WO2022160836A1 - Porous iron-manganese composite material for efficiently fixing and removing antimony pollution, preparation method therefor and use thereof - Google Patents
Porous iron-manganese composite material for efficiently fixing and removing antimony pollution, preparation method therefor and use thereof Download PDFInfo
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- WO2022160836A1 WO2022160836A1 PCT/CN2021/127801 CN2021127801W WO2022160836A1 WO 2022160836 A1 WO2022160836 A1 WO 2022160836A1 CN 2021127801 W CN2021127801 W CN 2021127801W WO 2022160836 A1 WO2022160836 A1 WO 2022160836A1
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 71
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 71
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 44
- 239000012266 salt solution Substances 0.000 claims abstract description 22
- 150000002696 manganese Chemical class 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 150000002505 iron Chemical class 0.000 claims description 15
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 12
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 235000002867 manganese chloride Nutrition 0.000 claims description 12
- 239000011565 manganese chloride Substances 0.000 claims description 12
- 229940099607 manganese chloride Drugs 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 2
- 159000000014 iron salts Chemical class 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 7
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 abstract description 6
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 208000004998 Abdominal Pain Diseases 0.000 description 1
- 206010010774 Constipation Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 description 1
- 230000004596 appetite loss Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 208000019017 loss of appetite Diseases 0.000 description 1
- 235000021266 loss of appetite Nutrition 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
Definitions
- the invention belongs to the technical field of adsorption materials, and in particular relates to a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, and a preparation method and application thereof.
- Natural antimony mainly exists in the form of ore, and the main valence states are Sb(III) and Sb(V).
- the global antimony reserves are 4-5 million tons, and China's antimony reserves ranks first in the world.
- China's output accounts for about 79.6% of the world's total.
- the unreasonable mining of antimony ore and the irregular use of antimony-containing products have led to a sharp rise in the content of antimony in China's soil, water and atmosphere.
- the antimony content in the antimony-rich regions such as Hunan, Guizhou and Guangxi far exceeds the background value.
- the concentration of Sb in mine drainage and flotation industrial wastewater in China is as high as 30 mg ⁇ L -1 .
- Antimony has received increasing attention due to its toxicity and biological effects. Since antimony can inhibit the growth of microorganisms and affect the activity of soil enzymes, excessive antimony content in soil has a great impact on the growth and quality of crops, and also has potential harm to human health. Exposure to antimony-containing dust in the air can cause respiratory illness in workers. Antimony poisoning can cause headache, dizziness, abdominal pain, constipation, and loss of appetite. Antimony has been listed as a priority pollutant by the US EPA and the European Union. The World Health Organization stipulates that the hygienic standard for antimony in drinking water is 20ug/L. The limit of antimony concentration in China's "Environmental Quality Standard for Surface Water" (GB3838-2002) is 0.005mg/L.
- the purpose of the present invention is to provide a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, and a preparation method and application thereof.
- the primary purpose of the present invention is to provide a method for preparing an antimony-contaminated porous iron-manganese composite material.
- the prepared porous iron-manganese composite material can be used to deal with trivalent antimony and pentavalent antimony pollution, not only the removal rate is fast but also the adsorption capacity is high.
- One of the objects of the present invention is to provide a porous iron-manganese composite material prepared by the above preparation method.
- the porous iron-manganese composite material has the characteristics of rich pore structure, high specific surface area and stability.
- Another object of the present invention is to provide the application of the above-mentioned porous iron-manganese composite material.
- the porous iron-manganese composite material is used to deal with the problem of antimony pollution (trivalent antimony and pentavalent antimony) in the environment.
- the object of the present invention is achieved by at least one of the following technical solutions.
- the porous iron-manganese composite material for efficiently fixing and removing antimony pollution provided by the invention is a porous iron-manganese composite material.
- the preparation method of the porous iron-manganese composite material for efficiently fixing and removing antimony pollution provided by the present invention comprises the following steps:
- step (3) slowly adding the iron salt solution to the suspension described in step (2), and stirring to obtain a mixed solution
- step (3) Adjusting the pH value of the mixed solution in step (3) to 6.5-8.5, and then performing aging treatment, centrifuging to obtain the precipitate, washing, drying, grinding, and sieving, to obtain the described solution for high-efficiency immobilization and removal of antimony pollution.
- Porous ferromanganese composites Porous ferromanganese composites.
- the permanganate in step (1) is one or more of potassium permanganate and sodium permanganate;
- the manganese salt is one or more of manganese chloride, manganese nitrate and manganese sulfate; Described ferric salt is more than one in ferric nitrate, ferric sulfate and ferric chloride; the molar ratio of described permanganate, manganese salt and ferric salt is (1.5-9): (1-6): (2.5-15 ).
- the permanganate in step (1) is potassium permanganate; the manganese salt is manganese chloride; and the soluble iron salt is ferric chloride.
- the molar ratio of the permanganate, manganese and iron salt is (3-6):(2-4):(5-10).
- the concentration of the permanganate solution in step (1) is 0.015 mol/L-0.090 mol/L; the concentration of the manganese salt solution is 0.010 mol/L-0.060 mol/L; the concentration of the iron salt solution is 0.025 mol/L-0.150 mol/L.
- the solvents of the permanganate solution, the manganese salt solution and the iron salt solution in step (1) are all deionized water.
- the rate of dropping the permanganate solution into the manganese salt solution in step (2) is 0.1-5 mL/min; the stirring treatment time is 1-3 h.
- the rate at which the iron salt solution is added to the suspension in step (3) is 5-10ml/min, and the time for the stirring treatment is 1-3h.
- step (4) the time of the aging treatment in step (4) is 6-18h.
- the centrifugal speed is 2000-6000 rpm, and the centrifugal time is 10-20 min; the drying temperature is 40-80°C, and the drying time is 18-36 h; The hole size is 100-500 mesh.
- step (4) ammonia water is used to adjust the mixed solution to 6.5-8.5.
- step (4) ammonia water is used to adjust the mixed solution to be 7.0-8.0.
- the washing in step (4) is to wash the precipitate with deionized water, and the number of washings is 3-5 times.
- the present invention provides a porous iron-manganese composite material prepared by the above-mentioned preparation method for efficiently fixing and removing antimony pollution.
- porous iron-manganese composite material for efficiently fixing and removing antimony pollution provided by the present invention can be applied to the treatment of heavy metal-containing antimony pollution.
- the porous iron-manganese composite material for efficiently fixing and removing antimony pollution of the present invention is a kind of antimony based on the strong oxidizing property of manganese oxide, the strong affinity of iron oxide for antimony and the high adsorption property of high surface area material for pollutants.
- the porous iron-manganese composite material prepared with high fixing performance can be used to deal with the problem of antimony pollution in the environment.
- the present invention has the following advantages and beneficial effects:
- the preparation process of the present invention is simple, the reaction conditions are mild, the energy consumption is low, the yield is high, and the application prospect is broad;
- the elements in the iron-manganese oxide used are natural constituents, which are characterized by low price, wide sources, and no environmental pollution; the selected reagents are inexpensive and non-toxic.
- the porous iron-manganese composite material provided by the present invention for efficient fixation and removal of antimony pollution has developed pores and a large specific surface area, which is conducive to the removal of pollutants;
- the porous iron-manganese composite material provided by the present invention for efficient fixation and removal of antimony contamination is effective against Sb(III) Or the removal of Sb(V) has excellent adsorption, with the characteristics of fast adsorption rate and large adsorption capacity.
- Figure 1a and Figure 1b are the SEM image and the EDS image of the porous iron-manganese composite material prepared in Example 1 for efficient fixation and removal of antimony pollution, respectively;
- Fig. 2 is the BET diagram of the porous iron-manganese composite material prepared in Example 1;
- Example 3 is a SEM image of the porous iron-manganese composite material prepared in Example 2 for efficient fixation and removal of antimony pollution;
- Example 4 is a SEM image of the porous iron-manganese composite material prepared in Example 3 for efficient fixation and removal of antimony pollution;
- Fig. 5a and Fig. 5b are graphs showing the result of immobilizing antimony on the porous iron-manganese composite material used for high-efficiency immobilization and removal of antimony pollution in Example 4;
- 6a and 6b are graphs showing the result of fixing antimony on the porous iron-manganese composite material for high-efficiency fixing and removing antimony pollution in Example 5 with initial concentration.
- a preparation method of a porous iron-manganese composite material for efficiently fixing and removing antimony pollution comprising the following steps:
- step (3) Add the ferric chloride solution to the suspension obtained in step (2) at a dropping rate of 7.5 mL/min, and stir for 2 h to obtain a mixed solution;
- step (3) Adjust the pH of the mixture in step (3) to 7.5 with ammonia water, age for 12 h, centrifuge at 4000 rpm for 15 min, remove the supernatant, rinse with deionized water several times, and dry at 60 °C After 24 hours, grinding through a 200-mesh sieve to obtain the porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution.
- FIG. 1a is the SEM image
- Fig. 1b is the EDS image
- Fig. 2 is the BET image. It can be seen from Figure 1a, Figure 1b and Figure 2 that the obtained iron-manganese composite material has a rich pore structure, and the nano-sized particles are uniformly distributed on the stacked flakes, and its specific surface area is large, which is conducive to the pollution of pollutants. remove.
- a preparation method of a porous iron-manganese composite material for efficiently fixing and removing antimony pollution comprising the following steps:
- step (3) Add the ferric chloride solution to the suspension obtained in step (2) at a dropping rate of 5.0 mL/min, and stir for 1 h to obtain a mixed solution;
- step (3) Adjust the pH of the mixed solution in step (3) to 7.0 with ammonia water, age for 6 h, centrifuge at 2000 rpm for 10 min, remove the supernatant, rinse with deionized water several times, and dry at 40 °C 18h, grinding through a 100-mesh sieve to obtain the porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution.
- the morphology of the prepared porous iron-manganese composites is shown in Figure 3. It can be seen from Figure 3 that the obtained iron-manganese composite material also has a rich pore structure, and the nano-sized particles are uniformly distributed on the stacked flakes.
- a preparation method of a porous iron-manganese composite material for efficiently fixing and removing antimony pollution comprising the following steps:
- step (3) adding the ferric chloride solution to the suspension obtained in step (2) at a dropping rate of 10 mL/min, and stirring for 3 h to obtain a mixed solution;
- step (3) Adjust the pH of the mixture in step (3) to 8.0 with ammonia water, age for 18 h, centrifuge at 6000 rpm for 20 min, remove the supernatant, rinse with deionized water several times, and dry at 80 °C 36h, grinding through a 500-mesh sieve to obtain the porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution.
- the morphology of the as-prepared porous iron-manganese composites is shown in Figure 4. It can be seen from Figure 4 that the obtained iron-manganese composite material also has a rich pore structure, and the nano-sized particles are uniformly distributed on the stacked flakes.
- This test includes:
- Fig. 5a shows the adsorption kinetics curve of Sb(III) by the porous iron-manganese composite material for high-efficiency immobilization and removal of antimony pollution
- Fig. 5b is the adsorption kinetics curve of the porous iron-manganese composite material for high-efficiency immobilization and removal of antimony pollution.
- Sb(V) adsorption kinetics curve.
- This test includes:
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention belongs to the technical field of adsorption materials, and discloses a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, a preparation method therefor and the use thereof. The method comprises: formulating a permanganate, a manganese salt and a ferric salt into a permanganate solution, a manganese salt solution and a ferric salt solution, respectively; dropwise adding the permanganate solution into the manganese salt solution, and stirring same to obtain a suspension; adding the ferric salt solution into the suspension, and stirring same to obtain a mixed solution; and adjusting the pH value of the mixed solution to 6.5-8.5, subjecting same to an aging treatment, centrifuging same, taking the precipitate, and washing, drying, grinding and sieving same to obtain the porous iron-manganese composite material for efficiently fixing and removing the antimony pollution. The material has the characteristics of being porous, and having a high specific surface area and a stable adsorption; and the material can be used for treating trivalent antimony and pentavalent antimony pollution, and has a high removal rate and a high adsorption capacity. The method of the present invention is simple, and has mild reaction conditions and a low energy consumption.
Description
本发明属于吸附材料的技术领域,具体涉及一种用于高效固定去除锑污染的多孔铁锰复合材料及其制备方法与应用。 The invention belongs to the technical field of adsorption materials, and in particular relates to a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, and a preparation method and application thereof.
天然锑主要以矿石的形式存在,主要价态为Sb(III)和Sb(V)。全球锑的储量为4-5百万吨,而中国锑储量位居世界第一。作为产锑大国,中国产量约占世界总量的79.6%。近年来,锑矿的不合理开采和含锑产品的不规范使用,导致中国土壤、水和大气中锑的含量急剧上升。其中湖南、贵州和广西等锑矿丰富的地区环境中锑的含量远远超过背景值。在我国矿井排水和浮选工业废水中Sb的浓度高达30 mg·L
-1。调查发现大宝山铜铁矿和大冶铁矿邻近河流中Sb的浓度高达900和52.7μg/L。
Natural antimony mainly exists in the form of ore, and the main valence states are Sb(III) and Sb(V). The global antimony reserves are 4-5 million tons, and China's antimony reserves ranks first in the world. As a major producer of antimony, China's output accounts for about 79.6% of the world's total. In recent years, the unreasonable mining of antimony ore and the irregular use of antimony-containing products have led to a sharp rise in the content of antimony in China's soil, water and atmosphere. Among them, the antimony content in the antimony-rich regions such as Hunan, Guizhou and Guangxi far exceeds the background value. The concentration of Sb in mine drainage and flotation industrial wastewater in China is as high as 30 mg·L -1 . The investigation found that the concentration of Sb in the adjacent rivers of Dabaoshan copper-iron mine and Daye iron mine was as high as 900 and 52.7 μg/L.
锑因其毒性和生物效应受到越来越多的关注。由于锑会抑制微生物生长和影响土壤酶活性,土壤中锑含量的超标对于农作物的生长、品质都有较大影响,且对于人类健康也有潜在的危害。暴露在空气中的含锑粉尘会造成工人呼吸道疾病。锑中毒会引起头痛,头晕,腹痛,便秘和食欲不振等。美国环保局和欧盟已将锑列为优先污染物。世界卫生组织规定饮用水中锑的卫生标准为20ug/L。而中国《地表水环境质量标准》(GB3838-2002)中锑浓度限值为0.005mg/L。Antimony has received increasing attention due to its toxicity and biological effects. Since antimony can inhibit the growth of microorganisms and affect the activity of soil enzymes, excessive antimony content in soil has a great impact on the growth and quality of crops, and also has potential harm to human health. Exposure to antimony-containing dust in the air can cause respiratory illness in workers. Antimony poisoning can cause headache, dizziness, abdominal pain, constipation, and loss of appetite. Antimony has been listed as a priority pollutant by the US EPA and the European Union. The World Health Organization stipulates that the hygienic standard for antimony in drinking water is 20ug/L. The limit of antimony concentration in China's "Environmental Quality Standard for Surface Water" (GB3838-2002) is 0.005mg/L.
如何开发一种可以高效固定三价锑和五价锑的材料,已成为人们研究的重点之一。虽然目前已有一种铁锰复合氧化物的制备及其原位除锑的方法(CN201910961787.0),但文献所报道的铁锰复合物因不具备多孔结构,而吸附材料的比表面积是影响吸附性能的重要特性,所以对五价锑的去除性能有进一步提升的空间。而且该文献并没有探讨铁锰复合材料对三价锑的去除效果。三价锑对生态系统的危害性更大,更需要被关注。How to develop a material that can efficiently fix trivalent antimony and pentavalent antimony has become one of the focuses of research. Although there is a method for the preparation of iron-manganese composite oxides and its in-situ antimony removal (CN201910961787.0), the iron-manganese composites reported in the literature do not have a porous structure, and the specific surface area of the adsorption material affects the adsorption. Therefore, there is room for further improvement in the removal performance of pentavalent antimony. Moreover, this document does not discuss the removal effect of iron-manganese composites on trivalent antimony. Trivalent antimony is more harmful to the ecosystem and needs more attention.
为了克服现有技术存在的不足,本发明的目的是提供一种用于高效固定去除锑污染的多孔铁锰复合材料及其制备方法与应用。In order to overcome the deficiencies of the prior art, the purpose of the present invention is to provide a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, and a preparation method and application thereof.
本发明的首要目的在于提供一种锑污染的多孔铁锰复合材料的制备方法。所制备的多孔铁锰复合材料能用于处理三价锑和五价锑污染,不仅去除速率快而且吸附量高。The primary purpose of the present invention is to provide a method for preparing an antimony-contaminated porous iron-manganese composite material. The prepared porous iron-manganese composite material can be used to deal with trivalent antimony and pentavalent antimony pollution, not only the removal rate is fast but also the adsorption capacity is high.
本发明的其中一个目的在于提供由上述制备方法制备得到的多孔铁锰复合材料。所述多孔铁锰复合材料具有丰富的孔隙结构、比表面积高和稳定的特性。 One of the objects of the present invention is to provide a porous iron-manganese composite material prepared by the above preparation method. The porous iron-manganese composite material has the characteristics of rich pore structure, high specific surface area and stability.
本发明的另一目的在于提供上述多孔铁锰复合材料的应用。所述多孔铁锰复合材料用于处理环境中锑污染(三价锑和五价锑)的问题。Another object of the present invention is to provide the application of the above-mentioned porous iron-manganese composite material. The porous iron-manganese composite material is used to deal with the problem of antimony pollution (trivalent antimony and pentavalent antimony) in the environment.
本发明的目的至少通过如下技术方案之一实现。The object of the present invention is achieved by at least one of the following technical solutions.
本发明提供的用于高效固定去除锑污染的多孔铁锰复合材料是一种多孔铁锰复合材料。The porous iron-manganese composite material for efficiently fixing and removing antimony pollution provided by the invention is a porous iron-manganese composite material.
本发明提供的用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,包括如下步骤:The preparation method of the porous iron-manganese composite material for efficiently fixing and removing antimony pollution provided by the present invention comprises the following steps:
(1)将可溶性的高锰酸盐、可溶性的锰盐及可溶性的铁盐分别配制成高锰酸盐溶液、锰盐溶液及铁盐溶液;(1) Prepare soluble permanganate, soluble manganese salt and soluble iron salt into permanganate solution, manganese salt solution and iron salt solution respectively;
(2)将步骤(1)所述高锰酸盐溶液缓慢滴加至锰盐溶液中,搅拌处理,得到悬浮液;(2) slowly dropping the permanganate solution described in step (1) into the manganese salt solution, and stirring to obtain a suspension;
(3)将铁盐溶液缓慢加入步骤(2)所述悬浮液中,搅拌处理,得到混合液;(3) slowly adding the iron salt solution to the suspension described in step (2), and stirring to obtain a mixed solution;
(4)调节步骤(3)所述混合液的pH值为6.5-8.5,然后进行陈化处理,离心取沉淀,洗涤,干燥,研磨,过筛,得到所述用于高效固定去除锑污染的多孔铁锰复合材料。(4) Adjusting the pH value of the mixed solution in step (3) to 6.5-8.5, and then performing aging treatment, centrifuging to obtain the precipitate, washing, drying, grinding, and sieving, to obtain the described solution for high-efficiency immobilization and removal of antimony pollution. Porous ferromanganese composites.
进一步地,步骤(1)所述高锰酸盐为高锰酸钾、高锰酸钠中的一种以上;所述锰盐为氯化锰、硝酸锰及硫酸锰中的一种以上;所述铁盐为硝酸铁、硫酸铁及氯化铁中一种以上;所述高锰酸盐、锰盐及铁盐的摩尔比为(1.5-9):(1-6):(2.5-15)。Further, the permanganate in step (1) is one or more of potassium permanganate and sodium permanganate; the manganese salt is one or more of manganese chloride, manganese nitrate and manganese sulfate; Described ferric salt is more than one in ferric nitrate, ferric sulfate and ferric chloride; the molar ratio of described permanganate, manganese salt and ferric salt is (1.5-9): (1-6): (2.5-15 ).
优选地,步骤(1)所述高锰酸盐为高锰酸钾;所述锰盐为氯化锰;所述可溶性铁盐为氯化铁。Preferably, the permanganate in step (1) is potassium permanganate; the manganese salt is manganese chloride; and the soluble iron salt is ferric chloride.
优选地,所述高锰酸盐、锰盐及铁盐的摩尔比为(3-6):(2-4):(5-10)。Preferably, the molar ratio of the permanganate, manganese and iron salt is (3-6):(2-4):(5-10).
进一步地,步骤(1)所述高锰酸盐溶液的浓度为0.015 mol/L-0.090 mol/L;所述锰盐溶液的浓度为0.010
mol/L-0.060 mol/L;所述铁盐溶液的浓度为0.025 mol/L-0.150
mol/L。Further, the concentration of the permanganate solution in step (1) is 0.015 mol/L-0.090 mol/L; the concentration of the manganese salt solution is 0.010
mol/L-0.060 mol/L; the concentration of the iron salt solution is 0.025 mol/L-0.150
mol/L.
优选地,步骤(1)所述高锰酸盐溶液、锰盐溶液及铁盐溶液的溶剂均为去离子水。Preferably, the solvents of the permanganate solution, the manganese salt solution and the iron salt solution in step (1) are all deionized water.
进一步地,步骤(2)所述高锰酸盐溶液滴加至锰盐溶液中的滴加速率为0.1-5 mL/min;所述搅拌处理的时间为1-3h。Further, the rate of dropping the permanganate solution into the manganese salt solution in step (2) is 0.1-5 mL/min; the stirring treatment time is 1-3 h.
进一步地,步骤(3)所述铁盐溶液加入悬浮液中的速率为5-10ml/min,所述搅拌处理的时间为1-3h。Further, the rate at which the iron salt solution is added to the suspension in step (3) is 5-10ml/min, and the time for the stirring treatment is 1-3h.
进一步地,步骤(4)所述陈化处理的时间为6-18h。Further, the time of the aging treatment in step (4) is 6-18h.
进一步地,步骤(4)所述离心的速率为2000-6000rpm,离心的时间为10-20min;所述干燥的温度为40-80℃,干燥的时间为18-36h;所述过筛的筛孔大小为100-500目。Further, in step (4), the centrifugal speed is 2000-6000 rpm, and the centrifugal time is 10-20 min; the drying temperature is 40-80°C, and the drying time is 18-36 h; The hole size is 100-500 mesh.
优选地,步骤(4)中,使用氨水调节所述混合液为6.5-8.5。Preferably, in step (4), ammonia water is used to adjust the mixed solution to 6.5-8.5.
进一步优选地,步骤(4)中,使用氨水调节所述混合液为7.0-8.0。Further preferably, in step (4), ammonia water is used to adjust the mixed solution to be 7.0-8.0.
优选地,步骤(4)所述洗涤为用去离子水对沉淀进行洗涤,洗涤的次数为3-5次。Preferably, the washing in step (4) is to wash the precipitate with deionized water, and the number of washings is 3-5 times.
本发明提供一种由上述的制备方法制得的用于高效固定去除锑污染的多孔铁锰复合材料。The present invention provides a porous iron-manganese composite material prepared by the above-mentioned preparation method for efficiently fixing and removing antimony pollution.
本发明提供的用于高效固定去除锑污染的多孔铁锰复合材料能够应用在处理含重金属锑污染的方面。The porous iron-manganese composite material for efficiently fixing and removing antimony pollution provided by the present invention can be applied to the treatment of heavy metal-containing antimony pollution.
本发明的用于高效固定去除锑污染的多孔铁锰复合材料是一种基于锰氧化物的强氧化性、铁氧化物对锑的强亲和力与高表面积材料对污染物的高吸附性对锑的高固定性能而制备的多孔铁锰复合材料,可以利用该材料处理环境中锑污染问题。The porous iron-manganese composite material for efficiently fixing and removing antimony pollution of the present invention is a kind of antimony based on the strong oxidizing property of manganese oxide, the strong affinity of iron oxide for antimony and the high adsorption property of high surface area material for pollutants. The porous iron-manganese composite material prepared with high fixing performance can be used to deal with the problem of antimony pollution in the environment.
与现有技术相比,本发明具有如下优点和有益效果:Compared with the prior art, the present invention has the following advantages and beneficial effects:
(1)本发明的制备过程简单,反应条件温和,低耗能、产率高、应用前景广阔;(1) The preparation process of the present invention is simple, the reaction conditions are mild, the energy consumption is low, the yield is high, and the application prospect is broad;
(2)本发明提供的制备方法,所用铁锰氧化物中的元素为自然界的组成成分,价格低廉,来源广泛,无环境污染等特点;所选用试剂价格低廉且无毒。(2) In the preparation method provided by the present invention, the elements in the iron-manganese oxide used are natural constituents, which are characterized by low price, wide sources, and no environmental pollution; the selected reagents are inexpensive and non-toxic.
(3)本发明提供的用于高效固定去除锑污染的多孔铁锰复合材料,孔隙发达,比表面积较大,有利于对污染物的去除;(3) The porous iron-manganese composite material provided by the present invention for efficient fixation and removal of antimony pollution has developed pores and a large specific surface area, which is conducive to the removal of pollutants;
(4)本发明提供的用于高效固定去除锑污染的多孔铁锰复合材料对Sb(III)
或Sb(V)的去除具有优异的吸附性,具有吸附速率快而且吸附量大的特点。(4) The porous iron-manganese composite material provided by the present invention for efficient fixation and removal of antimony contamination is effective against Sb(III)
Or the removal of Sb(V) has excellent adsorption, with the characteristics of fast adsorption rate and large adsorption capacity.
图1 a和图1b分别为实施例1制备的用于高效固定去除锑污染的多孔铁锰复合材料的SEM图和EDS图;Figure 1a and Figure 1b are the SEM image and the EDS image of the porous iron-manganese composite material prepared in Example 1 for efficient fixation and removal of antimony pollution, respectively;
图2为实施例1制备的多孔铁锰复合材料的BET图;Fig. 2 is the BET diagram of the porous iron-manganese composite material prepared in Example 1;
图3为实施例2制备的用于高效固定去除锑污染的多孔铁锰复合材料的SEM图;3 is a SEM image of the porous iron-manganese composite material prepared in Example 2 for efficient fixation and removal of antimony pollution;
图4为实施例3制备的用于高效固定去除锑污染的多孔铁锰复合材料的SEM图;4 is a SEM image of the porous iron-manganese composite material prepared in Example 3 for efficient fixation and removal of antimony pollution;
图5a和图5b为实施例4中时间对所述用于高效固定去除锑污染的多孔铁锰复合材料固定锑结果图;Fig. 5a and Fig. 5b are graphs showing the result of immobilizing antimony on the porous iron-manganese composite material used for high-efficiency immobilization and removal of antimony pollution in Example 4;
图6a和图6b为实施例5中初始浓度对所述用于高效固定去除锑污染的多孔铁锰复合材料固定锑结果图。6a and 6b are graphs showing the result of fixing antimony on the porous iron-manganese composite material for high-efficiency fixing and removing antimony pollution in Example 5 with initial concentration.
以下结合实例对本发明的具体实施作进一步说明,但本发明的实施和保护不限于此。需指出的是,以下若有未特别详细说明之过程,均是本领域技术人员可参照现有技术实现或理解的。所用试剂或仪器未注明生产厂商者,视为可以通过市售购买得到的常规产品。The specific implementation of the present invention will be further described below with reference to examples, but the implementation and protection of the present invention are not limited thereto. It should be pointed out that, if there are any processes that are not described in detail below, those skilled in the art can realize or understand them with reference to the prior art. If the reagents or instruments used do not indicate the manufacturer, they are regarded as conventional products that can be purchased in the market.
实施例Example
1 1
一种用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,包括以下步骤:A preparation method of a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, comprising the following steps:
(1)分别准确称取0.045 mol高锰酸钾、0.030 mol氯化锰和0.075 mol氯化铁,分别加入1000 mL去离子水中,溶解均匀后得到浓度为0.045mol/L的高锰酸钾溶液、浓度为0.030 mol/L的氯化锰溶液及浓度为0.075 mol/L的氯化铁溶液;(1) Accurately weigh 0.045 mol potassium permanganate, 0.030 mol manganese chloride and 0.075 mol ferric chloride, respectively, add them into 1000 mL of deionized water, and dissolve them uniformly to obtain a potassium permanganate solution with a concentration of 0.045 mol/L. , a manganese chloride solution with a concentration of 0.030 mol/L and a ferric chloride solution with a concentration of 0.075 mol/L;
(2)将高锰酸钾溶液以滴加速度1mL/min滴入氯化锰溶液后,再搅拌2 h,得到悬浮液;(2) The potassium permanganate solution was added dropwise to the manganese chloride solution at a dropping rate of 1 mL/min, and then stirred for 2 h to obtain a suspension;
(3)将氯化铁溶液以滴加速度7.5 mL/min加入到步骤(2)所得的悬浮液中,并搅拌2 h,得到混合液;(3) Add the ferric chloride solution to the suspension obtained in step (2) at a dropping rate of 7.5 mL/min, and stir for 2 h to obtain a mixed solution;
(4)用氨水调节步骤(3)所述混合液的pH 为7.5,陈化12 h,以4000 rpm离心15 min后去除上清液,用去离子水冲洗数次,在60℃温度下干燥24h,研磨过200目筛,得到所述用于高效固定去除锑污染的多孔铁锰复合材料。(4) Adjust the pH of the mixture in step (3) to 7.5 with ammonia water, age for 12 h, centrifuge at 4000 rpm for 15 min, remove the supernatant, rinse with deionized water several times, and dry at 60 °C After 24 hours, grinding through a 200-mesh sieve to obtain the porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution.
所制备的多孔铁锰复合材料的形貌和比表面积表征如图1a、图1b和图2所示。其中图1a为SEM图、图1b为EDS图、图2为BET图。从图1a、图1b和图2中可知,所得的铁锰复合材料具有丰富的孔隙结构,层层堆叠的薄片上均匀的分布着纳米小颗粒,其比表面积较大,有利于对污染物的去除。The morphology and specific surface area of the as-prepared porous Fe-Mn composites are shown in Figure 1a, Figure 1b, and Figure 2. Fig. 1a is the SEM image, Fig. 1b is the EDS image, and Fig. 2 is the BET image. It can be seen from Figure 1a, Figure 1b and Figure 2 that the obtained iron-manganese composite material has a rich pore structure, and the nano-sized particles are uniformly distributed on the stacked flakes, and its specific surface area is large, which is conducive to the pollution of pollutants. remove.
实施例Example
22
一种用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,包括以下步骤:A preparation method of a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, comprising the following steps:
(1)分别准确称取0.015 mol高锰酸钾、0.010 mol氯化锰和0.025 mol氯化铁,分别加入1000 mL去离子水中,溶解均匀后得到浓度为0.015 mol/L的高锰酸钾溶液、浓度为0.010 mol/L的氯化锰溶液及浓度为0.025 mol/L的氯化铁溶液;(1) Accurately weigh 0.015 mol potassium permanganate, 0.010 mol manganese chloride and 0.025 mol ferric chloride, respectively, add them to 1000 mL of deionized water, and dissolve them uniformly to obtain a potassium permanganate solution with a concentration of 0.015 mol/L. , a manganese chloride solution with a concentration of 0.010 mol/L and a ferric chloride solution with a concentration of 0.025 mol/L;
(2)将高锰酸钾溶液以滴加速度0.1mL/min滴入氯化锰溶液后,再搅拌1 h,得到悬浮液;(2) The potassium permanganate solution was added dropwise to the manganese chloride solution at a rate of 0.1 mL/min, followed by stirring for 1 h to obtain a suspension;
(3)将氯化铁溶液以滴加速度5.0 mL/min加入到步骤(2)所得的悬浮液中,并搅拌1 h,得到混合液;(3) Add the ferric chloride solution to the suspension obtained in step (2) at a dropping rate of 5.0 mL/min, and stir for 1 h to obtain a mixed solution;
(4)用氨水调节步骤(3)所述混合液的pH 为7.0,陈化6 h,以2000 rpm离心10 min后去除上清液,用去离子水冲洗数次,在40℃温度下干燥18h,研磨过100目筛,得到所述用于高效固定去除锑污染的多孔铁锰复合材料。(4) Adjust the pH of the mixed solution in step (3) to 7.0 with ammonia water, age for 6 h, centrifuge at 2000 rpm for 10 min, remove the supernatant, rinse with deionized water several times, and dry at 40 °C 18h, grinding through a 100-mesh sieve to obtain the porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution.
所制备的多孔铁锰复合材料的形貌如图3所示。从图3中可知,所得的铁锰复合材料也具有丰富的孔隙结构,层层堆叠的薄片上均匀的分布着纳米小颗粒。The morphology of the prepared porous iron-manganese composites is shown in Figure 3. It can be seen from Figure 3 that the obtained iron-manganese composite material also has a rich pore structure, and the nano-sized particles are uniformly distributed on the stacked flakes.
实施例Example
33
一种用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,包括以下步骤:A preparation method of a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, comprising the following steps:
(1)分别准确称取0.090 mol高锰酸钾、0.060 mol氯化锰和0.150 mol氯化铁,分别加入1000 mL去离子水中,溶解均匀后得到浓度为0.090 mol/L的高锰酸钾溶液、浓度为0.060 mol/L的氯化锰溶液及浓度为0.150 mol/L的氯化铁溶液;(1) Accurately weigh 0.090 mol potassium permanganate, 0.060 mol manganese chloride and 0.150 mol ferric chloride, respectively, add them into 1000 mL of deionized water, and dissolve them uniformly to obtain a potassium permanganate solution with a concentration of 0.090 mol/L. , a manganese chloride solution with a concentration of 0.060 mol/L and a ferric chloride solution with a concentration of 0.150 mol/L;
(2)将高锰酸钾溶液以滴加速度5 mL/min滴入氯化锰溶液后,再搅拌3 h,得到悬浮液;(2) The potassium permanganate solution was added dropwise to the manganese chloride solution at a dropping rate of 5 mL/min, and then stirred for 3 h to obtain a suspension;
(3)将氯化铁溶液以滴加速度10 mL/min加入到步骤(2)所得的悬浮液中,并搅拌3 h,得到混合液;(3) adding the ferric chloride solution to the suspension obtained in step (2) at a dropping rate of 10 mL/min, and stirring for 3 h to obtain a mixed solution;
(4)用氨水调节步骤(3)所述混合液的pH 为8.0,陈化18 h,以6000 rpm离心20 min后去除上清液,用去离子水冲洗数次,在80℃温度下干燥36h,研磨过500目筛,得到所述用于高效固定去除锑污染的多孔铁锰复合材料。(4) Adjust the pH of the mixture in step (3) to 8.0 with ammonia water, age for 18 h, centrifuge at 6000 rpm for 20 min, remove the supernatant, rinse with deionized water several times, and dry at 80 °C 36h, grinding through a 500-mesh sieve to obtain the porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution.
所制备的多孔铁锰复合材料的形貌如图4所示。从图4中可知,所得的铁锰复合材料也具有丰富的孔隙结构,层层堆叠的薄片上均匀的分布着纳米小颗粒。The morphology of the as-prepared porous iron-manganese composites is shown in Figure 4. It can be seen from Figure 4 that the obtained iron-manganese composite material also has a rich pore structure, and the nano-sized particles are uniformly distributed on the stacked flakes.
实施例Example
44
为了探究制备的用于高效固定去除锑污染的多孔铁锰复合材料在处理含重金属锑污染的废水效果与时间之间的关系。以下采用Sb(III)溶液和Sb(V)溶液作为模拟废水进行测试。In order to explore the relationship between the effect and time of the prepared porous iron-manganese composites for efficient immobilization and removal of antimony pollution in the treatment of wastewater containing heavy metal antimony pollution. The following uses Sb(III) solution and Sb(V) solution as simulated wastewater for testing.
该测试,包括:This test includes:
准确称取多份0.005g多孔铁锰复合材料分别置于50ml离心管中,分别向离心管中移取25mL浓度为20 mg·L
-1
Sb(III)溶液或Sb(V)溶液,充分混合均匀后置于30 ± 1℃水浴振荡器上震荡,在震荡时间为1min,
2.5min, 5min, 8min, 10min, 20min, 30min, 60min, 120min, 240min和 480 min的时候,取溶液过0.45μm滤膜,原子吸收分光光度计测定溶液中Sb(III) 或Sb(V)的浓度,测试结果如图5a和图5b所示。图5 a为所述用于高效固定去除锑污染的多孔铁锰复合材料对Sb(III) 吸附动力学曲线图,图5 b为所述用于高效固定去除锑污染的多孔铁锰复合材料对Sb(V)吸附动力学曲线图。
Accurately weigh a number of 0.005g porous iron-manganese composite materials and place them in 50ml centrifuge tubes, respectively, pipette 25ml of Sb(III) solution or Sb(V) solution with a concentration of 20 mg·L -1 into the centrifuge tube, and mix thoroughly. After homogenization, place it on a water bath shaker at 30 ± 1°C and shake it. When the shaking time is 1min, 2.5min, 5min, 8min, 10min, 20min, 30min, 60min, 120min, 240min and 480min, take the solution and filter it through 0.45 μm. film, the concentration of Sb(III) or Sb(V) in the solution was measured by atomic absorption spectrophotometer, and the test results are shown in Fig. 5a and Fig. 5b. Fig. 5a shows the adsorption kinetics curve of Sb(III) by the porous iron-manganese composite material for high-efficiency immobilization and removal of antimony pollution, and Fig. 5b is the adsorption kinetics curve of the porous iron-manganese composite material for high-efficiency immobilization and removal of antimony pollution. Sb(V) adsorption kinetics curve.
从图5a和图5b可知,所述用于高效固定去除锑污染的多孔铁锰复合材料对Sb(III) 或Sb(V)吸附分别在60分钟和120分钟内就达到吸附平衡,之后Sb(III) 或Sb(V)的吸附随着时间的变化不大,说明该多孔铁锰复合材料能快速地对Sb(III) 或Sb(V)进行固定去除,平衡吸附量分别为99.5 和62.1 mg·g
-1.
It can be seen from Fig. 5a and Fig. 5b that the porous iron-manganese composites for high-efficiency immobilization and removal of antimony contamination reach the adsorption equilibrium for Sb(III) or Sb(V) within 60 minutes and 120 minutes, respectively, and then Sb( The adsorption of Sb(III) or Sb(V) did not change much with time, indicating that the porous iron-manganese composites could rapidly remove Sb(III) or Sb(V), and the equilibrium adsorption amounts were 99.5 and 62.1 mg, respectively. ·g -1 .
实施例Example
55
为了探究制备的用于高效固定去除锑污染的多孔铁锰复合材料在处理含重金属锑污染的废水效果与废水锑浓度之间的关系。以下采用Sb(III)溶液和Sb(V)溶液作为模拟废水进行测试。In order to explore the relationship between the effect of the prepared porous iron-manganese composites for high-efficiency immobilization and removal of antimony pollution in the treatment of wastewater containing heavy metal antimony pollution and the concentration of antimony in wastewater. The following uses Sb(III) solution and Sb(V) solution as simulated wastewater for testing.
该测试,包括:This test includes:
准确称取多份0.005g多孔铁锰复合材料分别置于50ml离心管中,分别向离心管中移取25mL不同初始浓度的Sb(III) 溶液或Sb(V)溶液(初始浓度设置为50 mg L
-1,100 mg L
-1,
150 mg L
-1, 200 mg L
-1, 300 mg L
-1, 400 mg L
-1,500 mg L
-1),充分混合均匀后置于30 ± 1℃水浴振荡器上震荡24 h后,取上清液过0.45μm滤膜,原子吸收分光光度计测定溶液中Sb(III) 或Sb(V)的浓度。测试结果如图6a和图6b所示。图6 a为所述用于高效固定去除锑污染的多孔铁锰复合材料对Sb(III) 的等温吸附曲线图;图6 b为所述用于高效固定去除锑污染的多孔铁锰复合材料对Sb(V) 的等温吸附曲线图。
Accurately weigh multiple 0.005g porous iron-manganese composite materials and place them in 50ml centrifuge tubes, respectively, and pipette 25mL of Sb(III) solutions or Sb(V) solutions with different initial concentrations into the centrifuge tubes (the initial concentration is set to 50 mg). L -1 , 100 mg L -1 , 150 mg L -1 , 200 mg L -1 , 300 mg L -1 , 400 mg L -1 , 500 mg L -1 ), mix well and place at 30 ± 1 After shaking on a water bath shaker for 24 h, the supernatant was taken through a 0.45 μm filter, and the concentration of Sb(III) or Sb(V) in the solution was measured by atomic absorption spectrophotometer. The test results are shown in Figure 6a and Figure 6b. Figure 6a shows the isotherm adsorption curve of Sb(III) by the porous iron-manganese composite material for high-efficiency immobilization and removal of antimony contamination; Plot of the adsorption isotherm for Sb(V).
从图6a和图6b中可以看出,所述用于高效固定去除锑污染的多孔铁锰复合材料对Sb(III)
或Sb(V)的最大吸附量分别为278.3和185.7 mg·g
-1,说明了该多孔铁锰复合材料材对Sb(III) 或Sb(V)的高效吸附性。
It can be seen from Fig. 6a and Fig. 6b that the maximum adsorption capacity of Sb(III) or Sb(V) by the porous iron-manganese composite for high-efficiency immobilization and removal of antimony pollution is 278.3 and 185.7 mg·g -1 , respectively , indicating the high-efficiency adsorption of Sb(III) or Sb(V) by the porous iron-manganese composite material.
以上实施例仅为本发明较优的实施方式,仅用于解释本发明,而非限制本发明,本领域技术人员在未脱离本发明精神实质下所作的改变、替换、修饰等均应属于本发明的保护范围。The above examples are only preferred embodiments of the present invention, and are only used to explain the present invention, but not to limit the present invention. Changes, substitutions, modifications, etc. made by those skilled in the art without departing from the spirit of the present invention shall belong to the present invention. the scope of protection of the invention.
Claims (10)
- 一种用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,其特征在于,包括如下步骤:A preparation method of a porous iron-manganese composite material for efficiently fixing and removing antimony pollution is characterized in that, comprising the following steps:(1)将高锰酸盐、锰盐及铁盐分别配制成高锰酸盐溶液、锰盐溶液及铁盐溶液;(1) Prepare permanganate, manganese and iron salts into permanganate solution, manganese salt solution and iron salt solution respectively;(2)将步骤(1)所述高锰酸盐溶液滴加至锰盐溶液中,搅拌处理,得到悬浮液;(2) dropping the permanganate solution described in step (1) into the manganese salt solution, and stirring to obtain a suspension;(3)将铁盐溶液加入步骤(2)所述悬浮液中,搅拌处理,得到混合液;(3) adding the iron salt solution to the suspension described in step (2), and stirring to obtain a mixed solution;(4)调节步骤(3)所述混合液的pH值为6.5-8.5,然后进行陈化处理,离心取沉淀,洗涤,干燥,研磨,过筛,得到所述用于高效固定去除锑污染的多孔铁锰复合材料。(4) Adjusting the pH value of the mixed solution in step (3) to 6.5-8.5, and then performing aging treatment, centrifuging to obtain the precipitate, washing, drying, grinding, and sieving, to obtain the described solution for high-efficiency immobilization and removal of antimony pollution. Porous ferromanganese composites.
- 根据权利要求1所述的用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,其特征在于,步骤(1)所述高锰酸盐为高锰酸钾、高锰酸钠中的一种以上;所述锰盐为氯化锰、硝酸锰及硫酸锰中的一种以上;所述铁盐为硝酸铁、硫酸铁及氯化铁中一种以上;所述高锰酸盐、锰盐及铁盐的摩尔比为(1.5-9):(1-6):(2.5-15)。The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the permanganate in step (1) is potassium permanganate and sodium permanganate. more than one; the manganese salt is more than one of manganese chloride, manganese nitrate and manganese sulfate; the iron salt is more than one of ferric nitrate, ferric sulfate and ferric chloride; the permanganate, The molar ratio of manganese salt and iron salt is (1.5-9):(1-6):(2.5-15).
- 根据权利要求2所述的用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,其特征在于,所述高锰酸盐、锰盐及铁盐的摩尔比为(3-6):(2-4):(5-10)。The preparation method of the porous iron-manganese composite material for efficiently fixing and removing antimony pollution according to claim 2, wherein the molar ratio of the permanganate, manganese salt and iron salt is (3-6): (2-4): (5-10).
- 根据权利要求1所述的用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,其特征在于,步骤(1)所述高锰酸盐溶液的浓度为0.015 mol/L-0.090 mol/L;所述锰盐溶液的浓度为0.010 mol/L-0.060 mol/L;所述铁盐溶液的浓度为0.025 mol/L-0.150 mol/L。The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the concentration of the permanganate solution in step (1) is 0.015 mol/L-0.090 mol/L; the concentration of the manganese salt solution is 0.010 mol/L-0.060 mol/L; the concentration of the iron salt solution is 0.025 mol/L-0.150 mol/L.
- 根据权利要求1所述的用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,其特征在于,步骤(2)所述高锰酸盐溶液滴加至锰盐溶液中的滴加速率为0.1-5 mL/min;所述搅拌处理的时间为1-3h。The method for preparing a porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution according to claim 1, characterized in that, in step (2), the rate of dropping of the permanganate solution into the manganese salt solution dropwise is 0.1-5 mL/min; the stirring treatment time is 1-3h.
- 根据权利要求1所述的用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,其特征在于,步骤(3)所述铁盐溶液加入悬浮液中的速率为5-10ml/min,所述搅拌处理的时间为1-3h。The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the rate at which the iron salt solution is added to the suspension in step (3) is 5-10ml/min, The time of the stirring treatment is 1-3h.
- 根据权利要求1所述的用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,其特征在于,步骤(4)所述陈化处理的时间为6-18h。The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the aging treatment time in step (4) is 6-18 hours.
- 根据权利要求1所述的用于高效固定去除锑污染的多孔铁锰复合材料的制备方法,其特征在于,步骤(4)所述离心的速率为2000-6000rpm,离心的时间为10-20min;所述干燥的温度为40-80℃,干燥的时间为18-36h;所述过筛的筛孔大小为100-500目。The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the centrifugation rate in step (4) is 2000-6000rpm, and the centrifugation time is 10-20min; The drying temperature is 40-80° C., and the drying time is 18-36 h; the mesh size of the sieving is 100-500 mesh.
- 一种由权利要求1-8任一项所述的制备方法制得的用于高效固定去除锑污染的多孔铁锰复合材料。A porous iron-manganese composite material prepared by the preparation method according to any one of claims 1 to 8 and used for high-efficiency fixation and removal of antimony pollution.
- 权利要求9所述的用于高效固定去除锑污染的多孔铁锰复合材料在处理含重金属锑污染中的应用。Application of the porous iron-manganese composite material for efficiently fixing and removing antimony pollution according to claim 9 in the treatment of heavy metal antimony pollution.
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