CN112221469A - Adsorbing material for removing nitrate in water and preparation method thereof - Google Patents
Adsorbing material for removing nitrate in water and preparation method thereof Download PDFInfo
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- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 83
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 61
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000001291 vacuum drying Methods 0.000 claims abstract description 19
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 34
- 239000011777 magnesium Substances 0.000 description 34
- 238000001179 sorption measurement Methods 0.000 description 27
- 239000003463 adsorbent Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000002798 spectrophotometry method Methods 0.000 description 7
- -1 methemoglobinemia Chemical compound 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 231100000234 hepatic damage Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 230000008818 liver damage Effects 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 208000005135 methemoglobinemia Diseases 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention provides an adsorbing material for removing nitrate in water and a preparation method thereof, (1) weighing two metal precursors to prepare a mixed solution; (2) adding a porous carbon material into the mixed solution, and stirring to form a dispersion system; (3) adjusting the pH value of the mixture to 10 by using alkali liquor; (4) periodically stirring by using a magnetic stirrer, standing at room temperature for 24h, and drying the obtained composite material in a constant-temperature vacuum drying oven at 80-100 ℃ for 10-12 h; (5) naturally cooling to room temperature and grinding; (6) placing into an aluminum porcelain boat, and roasting for 1-2h in a tubular furnace under the condition of nitrogen; (7) washing and dehydrating by using deionized water after roasting; (8) drying for 10-12 hours at 70-80 ℃ by using a vacuum drying oven. The structure of the carbon-extracted base material can be used as a matrix for supporting LDH, and the LDH can ensure the excellent ion exchange capacity of the composite material; the preparation method is simple, the nitrate nitrogen removal effect is good, and the removal rate is less influenced by the pH value of the receptor system and the initial concentration of the nitrate.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to an adsorption material for removing nitrates from water and a preparation method thereof.
Background
With the development of socio-economic, excess nitrate in water has become a serious environmental concern worldwide. Nitrate pollution mainly comes from agricultural runoff, animal manure, septic tank systems, industrial discharge and the like. Excess nitrate in water poses a serious threat to human health and water environmental safety. The excessive nitrate discharged into the water body can cause eutrophication of the water body, or the nitrate can cause serious threats to human health when being reduced into nitrite, such as methemoglobinemia, cancer and liver damage. The maximum pollution level of drinking water regulated by the United states Environmental Protection Agency (EPA) is 10mg/L NO3 -N, and the maximum pollution level of the World Health Organization (WHO) drinking water is 50mg/L NO3 --N. In order to prevent the pollution of nitrate, the nitrate-containing wastewater is effectively treated by adopting a proper process before being discharged into a water body. However, in most municipal wastewater treatment plants, conventional biological treatment techniques are used to treat NO due to lack of carbon source or improper operation3 -The removal of-N is generally poor. Therefore, to reduce the total nitrogen level discharged from a sewage treatment plant, effective techniques must be employed to remove nitrate from the water.
There are many techniques for removing nitrate from water, such as using zero-valent iron and zero-valent magnesium, reverse osmosis, ion exchange, electrodialysis, catalytic denitrification, biological denitrification, etc. However, these conventional treatment techniques have inherent drawbacks that make them difficult to popularize on a large scale in the field of wastewater treatment. For example, the zero-valent iron reduction process can generate ammonium salt and change the initial pH of the water body; the biological denitrification process is difficult to be applied to inorganic wastewater, and extra organic matters are required to be added as electron donors; high salt content NO produced by ion exchange, reverse osmosis and electrodialysis techniques3 -Concentrated solution, and the process is complex and has high cost. The adsorption technology has excellent performance and simple operationThe advantages of simple structure, low cost, small occupied area and the like are considered as an effective water treatment technology. The adsorption technology can remove or reduce different types of organic and inorganic pollutants in the water body, and the adsorption process can simultaneously remove various different types of inorganic anions, such as fluoride, nitrate, bromate, perchlorate and the like.
The activated carbon adsorption process is considered to be the most economical and feasible selection for the advanced treatment of the municipal sewage due to the characteristics of strong adaptability, flexible operation, no by-products and the like. The activated carbon adsorption technology can obviously improve the effluent quality of sewage plants, such as can obviously reduce BOD, COD, SS, chromaticity and discharge of a plurality of environment sensitive micro-pollutants. However, due to the limitations of the characteristics and processes of the traditional activated carbon materials, the removal efficiency of the existing activated carbon adsorption technology on total nitrogen, especially nitrate nitrogen, is not high, which has become an important factor influencing the further popularization of the activated carbon adsorption technology in the field of advanced wastewater treatment. Therefore, the development of the activated carbon material with high adsorption capacity on nitrate nitrogen, low cost and stable source has important significance on the popularization of the activated carbon adsorption technology in the field of sewage advanced treatment and the improvement of regional water environment.
The carbon-based adsorbent can enhance the adsorption of the carbon-based adsorbent to nitrate by surface modification, and the main techniques of the surface modification are as follows: protonation, metal and metal oxide impregnation, amine grafting, organic modification and the like. These modifications can alter the surface area and pore volume and surface chemical properties of activated carbon by introducing new surface functional groups, thereby altering its adsorption capacity for nitrate, and studies have found that surface chemistry, rather than structural properties, appear to play a key role in nitrate uptake. However, several common modification methods have certain disadvantages, such as low adsorption selectivity of metal and metal oxide modified adsorbents on nitrates and low removal rate; the surfactant and amine graft modification can have the problem of modifier dissolution. The preparation of carbon-based adsorbents with high selectivity to nitrates by surface modification methods is not an effective method.
Disclosure of Invention
The invention provides an adsorption material for removing nitrate in water and a preparation method thereof, which are used for preparing an LDH porous carbon composite material with a selective removal effect on nitrate, improving the removal efficiency on nitrate and reducing the cost.
The specific technical scheme is as follows:
an adsorbing material for removing nitrate in water is prepared by the following preparation method, and the preparation method comprises the following steps:
(1) weighing two metal precursors in a certain target proportion to prepare a mixed solution;
(2) adding a porous carbon material into the mixed solution obtained in the step (1) and stirring to form a dispersion system of two metals with a certain molar ratio;
(3) adjusting the pH value of the mixture to 10 by using alkali liquor;
(4) periodically stirring the mixture obtained in the step (3) by using a magnetic stirrer, standing for 24 hours at room temperature, and drying the obtained composite material in a constant-temperature vacuum drying oven at 80-100 ℃ for 10-12 hours;
(5) naturally cooling to room temperature and grinding;
(6) placing into an aluminum porcelain boat, and roasting for 1-2h in a tubular furnace under the condition of nitrogen;
(7) washing and dehydrating by using deionized water after roasting;
(8) drying for 10-12 hours at 70-80 ℃ by using a vacuum drying oven to obtain the adsorbing material.
The two metal precursors in the step (1) are as follows: MgCl2、AlCl3. The molar ratio of the two metals is 1:1, 1:2, 1:3, 2:1 and 3: 1.
The basic parameters of the porous carbon material in the step (2) are as follows: the bulk density is 0.5-0.55g/ml, the water content is less than 5%, the ash content is 7-10%, and the iodine value is 900-950 mg/g.
The alkali liquor in the step (3) is NaOH solution with the molar concentration of 0.5 mol/L.
And (4) drying the composite material in the step (4) at 80 ℃ for 12 h.
And (5) roasting for 1.5h in the step (6).
And (3) drying in a vacuum drying oven for 12 hours at the drying condition of 75 ℃.
Table 1: adsorbent specific surface area and pore diameter
Compared with the prior art, the adsorbing material for removing nitrate in water and the preparation method thereof have the advantages that the structure of the carbon-based material can be used as a matrix for supporting LDH, and the LDH can ensure excellent ion exchange capacity of the composite material. The composite material is prepared by co-compounding an LDH material and porous carbon, so that the surface area of the composite material can be greatly enhanced, the mechanical strength, the chemical strength and the hydrophilicity are improved, and a macroporous structure is provided, so that more favorable active point positions for adsorbing nitrate in wastewater are generated.
The preparation method is simple, has good effect of removing nitrate nitrogen, and has small influence on the removal rate by the pH value of a receptor system and the initial concentration of nitrate. When the pH is 7 and the nitrate concentration is 20mg/l, the removal rate of the composite material for nitrate can reach 90.2%, while the carbon material adsorbent disclosed in patent CN105664874 only shows a certain adsorption effect under acidic conditions (pH 3), and has a poor adsorption effect for low-concentration nitrate, and the removal rate for 20mg/l nitrate is only 14.4%.
When the composite material prepared by the invention is used for removing nitrate in water, the adsorption capacity is high, and the composite material can be regenerated and recycled.
Drawings
FIG. 1(a) is a topography (SEM) of a porous carbon material;
FIG. 1(b) is a morphology (SEM) of the composite AC-Mg/Al-LDH prepared in example 2;
FIG. 2(a) is an elemental distribution diagram (EDS) of magnesium and aluminum in a porous carbon material;
FIG. 2(b) is an element distribution diagram (EDS) of magnesium and aluminum in the composite material AC-Mg/Al-LDH prepared in example 3;
FIG. 3 is an XRD pattern of a porous carbon material and the composite material AC-Mg/Al-LDH prepared in example 3;
FIG. 4 is a FT-IR plot of porous carbon material and composite material AC-Mg/Al-LDH prepared in example 3;
FIG. 5 is a graph of the effect of pH on the removal of nitrate nitrogen from water by a composite material;
FIG. 6 is a graph showing the effect of the amount of the added composite material on the removal of nitrate nitrogen from water;
FIG. 7 is a graph of the effect of initial nitrate nitrogen concentration on the efficiency of the composite material in removing nitrate nitrogen;
FIG. 8(a) is the adsorption isotherm of the composite material for nitrate in water;
FIG. 8(b) is a Langmuir adsorption curve;
FIG. 8(c) is a Freundlich adsorption curve.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
Example 1:
a composite material for removing nitrate in water is prepared by the following steps:
preparing 0.2mol/l MgCl2And 0.2mol/l AlCl3300ml of the mixed solution, 3.0g of activated carbon was weighed by an analytical balance and added to the mixed solution, and stirred for 2 hours by a magnetic stirrer to form a dispersion system in which the molar ratio of magnesium ions to aluminum ions was 1: 1. Adjusting the pH value of the mixture to 10 (+ -0.3) by using 0.5mol/l NaOH, stirring the mixed solution for 4 hours by using a magnetic stirrer, standing for 24 hours at room temperature, drying the obtained Mg/Al composite material in a constant-temperature vacuum drying oven at 80 ℃, placing the Mg/Al composite material into an aluminum ceramic boat after grinding, heating for 1 hour at 600 ℃ under the condition of nitrogen in a tube furnace, washing the final product by using deionized water, and drying at 80 ℃ by using the vacuum drying oven to obtain the AC-Mg/Al-LDH.
0.125g of the adsorbent was weighed into a 100ml conical flask with a stopper, and 50ml of NaNO with a concentration of 20mg/l was added to the flask3The solution is shaken for 10h under the conditions of the temperature of 25 ℃ and the rotating speed of 120r/min, filtered by a needle type filter head with the diameter of 0.45 mu m, and the concentration of nitrate in the water phase is detected by using a spectrophotometry, and the removal rate of the nitrate is calculated to be 56%.
Example 2:
a preparation method of a composite material for removing nitrate in water comprises the following steps:
preparing 0.4mol/l MgCl2And 0.2mol/l AlCl3300ml of the mixed solution, 3.0g of activated carbon is weighed by an analytical balance and added into the mixed solution, and a magnetic stirrer is used for stirring for 2 hours to form a dispersion system with the molar ratio of magnesium ions to aluminum ions being 2: 1. Adjusting the pH value of the mixture to 10 (+ -0.3) by using 0.5mol/l NaOH, stirring the mixed solution for 4 hours by using a magnetic stirrer, standing for 24 hours at room temperature, drying the obtained Mg/Al composite material in a constant-temperature vacuum drying oven at 80 ℃, placing the Mg/Al composite material into an aluminum ceramic boat after grinding, heating for 1 hour at 600 ℃ under the condition of nitrogen in a tube furnace, washing the final product by using deionized water, and drying at 80 ℃ by using the vacuum drying oven to obtain the AC-Mg/Al-LDH.
0.125g of the adsorbent was weighed into a 100ml conical flask with a stopper, and 50ml of NaNO with a concentration of 20mg/l was added to the flask3The solution is shaken for 10h under the conditions of the temperature of 25 ℃ and the rotating speed of 120r/min, filtered by a needle type filter head with the diameter of 0.45 mu m, and the concentration of nitrate in the water phase is detected by using a spectrophotometry method, and the removal rate of the nitrate is calculated to be 61%.
Elemental analysis of the composite material AC-Mg/Al-LDH prepared in this example and the surface of the original porous carbon material are shown in table 2:
TABLE 2
| Sample (I) | C％ | H％ | O％ | N％ | O/C | H/C | (O+N)/C |
| AC | 71.8 | 2.188 | 15.384 | 0.235 | 0.214262 | 0.030474 | 0.217535 |
| Mg-Al/AC | 14.86 | 1.6075 | 24.044 | 0 | 1.618035 | 0.108176 | 1.618035 |
As can be seen from Table 2, the composites have lower C% and higher O%, the composites also have higher O/C, H/C and (O + N)/C values, indicating the presence of a significant amount of oxygen-containing functional groups in the structure.
The SEM image of the composite material AC-Mg/Al-LDH prepared in this example is shown in fig. 1(b), and it can be seen from fig. 1(b) that the nano-flakes are uniformly dispersed on the surface of the porous carbon material, and the composite of the LDH material smoothens the rough surface of the porous carbon material compared with the SEM image of the original porous carbon material, i.e., fig. 1 (a).
EDS diagrams of the original porous carbon material and the composite material AC-Mg/Al-LDH prepared in this example are shown in FIG. 2(a) and FIG. 2 (b). As can be seen from the figure, the content ratio of Mg and Al in the composite material reaches 20.9 percent, but the original content is muchThe contents of Mg and Al in the porous carbon material are very low, and are only 0.9 percent, and the result shows that the Mg and the Al are successfully compounded on the surface of the activated carbon. FIG. 2(b) intensity data shows a Mg: A molar ratio of 1.66:1, similar to the set point, and analyzed for the presence of MgO, AlOOH, and MgAl2O4。
The XRD pattern of the composite material AC-Mg/Al-LDH prepared in the example is shown in figure 3, from which MgAl can be seen2O4Spinel is the main crystalline phase on AC-Mg/Al-LDH and in addition contains MgO of low strength.
The FT-IR chart of the composite material AC-Mg/Al-LDH prepared in the example is shown in FIG. 4, the absorption peak at 3300-3700cm-1 is attributed to the tensile shock of O-H, the absorption peak at 1460cm-1 is attributed to the shock of-CH 2, and the peaks at 880cm-1 and 648cm-1 are attributed to Al-O or Mg-O bonds. In addition, it can be seen from the figure that the absorption peak of the AC-Mg/Al-LDH in the spectrum is significantly higher than that of the original porous carbon material.
Example 3:
a preparation method of a composite material for removing nitrate in water comprises the following steps:
preparing 0.6mol/l MgCl2And 0.2mol/l AlCl3300ml of the mixed solution, 3.0g of activated carbon is weighed by an analytical balance and added into the mixed solution, and a magnetic stirrer is used for stirring for 2 hours to form a dispersion system with the molar ratio of magnesium ions to aluminum ions being 3: 1. Adjusting the pH value of the mixture to 10 (+ -0.3) by using 0.5mol/l NaOH, stirring the mixed solution for 4 hours by using a magnetic stirrer, standing for 24 hours at room temperature, drying the obtained Mg/Al composite material in a constant-temperature vacuum drying oven at 80 ℃, placing the Mg/Al composite material into an aluminum ceramic boat after grinding, heating for 1 hour at 600 ℃ under the condition of nitrogen in a tube furnace, washing the final product by using deionized water, and drying at 80 ℃ by using the vacuum drying oven to obtain the AC-Mg/Al-LDH.
0.125g of the adsorbent was weighed into a 100ml conical flask with a stopper, and 50ml of NaNO with a concentration of 20mg/l was added to the flask3The solution is shaken for 10h under the conditions of the temperature of 25 ℃ and the rotating speed of 120r/min, filtered by a needle type filter head with the diameter of 0.45 mu m, and the concentration of nitrate in the water phase is detected by using a spectrophotometry, and the removal rate of the nitrate is calculated to be 62%.
Example 4:
a preparation method of a composite material for removing nitrate in water comprises the following steps:
preparing 0.2mol/l MgCl2And 0.4mol/l AlCl3300ml of the mixed solution, 3.0g of activated carbon was weighed by an analytical balance and added to the mixed solution, and stirred for 2 hours by a magnetic stirrer to form a dispersion system in which the molar ratio of magnesium ions to aluminum ions was 1: 2. Adjusting the pH value of the mixture to 10 (+ -0.3) by using 0.5mol/l NaOH, stirring the mixed solution for 4 hours by using a magnetic stirrer, standing for 24 hours at room temperature, drying the obtained Mg/Al composite material in a constant-temperature vacuum drying oven at 80 ℃, placing the Mg/Al composite material into an aluminum ceramic boat after grinding, heating for 1 hour at 600 ℃ under the condition of nitrogen in a tube furnace, washing the final product by using deionized water, and drying at 80 ℃ by using the vacuum drying oven to obtain the AC-Mg/Al-LDH.
0.125g of the adsorbent was weighed into a 100ml conical flask with a stopper, and 50ml of NaNO with a concentration of 20mg/l was added to the flask3The solution is shaken for 10h under the conditions of the temperature of 25 ℃ and the rotating speed of 120r/min, filtered by a needle type filter head with the diameter of 0.45 mu m, and the concentration of nitrate in the water phase is detected by using a spectrophotometry, and the removal rate of the nitrate is calculated to be 53 percent.
Example 5:
preparing 0.2mol/l MgCl2And 0.6mol/l AlCl3300ml of the mixed solution, 3.0g of activated carbon is weighed by an analytical balance and added into the mixed solution, and a magnetic stirrer is used for stirring for 2 hours to form a dispersion system with the molar ratio of magnesium ions to aluminum ions being 1: 3. Adjusting the pH value of the mixture to 10 (+ -0.3) by using 0.5mol/l NaOH, stirring the mixed solution for 4 hours by using a magnetic stirrer, standing for 24 hours at room temperature, drying the obtained Mg/Al composite material in a constant-temperature vacuum drying oven at 80 ℃, placing the Mg/Al composite material into an aluminum ceramic boat after grinding, heating for 1 hour at 600 ℃ under the condition of nitrogen in a tube furnace, washing the final product by using deionized water, and drying at 80 ℃ by using the vacuum drying oven to obtain the AC-Mg/Al-LDH.
0.125g of the adsorbent was weighed into a 100ml conical flask with a stopper, and 50ml of NaNO with a concentration of 20mg/l was added to the flask3Shaking the solution at 25 deg.C and 120r/min for 10 hr, filtering with 0.45 μm needle filter head, detecting the concentration of nitrate in water phase by spectrophotometry, and calculatingThe removal rate of the nitrate is 50%.
In order to study the reaction conditions of the composite material AC-Mg/Al-LDH prepared by the invention on the removal of nitrate in water, the influence of pH, the adding amount of the composite material and the initial concentration of nitrate on the removal effect of nitrate is studied by selecting the composite material prepared in the embodiment 2.
Influence of pH on the effect of the composite material in removing nitrate in water:
0.125g of the composite material was weighed into a 100mL Erlenmeyer flask, and 50mL NaNO was added to the Erlenmeyer flask at a concentration of 20mg/l3And (3) respectively adjusting the pH values of the solutions to 5,6,7 and 8. Shaking at 25 deg.C and 120r/min for 12 hr, filtering with 0.45 μm needle filter, and spectrophotometrically detecting the concentration of nitrate in water phase, respectively, and the results are shown in FIG. 5.
It can be seen from fig. 5 that the pH value has a greater effect on the removal of nitrate from the composite material, and that the nitrate removal rate increases with increasing pH value within a certain range. The nitrate removal rate was only 34.52% when pH 5, and increased to 60.27% when pH 7, followed by a slight decrease. The neutral and weak alkaline condition is favorable for the adsorption of the layered double hydroxide on the surface layer of the composite material, and the acidic condition inhibits the adsorption capacity of the composite material to nitrate to a certain extent.
The influence of the adding amount on the effect of the composite material on removing the nitrate in water:
0.05g (1g/L), 0.1g (2g/L), 0.15g (3g/L), 0.2g (4g/L) and 0.25g (5g/L) of the composite material were weighed into a 100mL Erlenmeyer flask, and 50mL of NaNO with a concentration of 20mg/L was added to the Erlenmeyer flask3The solution was shaken at a temperature of 25 ℃ and a rotational speed of 120r/min for 10 hours, filtered through a 0.45 μm needle filter, and the concentration of nitrate in the aqueous phase was measured by spectrophotometry, respectively, and the results are shown in FIG. 6.
As can be seen from FIG. 6, when the amount of the nitrate is 1g/l, the nitrate removal rate is 30.22%, the nitrate removal rate is remarkably increased with the increase of the amount of the composite material, when the amount of the nitrate is 4g/l, the nitrate removal rate reaches 88.95%, the nitrate removal rate is increased by 90.22% continuously, and the removal rate is increased slowly. In view of cost, the preferred amount of the composite material added in the invention is 4g of the composite material added in each liter of nitrate solution.
Influence of initial nitrate nitrogen concentration on the effect of the composite material in removing nitrate in water:
0.125g of the composite material was weighed into a 100mL Erlenmeyer flask, 50mL of NaNO3 solution with the concentration of 20mg/l, 40mg/l, 60mg/l, 80mg/l and 100mg/l was added into the Erlenmeyer flask, the mixture was shaken for 10 hours at the temperature of 25 ℃, the pH value of 7 and the rotation speed of 120r/min, and the mixture was filtered through a 0.45 μm needle filter head, and the concentration of the nitrate in the aqueous phase was measured by spectrophotometry, and the results are shown in FIG. 7.
As can be seen from FIG. 7, the composite material has a certain effect of removing nitrate with different concentrations, the nitrate removal rate is 61.77% when the initial concentration of nitrate is 20mg/l, the nitrate removal rate gradually decreases with the increase of the concentration of nitrate, and the nitrate removal rate is 16.84% when the concentration of nitrate is 100 mg/l.
As can be seen from FIGS. 8(a), 8(b) and 8(c), the composite material has good adsorption effect on nitrate, the fitting correlation coefficient of the Langmuir adsorption model to the nitrate adsorption experiment is the highest, the assumption of the Langmuir adsorption model is illustrated, and K is calculatedLThe value was 0.31, which is of the easy-adsorption type.
Claims (8)
1. The preparation method of the adsorbing material for removing the nitrate in the water is characterized by comprising the following steps of:
(1) weighing two metal precursors in a certain target proportion to prepare a mixed solution;
(2) adding a porous carbon material into the mixed solution obtained in the step (1) and stirring to form a dispersion system of two metals with a certain molar ratio;
(3) adjusting the pH value of the mixture to 10 by using alkali liquor;
(4) periodically stirring the mixture obtained in the step (3) by using a magnetic stirrer, standing for 24 hours at room temperature, and drying the obtained composite material in a constant-temperature vacuum drying oven at 80-100 ℃ for 10-12 hours;
(5) naturally cooling to room temperature and grinding;
(6) placing into an aluminum porcelain boat, and roasting for 1-2h in a tubular furnace under the condition of nitrogen;
(7) washing and dehydrating by using deionized water after roasting;
(8) drying for 10-12 hours at 70-80 ℃ by using a vacuum drying oven to obtain the adsorbing material.
2. The method for preparing the adsorbing material for removing the nitrate in the water according to the claim 1, wherein the two metal precursors in the step (1) are: MgCl2、AlCl3。
3. The method for preparing the adsorbing material for removing the nitrate in the water according to the claim 1, wherein the basic parameters of the porous carbon material in the step (2) are as follows: the bulk density is 0.5-0.55g/ml, the water content is less than 5%, the ash content is 7-10%, and the iodine value is 900-950 mg/g.
4. The method for preparing the adsorbing material for removing the nitrate in the water as claimed in claim 1, wherein the alkali solution in the step (3) is NaOH solution with a molar concentration of 0.5 mol/l.
5. The method for preparing the adsorbing material for removing the nitrate in the water as claimed in claim 1, wherein the composite material in the step (4) is dried for 12 hours at 80 ℃.
6. The method for preparing the adsorbing material for removing the nitrate in the water as claimed in claim 1, wherein the calcining of the step (6) is carried out for 1.5 h.
7. The method for preparing the adsorbing material for removing the nitrate in the water as claimed in claim 1, wherein the drying condition of the vacuum drying oven in the step (8) is vacuum drying for 12 hours at 75 ℃.
8. An adsorbing material for removing nitrate in water, which is prepared according to the preparation method of any one of claims 1 to 7.
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