CN113149125A - Method for removing antimony pollutants in water - Google Patents
Method for removing antimony pollutants in water Download PDFInfo
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- CN113149125A CN113149125A CN202110413581.1A CN202110413581A CN113149125A CN 113149125 A CN113149125 A CN 113149125A CN 202110413581 A CN202110413581 A CN 202110413581A CN 113149125 A CN113149125 A CN 113149125A
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 79
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 18
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 18
- 239000002689 soil Substances 0.000 claims abstract description 233
- 239000011521 glass Substances 0.000 claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 31
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011324 bead Substances 0.000 claims abstract description 26
- 239000006004 Quartz sand Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 14
- 239000004677 Nylon Substances 0.000 claims abstract description 10
- 229920001778 nylon Polymers 0.000 claims abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 102
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 32
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- 239000011591 potassium Substances 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- UCXOJWUKTTTYFB-UHFFFAOYSA-N antimony;heptahydrate Chemical compound O.O.O.O.O.O.O.[Sb].[Sb] UCXOJWUKTTTYFB-UHFFFAOYSA-N 0.000 claims description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
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- 238000005303 weighing Methods 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 3
- 210000004209 hair Anatomy 0.000 claims description 3
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- 239000011365 complex material Substances 0.000 abstract description 2
- 101100425816 Dictyostelium discoideum top2mt gene Proteins 0.000 abstract 1
- 101150082896 topA gene Proteins 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 description 46
- 230000035515 penetration Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 18
- 238000000926 separation method Methods 0.000 description 12
- 239000000284 extract Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 5
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 5
- 229920001661 Chitosan Polymers 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910001710 laterite Inorganic materials 0.000 description 4
- 239000011504 laterite Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229950005228 bromoform Drugs 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- AZTSDLGKGCQZQJ-UHFFFAOYSA-N antimony;hydrate Chemical compound O.[Sb] AZTSDLGKGCQZQJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
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- 238000000635 electron micrograph Methods 0.000 description 1
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- 210000003128 head Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01J20/06—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
-
- 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
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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)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for removing antimony pollutants in water, belongs to the technical field of water treatment, and particularly relates to the technical field of removal of antimony pollutants in water, aiming at solving the defects of complex materials and high cost in the prior art, comprising the following steps of: extracting metal oxides from soil; the system comprises a liquid supply bottle, a peristaltic pump and an adsorption device, wherein the peristaltic pump is communicated with the liquid supply bottle, the adsorption device is communicated with the peristaltic pump, the adsorption device comprises a small organic glass column with a scratch on the inner wall, the small column sequentially comprises a nylon net, a first glass bead layer, a first quartz sand layer, filter paper, a metal oxide layer in soil, a second quartz sand layer and a second glass bead from bottom to topA layer; the liquid inlet speed in the small column is controlled by a peristaltic pump, and the flow rate is 20ml H‑1. The red soil with good adsorption effect is selected as a raw material, and the high-concentration antimony-containing sewage can be treated to reach three standards of national underground water.
Description
Technical Field
The invention discloses a method for removing antimony pollutants in water, belongs to the technical field of water treatment, and particularly relates to the technical field of removal of antimony pollutants in water.
Background
Antimony is a toxic carcinogenic element and also a global pollutant with long-distance transmission characteristics (He et al, 2019; Sun et al, 2017). Most of the antimony released into the environment is concentrated and transported in the ecosystem and accumulates in the human body through the food chain, eventually affecting the metabolism of proteins and sugars, damaging the liver, heart, respiration and nervous system (Wang et al 2015). China is the largest antimony ore resource reserve and production country in the world, the antimony yield in 2019 accounts for about 62.5% of the total world amount, and the environmental pollution and ecological damage of antimony in mining areas caused by antimony ore mining and smelting are prominent (U.S. geographic Survey, 2020; Fei et al, 2017; Okkenhaug et al, 2016), and in provinces such as Hunan, Yunnan, Guizhou, Guangxi (Fei et al, 2017), the content of antimony in soil, underground water and plants around the mining areas is quite high (Okkenhaug et al, 2012), so that the antimony is potentially harmful to the health of surrounding residents. Antimony consumption has increased dramatically with the development of modern industry, and antimony contamination has attracted a high degree of international scientific interest (Hu et al, 2014). The european community and the united states environmental protection agency (USEPA,1979) have prioritized antimony as a priority contaminant early in 1976 and 1979, respectively (McCallum et al, 2005).
Application No.: 201710299890.4 discloses a method for preparing chitosan/cellulose acetate/iron composite adsorbent for removing antimony, which is compounded by chitosan, cellulose acetate and iron oxide, wherein the adsorbent is prepared by preparing a porous cellulose acetate skeleton, taking rich functional groups of chitosan as functional groups and taking iron oxide as active components of the adsorbent, thereby overcoming the defects of large head loss, difficult separation, poor chitosan stability, small specific surface area and the like when the iron oxide is directly adsorbed.
Application No.: 201910756385.7 discloses a method for removing antimony in wastewater, which takes primary ecological secondary iron oxide as adsorbent to remove antimony; the primary ecological secondary iron oxide is iron oxide generated in acid wastewater of a coal mine, is in a yellow brown granular shape, has a pore structure inside, mainly comprises Fe, S, 0 and H, is an iron sulfate secondary mineral, is non-toxic and harmless, can avoid the problem of secondary pollution caused by an adsorbent, has the adsorption quantity of 219.78mg/g for Sb (III) and 366.30mg/g for Sb (V), can effectively remove antimony ions in the wastewater, has low cost, changes waste into valuables, accords with the environmental protection strategy of treating waste with waste, and has important social and economic meanings.
The iron oxide of the patent is artificially synthesized or extracted from industrial products, namely coal mine acid wastewater, but the iron oxide material is complex to obtain and high in cost.
Disclosure of Invention
The invention aims to: provides a method for removing antimony pollution in water, which aims to solve the defects of complex materials and high cost.
The technical scheme adopted by the invention is as follows:
a method for removing antimony pollutants in water comprises the following steps:
In the technical scheme of the application, the metal oxide layer in the soil is an extract of red soil, moist soil, black soil or sandy soil, the inner wall of a small soil column is scraped to prevent the generation of a wall flow phenomenon, the extract of the red soil, the moist soil, the black soil or the sandy soil is ground to pass through a 2mm sieve, and the soil of the iron oxide layer in the soil is 1.19gcm red soil according to the actual dry volume weight-3Moisture soil 1.17gcm-31.20gcm of black soil-3Sand soil 1.43gcm-31.43gcm of quartz sand-3The small soil columns are filled in layers, before an experiment, a nylon net is firstly laid at the bottom of each small soil column to ensure the stability of each small soil column, a first glass bead layer and a first quartz sand layer are sequentially arranged on the nylon net, a layer of filter paper is laid later to prevent the soil from being washed away, then the soil with 2mm sieve is levigated by extracts of red soil, moist soil, black soil or sandy soil, the liquid inlet speed is controlled by a peristaltic pump, and the flow rate is controlled to be 20ml H-1The experiment was ended until the antimony concentration in the test leach solution was close to the background value (1 ppb). By extracting metal oxides from representative soils in several countries, filling the metal oxides serving as adsorption substances into small soil columns for adsorption verification of pollutants, selecting red soil with good adsorption effect as a raw material, and treating high-concentration antimony-containing sewage to meet the three national underground water standards of underground water quality (GB/T14848) -2017.
In the application, the moisture soil is collected from Beijing Changping test station of Chinese academy of agricultural sciences; the black soil is collected from a Helen agricultural ecological test station of Chinese academy of sciences; the red soil is collected from a Hunan Qiyang red soil test station of Chinese agricultural academy of sciences; the sandy soil is collected from Guangyong villages and villages in Beijing City.
Further, the soil in the step 1 comprises moist soil, black soil, red soil or sandy soil.
Further, the metal oxides in the metal oxide layer in the soil include iron oxide, aluminum oxide and manganese oxide.
Furthermore, the method for extracting the iron oxide, the aluminum oxide and the manganese oxide in the soil comprises the following steps of accurately weighing 1g of soil, putting the soil into a 50mL plastic centrifuge tube, and then adding 20mL of CHBr3Rho is 2.88g cm-3Placing the centrifugal tube on a constant temperature shaking table at 25 ℃, shaking for 1 hour, centrifuging the sample in a centrifuge for 5min at 3000rpm, taking out the substances separated from the lower part of the centrifugal tube, and air-drying to volatilize CHBr3The latter are iron oxide, aluminum oxide and manganese oxide in the soil.
Further, the content of iron oxide in the extracted moisture soil was 16.3%, the content of iron oxide in the black soil was 9.94%, the content of iron oxide in the red soil was 6.83%, and the content of iron oxide in the sand soil was 4.14% (before separation, the content of iron oxide in the moisture soil was 2.86%, the content of iron oxide in the black soil was 3.59%, the content of iron oxide in the red soil was 4.70%, and the content of iron oxide in the sand soil was 1.73%).
Furthermore, the height of the small soil column is 25cm, the inner diameter is 5cm, the thickness of the nylon net is 0.1mm, the thickness of the first quartz sand layer and the thickness of the second quartz sand layer are 2cm, the thickness of the first glass bead layer and the thickness of the second glass bead layer are 3cm, and the size of each glass bead in the first glass bead layer and the second glass bead layer is 3 mm.
Further, the feed liquor in the step 3 is 10mg L-1Potassium pyroantimonate or 100mg L pyroantimonate-1Potassium pyroantimonate.
The moisture soil, the black soil, the red soil and the sandy soil are domestic relatively common soil, and the application uses the moisture soil, the black soil, the red soil and the sandy soil as alternative objects of materials, obtains ideal soil through comparing the experimental effect after separating four kinds of soil, thereby separates and fills as main adsorption material in the small soil column.
Extracting metal oxides from the soil, wherein the metal oxides comprise iron oxides, aluminum oxides and manganese oxides.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in the invention, metal oxides are extracted from representative soils throughout the country and are used as adsorption substances to be filled into small soil columns for adsorption verification of pollutants, red soil with good adsorption effect is selected as a raw material, and high-concentration antimony-containing sewage can be treated to meet the three standards of national underground water standard underground water quality standard (GB/T14848-2017); the single metal oxide such as iron oxide is not as good as manganese oxide in capacity after adsorbing antimony, but the obtained cost is low compared with manganese oxide, and the single manganese oxide is expensive in cost compared with iron oxide and is not easy to obtain.
2. According to the invention, laterite is used as a raw material, and the extracted metal oxide is used as a main filler of an adsorption device, so that the adsorption device has very strong capacity of adsorbing antimony pollutants in an aqueous solution, and can be used as a simple removal device for antimony pollutants, and under the condition that the pollutants in water are 100000ppb, the device can purify the water to ensure that the concentration of antimony in the water is below 5pp, so that the quality standards of three types of underground water are met;
3. in the invention, the iron oxide is directly extracted from the soil, and simultaneously contains other metal oxides, the other metal oxides comprise aluminum oxide and manganese oxide, the cost is low, the operation is simple, and the adsorbing material is easy to obtain.
Drawings
FIG. 1 is a schematic diagram of the structure of the system for adsorbing antimony according to the present invention;
FIG. 2 is the iron oxide content of the soil before and after separation according to the invention;
FIG. 3 is the content of aluminum oxide in the soil before and after the separation according to the invention;
FIG. 4 is the content of oxides of manganese in the soil before and after separation according to the invention;
FIG. 5 shows 10mg L of the present invention-1Of solutions contaminated with antimony in different soils with adsorptionAdsorption effect;
FIG. 6 shows 100mg L of the present invention-1The adsorption effect of the antimony polluted solution in different adsorption soils;
FIG. 7 shows the results of X-ray diffraction analysis of a laterite extract according to the invention;
FIG. 8 is the results of X-ray diffraction analysis of a moisture soil extract of the present invention;
FIG. 9 shows the results of X-ray diffraction analysis of the black soil extract of the present invention;
FIG. 10 shows the results of X-ray diffraction analysis of the sand extract of the present invention;
FIG. 11 shows the results of X-ray diffraction analysis of laterite ores according to the present invention;
FIG. 12 shows the results of X-ray diffraction analysis of the original soil of the moisture soil of the present invention;
FIG. 13 shows the results of X-ray diffraction analysis of the original soil of black soil according to the present invention;
FIG. 14 shows the X-ray diffraction analysis results of the sandy original soil of the present invention;
FIG. 15 is an electron micrograph of the adsorption of antimony by different metal oxides according to the present invention.
The labels in the figure are: 1-liquid supply bottle, 2-peristaltic pump, 3-small earth pillar, 4-second glass bead layer, 5-second quartz sand layer, 6-iron oxide layer in soil, 7-filter paper, 8-first quartz sand layer, 9-first glass bead layer, 10-nylon net and 11-liquid containing tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
As shown in fig. 1, a method for removing antimony contaminants in water comprises the following steps:
The solution is drenched in the liquid containing tank.
Example 2
On the basis of example 1, the soil in step 1 comprises moist soil, black soil, red soil or sandy soil.
Example 3
On the basis of example 1, the metal oxides in the metal oxide layer in the soil include iron oxide, aluminum oxide and manganese oxide.
Example 4
Based on example 3, the method for extracting iron oxide, aluminum oxide and manganese oxide in soil in the steps comprises the following steps of accurately weighing 1g of soil, putting the soil into a 50mL plastic centrifuge tube, and adding 20mL of CHBr3Rho is 2.88g cm-3Placing the centrifugal tube on a constant temperature shaking bed at 25 ℃, shaking for 1 hour, centrifuging the sample in a centrifuge for 5min at 3000rpm, taking out the substance separated from the lower part of the centrifugal tube, and air-drying to volatilize CHBr3The latter are iron oxide, aluminum oxide and manganese oxide in the soil.
Example 5
Based on example 2, the content of iron oxide in the extracted moisture soil is 16.3%, the content of iron oxide in the black soil is 9.94%, the content of iron oxide in the red soil is 6.83%, and the content of iron oxide in the sandy soil is 4.14%.
Example 6
On the basis of the embodiment 1, the height of the small column is 25cm, the inner diameter is 5cm, the thickness of the nylon net is 0.1mm, the thickness of the first quartz sand layer and the second quartz sand layer is 2cm, the thickness of the first glass bead layer and the second glass bead layer is 3cm, and the size of each glass bead in the first glass bead layer and the second glass bead layer is 3 mm.
Example 7
Based on example 1, the feed solution in step 3 is 10mg L-1Potassium pyroantimonate or 100mg L pyroantimonate-1Potassium pyroantimonate.
Experimental example 1
Extraction of iron oxides from soil
The density of iron oxide present in the soil is between 3.60 and 5.18g cm-3However, the average density of several soils used in the experiments was between 2.57 and 2.79g cm-3In between, iron oxides in the soil may be removed by using bromoform (CHBr)3) The method comprises the following steps: accurately weighing 1g of soil, placing the soil into a 50mL plastic centrifuge tube, and then adding 20mL of CHBr3(ρ ═ 2.88g cm-3), the tube was placed on a constant temperature shaker at 25 ℃ and shaken for 1 hour, after which the sample was centrifuged in a centrifuge for 5min (3000 rpm). Taking out the separated substance from the lower part of the centrifuge tube, air drying to volatilize CHBr3The subsequent experiments were performed. HNO is adopted for measuring separated components Fe, Al and Mn3-HClO4HF digestion followed by determination by ICP-MS with a detection limit of 0.15 μ g L-1。。
The soil components separated using bromoform contain a relatively high content of iron. The iron oxide content before the four soils were not separated was: 4.70% of red soil, 2.86% of moisture soil, 3.59% of black soil and 1.73% of sandy soil, wherein the iron oxide content in the four kinds of soil after separation is as follows: 6.83% of red soil, 16.3% of moisture soil, 9.94% of black soil and 4.14% of sandy soil. The content of aluminum oxide before four soils were not separated was: 4.23% of red soil, 4.85% of moisture soil, 4.41% of black soil and 4.03% of sandy soil, wherein the content of aluminum oxide in the four kinds of separated soil is as follows: 4.39% of red soil, 4.51% of moisture soil, 4.23% of black soil and 3.84% of sandy soil. The content of manganese oxide before four soils were not separated was: 0.15% of red soil, 0.07% of moisture soil, 0.07% of black soil and 0.04% of sandy soil, wherein the contents of manganese oxides in the four kinds of soil after separation are as follows: 0.24% of red soil, 0.40% of moisture soil, 0.47% of black soil and 0.09% of sandy soil. Silica is the main mineral in the soil in the four raw soils, but no obvious crystalline iron oxides are found in the four soils; in the soil after separation, the existence of the crystalline iron oxide can be found in the moist soil and the sandy soil, and in the moist soil and the sandy soil, the soil after separation can adsorb more antimony than the original soil. The content of iron oxides in the soil after separation is shown in fig. 2, the content of aluminum oxides in the soil after separation is shown in fig. 3, and the content of oxides of total manganese in the soil after separation is shown in fig. 4.
As shown in fig. 7-14, the diffraction peaks in the original soil are less and smoother due to the lower content of crystalline metal oxide in the original soil, and after extraction, the diffraction peaks of the extracts of different soils are obviously increased, that is, the content of crystalline metal oxide which can be detected by an instrument is increased, and the peaks are steeper. Meanwhile, the curves of the fitted metal oxides are in different colors in the graph, and it can be seen that the fitted curve of the extracted soil is better than that of the original soil. That is to say the content of the given crystalline metal oxides in the soil is increased after extraction. In fig. 7-14, the diffraction spectrometer scans at an angle (2 θ).
Experimental example 2
10mg L-1Antimony penetration test: adding deionized water for 24 hr to stabilize the small column, adding 10mg L-1Inputting a potassium pyroantimonate (Sb (V)) standard solution into the soil column from the top end, finishing inputting antimony after inputting 1PV (pore volume), and inputting deionized water to wash the adsorbed soil instead. In the experimental process, the concentration of antimony in the solution is measured in each hour at the beginning, after the peak value is gradually reduced, the sampling interval is increased until the concentration of antimony in the experimental leaching solution is close to the background value, and the experiment is ended. 100mg L-1Antimony penetration test: the experimental procedure was the same as above, and the leaching solution was changed to 100mg L-1The potassium pyroantimonate (Sb (V)) solution shows no antimony detection in the leaching solution after leaching the red soil for 2 weeks.
At 10mg L-1The penetration curves of antimony in different soils differed significantly under the conditions of the potassium pyroantimonate solution (fig. 5). At 10mg L-1Migration speed of antimony in sandy soil under condition of potassium pyroantimonate solutionThe highest speed, no tailing phenomenon of desorption curve, and the highest peak value of 7mg L-1And the second peak in moisture is 2.8mg L-10.4mg L in black soil-1And no obvious penetration peak exists in red soil. The adsorption effect of antimony in the penetration process of sandy soil is weak. The penetration rate of antimony in other soils was: moisture soil>Black soil>And (4) red soil.
The penetration curve of antimony in moisture soil is similar to that of sandy soil, but the peak value is lower, and the tailing phenomenon is more obvious. The penetration curve of antimony in black soil has a large difference with other kinds of soil, no obvious penetration peak value exists, the peak value is relatively smooth, and the tailing phenomenon is more obvious. In the red soil, no obvious penetration exists, which indicates that the adsorption capacity of the red soil is strongest, and the input antimony is almost adsorbed by the red soil and cannot penetrate through the soil column.
At 10mg L-1The penetration curves of antimony in different soils differed significantly under the conditions of the potassium pyroantimonate solution (fig. 5). At 10mg L-1The antimony in the sand has the fastest migration speed under the condition of the potassium pyroantimonate solution, the desorption curve does not have trailing phenomenon, and the highest peak value can reach 7mg L-1And the second peak in moisture is 2.8mg L-10.4mg L in black soil-1And no obvious penetration peak exists in red soil. The adsorption effect of antimony in the penetration process of sandy soil is weak. The removal rate of antimony after passing through the red soil extract is more than 99%.
The penetration curve of antimony in moisture soil is similar to that of sandy soil, but the peak value is lower, and the tailing phenomenon is more obvious. The penetration curve of antimony in black soil has a large difference with other kinds of soil, no obvious penetration peak value exists, the peak value is relatively smooth, and the tailing phenomenon is more obvious. In red soil, the red soil is not penetrated obviously, which indicates that the adsorption capacity of the red soil is strongest, the input antimony is almost adsorbed by the red soil, the soil column can not be penetrated, and a device made of a red soil extract can well adsorb antimony polluted solution and can reach the national standard (the third-level standard of underground water).
At 100mg L-1Under the condition of potassium pyroantimonate solution, the penetration curve of antimony in black soil and red soil is 10mg L-1Pyro-stibiumThe conditions of potassium solution are clearly different. As shown in FIG. 6, in sandy soil and moist soil, 100mg L-1Shape of antimony penetration curve under condition of potassium pyroantimonate solution and 10mg L-1The conditions for potassium pyroantimonate solutions are similar. The penetration rate of antimony in four soils was: sand soil>Moisture soil>Black soil>The red soil has the fastest migration speed in sandy soil, the sandy soil has weaker adsorption effect on antimony, and the desorption curve does not have trailing phenomenon. The penetration curve of antimony in moisture soil is similar to that of sandy soil, but the peak value is lower, and the tailing phenomenon is more obvious. The penetration curve of antimony in black soil has a large difference with other soils, and has an obvious penetration peak value, but the peak value rises slowly, the tailing phenomenon is more obvious, and the penetration curve is not smooth in the analysis process. In red soil, if 100mg L of 1PV is input-1Under the condition of antimony, the antimony does not penetrate obviously, which indicates that the adsorption capacity of the red soil is strongest, the input antimony is almost adsorbed by the red soil, the earth pillar is not penetrated, and the adsorption rate is more than 99%.
It can be seen that after laterite is used as a raw material and the extracted iron oxide is used as a main filler of the device, the device has very strong capacity of adsorbing antimony pollutants in an aqueous solution, and can be used as a simple device for removing the antimony pollutants, and under the condition that the pollutants in water are 100000ppb, the device can purify the water to ensure that the concentration of the antimony in the water is below 5pp, so that the water reaches the quality standards of three types of underground water.
As shown in fig. 8, which is a transmission electron microscope observation picture after the soil adsorbs antimony, positions 2 and 3 in the picture are marked, the main component is a complex of iron oxide, aluminum oxide and manganese oxide, and a large amount of antimony is adsorbed, and the main element content is as follows: o: 59.85%, Al: 14.27, Si: 15.29, K: 2.08, Fe: 6.12, Sb: 2.39.
according to the research of Xuguang eyebrow of Hunan university (research of removing antimony and phosphorus by adsorbing quartz sand loaded with Iron Oxide (IOCS), the Hunan university 2006), under the condition of similar pure iron oxide content (1% -5%), after the experimental result similar to the principle of the invention is obtained, after 33ppm (10000 ppm in the invention) of antimony water is input, and after 8-63 hours, the effluent concentration exceeds 1.5ppm (500 hours in the invention is less than 0.005ppm), the antimony removing effect of the invention is far better than that of a single pure iron oxide.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A method for removing antimony pollutants in water is characterized by comprising the following steps:
step 1, extracting metal oxides in soil;
step 2, filling the extracted metal oxide in the soil as one of fillers into a system for adsorbing antimony, wherein the system comprises a liquid supply bottle, a peristaltic pump communicated with the liquid supply bottle and an adsorption device communicated with the peristaltic pump, the adsorption device comprises a small organic glass column with a hair on the inner wall, and the small organic glass column sequentially comprises a nylon net, a first glass bead layer, a first quartz sand layer, filter paper, a metal oxide layer in the soil, a second quartz sand layer and a second glass bead layer from bottom to top;
step 3, adsorption test, wherein the liquid inlet speed in the small soil column is controlled by a peristaltic pump, and the flow rate is 20ml H-1。
2. The method of claim 1, wherein the soil in step 1 comprises moist soil, black soil, red soil or sandy soil.
3. The method of claim 1, wherein the metal oxide in the metal oxide layer of the soil comprises iron oxide, aluminum oxide and manganese oxide.
4. The method for removing antimony contaminants in water as claimed in claim 3, wherein the method for extracting iron oxide, aluminum oxide and manganese oxide in soil comprises the steps of accurately weighing 1g of soil, putting the soil into a 50mL plastic centrifuge tube, and adding 20mL of CHBr3Rho is 2.88g cm-3Placing the centrifugal tube on a constant temperature shaking bed at 25 ℃, shaking for 1 hour, centrifuging the sample in a centrifuge for 5min at 3000rpm, taking out the substance separated from the lower part of the centrifugal tube, and air-drying to volatilize CHBr3The latter are iron oxide, aluminum oxide and manganese oxide in the soil.
5. The method as claimed in claim 2, wherein the content of iron oxide in the extracted moisture soil is 16.3%, the content of iron oxide in the black soil is 9.94%, the content of iron oxide in the red soil is 6.83%, and the content of iron oxide in the sandy soil is 4.14%.
6. The method as claimed in claim 1, wherein the height of the small column is 25cm, the inner diameter is 5cm, the thickness of the nylon net is 0.1mm, the thickness of the first quartz sand layer and the second quartz sand layer is 2cm, the thickness of the first glass bead layer and the second glass bead layer is 3cm, and the size of each glass bead in the first glass bead layer and the second glass bead layer is 3 mm.
7. The method for removing antimony pollutants in water as claimed in claim 1, wherein the feed liquid in the step 3 is 10mg L-1Potassium pyroantimonate or 100mg L pyroantimonate-1Potassium pyroantimonate.
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