uniformly mixed, 0.9g urea is added, stirs 20min, is uniformly mixed obtained composite diatomite solution；
S3, composite diatomite solution obtained in step S2 is placed in reaction kettle, it is anti-that unboiled water heat is issued at 120 DEG C It answers, reacts 8h, AlOOH/MnO is made2@diatomite composite material.
After the reaction was completed, cooling, it filters, washing, it is dry to get AlOOH/MnO2@diatomite composite material.
Sample topography, structure and performance test results: the AlOOH/MnO of growth in situ on diatomite disk2@composite diatomite Material, wherein AlOOH in the form of sheets, MnO2In flower-shaped, thickness 5-8nm, length 40-50nm, width 10-20nm；Specific surface area: 120m2/g；Arsenic (V) adsorption capacity: 135mg/g.
Embodiment 2
The embodiment of the present invention 2 provides a kind of AlOOH/MnO2The preparation method of@diatomite composite material, specifically include with Lower step:
S1, it weighs 1.5g diatomite and is added in the beaker of 200mL, be added 40mL deionized water, magnetic agitation 20min, 2.7g AlCl is then added3Stirring and dissolving, and by be added dropwise ammonium hydroxide adjust its pH value be 4.5 after, be added 0.09g dodecyl Diatomite mixed liquor is made after dispersing and dissolving for benzene sulfonic acid sodium salt；
S2,2.2g ammonium persulfate and 1.6g potassium permanganate are weighed respectively, be dissolved in 10mL deionized water that be prepared into ammonium manganese multiple Solution is closed, ammonium manganese composite solution is then added drop-wise to diatomite mixed liquor obtained in step S1 with 45 drops/minute speed In, 30min is stirred, is uniformly mixed, 1.5g urea is added, stirs 30min, is uniformly mixed obtained composite diatomite solution；
S3, composite diatomite solution obtained in step S2 is placed in reaction kettle, it is anti-that unboiled water heat is issued at 120 DEG C It answers, reacts 12h, AlOOH/MnO is made2@diatomite composite material.
After the reaction was completed, cooling, it filters, washing, it is dry to get AlOOH/MnO2@diatomite composite material.
Sample topography, structure and performance test results: Fig. 1 is AlOOH/MnO prepared by the embodiment of the present invention 22@diatom The XRD spectrum of soil composite material, wherein lower section is the XRD spectrum of diatomite original soil, top AlOOH/MnO2@tripolite compound The XRD spectrum of condensation material；Fig. 2 is AlOOH/MnO prepared by the embodiment of the present invention 22@diatomite composite material is put in difference SEM photograph under big multiplying power, it can be seen from the figure that on diatomite disk growth in situ AlOOH/MnO2@composite diatomite material AlOOH in material in the form of sheets, MnO2In flower-shaped, thickness 8-10nm, length 60-70nm, width 15-25nm；Fig. 3 is that the present invention is real Apply AlOOH/MnO prepared by example 22The EDS map of@diatomite composite material；Fig. 4 is prepared by the embodiment of the present invention 2 AlOOH/MnO2The XPS map of@diatomite composite material, wherein A is that AlOOH/MnO2@diatomite composite material adsorbs pentavalent The full spectrogram of XPS of the preceding < a > of As and rear < b >, B are Mn 2p trajectory diagram, and C is Al 2p trajectory diagram, and D is O1s trajectory diagram；Fig. 5 is this The adsorption isotherm of AlOOH/MnO2@diatomite composite material prepared by inventive embodiments 2, calculating learn that its specific surface area is 140m2/g；In addition, measuring AlOOH/MnO prepared by the embodiment of the present invention 22The arsenic (V) of@diatomite composite material, which adsorbs, to be held Amount: 160mg/g.
Embodiment 3
The embodiment of the present invention 3 provides a kind of AlOOH/MnO2The preparation method of@diatomite composite material, specifically include with Lower step:
S1, it weighs 2.0g diatomite and is added in the beaker of 200mL, be added 40mL deionized water, magnetic agitation 20min, 3.6g AlCl is then added3Stirring and dissolving, and by be added dropwise ammonium hydroxide adjust its pH value be 4.0 after, be added 0.12g dodecyl Diatomite mixed liquor is made after dispersing and dissolving for benzene sulfonic acid sodium salt；
S2,2.3g ammonium persulfate and 1.6g potassium permanganate are weighed respectively, be dissolved in 10mL deionized water that be prepared into ammonium manganese multiple Solution is closed, ammonium manganese composite solution is then added drop-wise to diatomite mixed liquor obtained in step S1 with 45 drops/minute speed In, 30min is stirred, is uniformly mixed, 1.8g urea is added, stirs 30min, is uniformly mixed obtained composite diatomite solution；
S3, composite diatomite solution obtained in step S2 is placed in reaction kettle, it is anti-that unboiled water heat is issued at 120 DEG C It answers, reacts 16h, AlOOH/MnO is made2@diatomite composite material.
After the reaction was completed, cooling, it filters, washing, it is dry to get AlOOH/MnO2@diatomite composite material.
Sample topography, structure and performance test results: the AlOOH/MnO of growth in situ on diatomite disk2@composite diatomite Material, wherein AlOOH in the form of sheets, MnO2In flower-shaped, thickness 8-12nm, length 60-80nm, width 20-30nm；Specific surface area: 146m2/g；Arsenic (V) adsorption capacity: 165mg/g.
Finally, being not intended to limit the scope of the present invention the above is only preferred embodiment of the invention.It is all this Within the spirit and principle of invention, any modification, equivalent replacement, improvement and so on should be included in protection model of the invention Within enclosing.

Claims (10)

1.一种AlOOH/MnO2@硅藻土复合材料的制备方法，其特征在于，包括以下步骤：1. a preparation method of AlOOH/MnO 2 @diatomite composite material, is characterized in that, comprises the following steps: S1、将硅藻土加入离子水中后搅拌制得硅藻土悬浮液，随后加入AlCl3搅拌溶解，并通过滴加氨水调节其pH值为3.5-5.8后，加入十二烷基苯磺酸钠，分散溶解后制得硅藻土混合液；S1, add diatomite into ionized water and stir to obtain a diatomite suspension, then add AlCl to stir and dissolve, and adjust its pH value by dropwise addition of ammonia to 3.5-5.8 , then add sodium dodecylbenzenesulfonate , after dispersing and dissolving, the diatomite mixture is obtained; S2、按比例称取过硫酸铵和高锰酸钾，溶于去离子水中制得铵锰复合溶液，随后将铵锰复合溶液缓慢滴加到步骤S1中所制得的硅藻土混合液中，搅拌均匀，再加入尿素混合均匀制得硅藻土复合溶液；S2, weigh ammonium persulfate and potassium permanganate in proportion, dissolve in deionized water to obtain ammonium-manganese composite solution, then slowly drop the ammonium-manganese composite solution into the diatomite mixed solution prepared in step S1 , stir evenly, then add urea and mix to obtain a diatomite composite solution; S3、将步骤S2中所制得的硅藻土复合溶液发生水热反应，即得AlOOH/MnO2@硅藻土复合材料。S3. The diatomite composite solution prepared in step S2 is subjected to a hydrothermal reaction to obtain an AlOOH/MnO 2 @diatomite composite material. 2.根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述AlCl3的加入量与所述硅藻土的质量之比为0.9-3.6：1，优选为1.8-2.4：1；2. The preparation method according to claim 1, characterized in that, in step S1, the ratio of the addition of the AlCl to the mass of the diatomite is 0.9-3.6:1, preferably 1.8-2.4: 1; 和/或，通过滴加所述氨水调节其pH值为4-5；And/or, adjust its pH value to be 4-5 by dripping described ammoniacal liquor; 和/或，所述十二烷基苯磺酸钠的加入量与所述硅藻土的质量之比为0.03-0.12：1，优选为0.08-0.10：1。And/or, 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. 3.根据权利要求1或2所述的制备方法，其特征在于，步骤S2中，所述高锰酸钾的加入量与所述硅藻土的质量之比为0.4-1.6：1，优选为0.8-1.2：1。3. preparation method according to claim 1 and 2 is characterized in that, in step S2, the ratio of the addition of described potassium permanganate to the mass of described diatomite is 0.4-1.6:1, preferably 0.8-1.2:1. 4.根据权利要求3所述的制备方法，其特征在于，步骤S2中，所述过硫酸铵与所述高锰酸钾的加入量摩尔比为0.8-1.2：1，优选为1：1。4. The preparation method according to claim 3, characterized in that, in step S2, the molar ratio of the added amount of the ammonium persulfate to the potassium permanganate is 0.8-1.2:1, preferably 1:1. 5.根据权利要求1-4任一项所述的制备方法，其特征在于，步骤S2中，5. The preparation method according to any one of claims 1-4, wherein in step S2, 所述铵锰复合溶液的滴加速度为45-55滴/分钟；The dropping rate of the ammonium-manganese composite solution is 45-55 drops/min; 和/或，所述尿素的加入量与所述硅藻土的质量之比为0.45-1.8：1，优选为0.8-1.5：1。And/or, the ratio of the added amount of the urea to the mass of the diatomaceous earth is 0.45-1.8:1, preferably 0.8-1.5:1. 6.根据权利要求1-5任一项所述的制备方法，其特征在于，步骤S3中，所述水热反应的反应温度为110-130℃，优选为120℃。6 . The preparation method according to claim 1 , wherein in step S3 , the reaction temperature of the hydrothermal reaction is 110-130° C., preferably 120° C. 7 . 7.根据权利要求6所述的制备方法，其特征在于，步骤S3中，所述水热反应的反应时间为5-14h，优选为6-10h。7. The preparation method according to claim 6, wherein in step S3, the reaction time of the hydrothermal reaction is 5-14h, preferably 6-10h. 8.根据权利要求6或7所述的制备方法，其特征在于，步骤S3中，还包括，水热反应完成并冷却后的过滤、洗涤和干燥；8. preparation method according to claim 6 or 7, is characterized in that, in step S3, also comprises, filtration, washing and drying after hydrothermal reaction is completed and cooled; 优选地，所述洗涤包括依次采用去离子水和无水乙醇各洗三次。Preferably, the washing includes successively washing with deionized water and absolute ethanol three times each. 9.权利要求1-8任一项所述制备方法制备得到的AlOOH/MnO2@硅藻土复合材料。9. The AlOOH/MnO 2 @diatomite composite material prepared by the preparation method of any one of claims 1-8. 10.权利要求1-8任一项所述的制备方法或权利要求9所述的AlOOH/MnO2@硅藻土复合材料在吸附处理重金属砷离子中的应用。10. The preparation method according to any one of claims 1-8 or the application of the AlOOH/MnO 2 @diatomite composite material according to claim 9 in the adsorption treatment of heavy metal arsenic ions.
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