CN114394641A - Method for adsorbing nitrosodiethylamine in water based on modified activated carbon - Google Patents
Method for adsorbing nitrosodiethylamine in water based on modified activated carbon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 264
- WBNQDOYYEUMPFS-UHFFFAOYSA-N N-nitrosodiethylamine Chemical compound CCN(CC)N=O WBNQDOYYEUMPFS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000001179 sorption measurement Methods 0.000 claims abstract description 83
- 238000012986 modification Methods 0.000 claims abstract description 24
- 230000004048 modification Effects 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims description 32
- 238000012360 testing method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000012216 screening Methods 0.000 claims description 11
- 238000002474 experimental method Methods 0.000 claims description 6
- QAXAHXNXXIWQIZ-UHFFFAOYSA-N n,n-diethylnitramide Chemical compound CCN(CC)[N+]([O-])=O QAXAHXNXXIWQIZ-UHFFFAOYSA-N 0.000 claims 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004659 sterilization and disinfection Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003651 drinking water Substances 0.000 description 6
- 235000020188 drinking water Nutrition 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000447 pesticide residue Substances 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 N-nitrosomethylamine diethylamine Chemical compound 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic 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)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention particularly relates to a method for adsorbing nitrosyldiethylamine in water based on modified activated carbon, which comprises the following specific steps: modification of activated carbon: washing original activated carbon with deionized water, filtering, baking in an oven at 80 ℃ for 6-10h, presoaking the activated carbon in a permanganate solution for 22-26h, and then placing in a muffle furnace for high-temperature baking for 2-7h to obtain modified activated carbon; adsorption of nitrosodiethylamine: adding the obtained modified activated carbon into a water body containing nitrosodiethylamine, reacting for 2-6h, and calculating to obtain the adsorption rate of the modified activated carbon to the nitrosodiethylamine. The method comprises the steps of presoaking the activated carbon by using a permanganate solution, then roasting at high temperature, forming more adsorption sites and surface functional groups on the surface of the activated carbon after composite modification, and improving the adsorption capacity.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for adsorbing nitrosodiethylamine in water based on modified activated carbon.
Background
Since the birth of chlorination disinfection process, the risk of human being infected by pathogenic microorganism in drinking water is greatly reduced. The disinfection by-products generated by the reaction of the chlorine disinfectant and organic matters in water gradually become a new problem affecting human health, the traditional chlorination disinfection by-products are Trihalomethanes (THMs) and haloacetic acids (HAAs), and the mass concentration of the trihalomethanes and the haloacetic acids in drinking water can reach 50-100 mug/L usually. Studies have shown that chloramine disinfection can reduce the mass concentration of THMs and HAAs to 10-30 mug/L, but chloramine disinfection generates a novel disinfection byproduct, namely Nitrosamine Substances (NAs), with higher carcinogenic risk. At present, 9N-nitrosamine substances such as NDMA, N-Nitrosodiethylamine (NDEA), N-nitrosomethylamine diethylamine (NMEA) and the like are detected in drinking water. Among them, NDMA and NDEA are classified as class 2A carcinogens by the International agency for research on cancer (IARC), but NDEA shows stronger genotoxicity than NDMA.
In order to ensure the safety of drinking water, a great deal of research on controlling and removing nitrogen disinfection byproducts (N-DBPs) in the drinking water is carried out by broad scholars. The control and removal of N-DBPs has been studied in three major areas: 1) Source control, mainly controlling precursor soluble organic nitrogen (DON) of N-DBPs; 2) process control, including methods such as controlling the disinfectant consumption, replacing the disinfectant, and optimizing and combining the disinfection process; 3) and (4) terminal control, namely removal of the N-DBPs. Although the source control and the process control have certain control effect on the N-DBPs in the water, certain N-DBPs still exist after the whole water purification and disinfection process. Therefore, it is very critical to investigate the direct removal of N-DBPs.
The methods for directly removing N-DBPs mainly include physical methods, chemical methods and biological methods. The physical method is mainly to directly remove N-DBPs through an adsorption material or a filter membrane, for example, Activated Carbon (AC) has a complex pore structure and a large specific surface area, so that various organic matters in a water body can be effectively removed, and the American Ring part (USEPA) has listed the activated carbon adsorption as one of the best treatment processes for removing the organic matters in water. The chemical method is mainly to remove pollutants by adding an oxidant to make the oxidant and the pollutants chemically react, and the oxidant widely used is Permanganate (PM) and sulfate. Currently, a single method is studied more on the removal effect of N-DBPs, but a plurality of methods are studied less on the coupling use. After the activated carbon adsorption NDMA was proposed by David Hanigan et al in 2012, the use of activated carbon in the removal of N-DBPs began to be favored by researchers. Currently, the widely studied activated carbon includes Biological Activated Carbon (BAC), Powdered Activated Carbon (PAC) and Granular Activated Carbon (GAC), and the three materials have certain adsorption effects on N-DBPs, but the adsorption rate is relatively low. Therefore, it is necessary to improve the adsorption effect of the activated carbon on N-DBPs under the combined action of a chemical method and a physical method.
Disclosure of Invention
The invention aims to provide a method for adsorbing nitrosodiethylamine in water based on modified activated carbon, which comprises the steps of presoaking activated carbon with permanganate solution, then roasting at high temperature, carrying out composite modification, forming more adsorption sites and surface functional groups on the surface of the activated carbon, and simultaneously optimizing adsorption reaction conditions through a mode of combining physical adsorption and chemical adsorption, so that the adsorption rate of the nitrosodiethylamine can be effectively improved, and the effect is obvious.
The invention provides a method for adsorbing Nitrosyldiethylamine (NDEA) in water based on modified activated carbon, which comprises the following specific steps:
s1, modification of activated carbon: washing original activated carbon with deionized water, filtering, baking in an oven at 80 ℃ for 6-10h, presoaking the dried activated carbon in a permanganate solution for 22-26h, and then baking the presoaked activated carbon in a resistance furnace at high temperature for 2-7h to obtain modified activated carbon;
s2, adsorbing nitrosodiethylamine: and adding the modified activated carbon obtained in the step S1 into a water body containing nitrosodiethylamine, reacting for 2-6h, measuring the content of nitrosodiethylamine in the water body, and calculating to obtain the adsorption rate of the modified activated carbon on the nitrosodiethylamine.
The adsorption principle of the modified activated carbon is as follows: after the original activated carbon is modified, the specific surface area and the pore volume of the original activated carbon are greatly increased, and the original activated carbon has an obvious pore structure, so that the adsorption quantity of the activated carbon to NDEA is increased. In the physical adsorption process, Van der Waals attractive force exists between NDEA and activated carbon molecules, so that the NDEA molecules can be adsorbed on the surface of the activated carbon until adsorption balance is achieved; the modified activated carbon mainly adopts multi-molecular-layer chemical adsorption to NDEA, and accords with the Freundlich equation, because the modified activated carbon has stronger hydrophobicity, and is impregnated with permanganate to increase oxygen-containing surface functional groups, promote adsorption and improve the adsorption effect to NDEA.
Preferably, after the technical scheme S1, the method further includes screening modified activated carbon, and the specific steps include: and respectively adding the same amount of modified activated carbon obtained from S1 into a nitrosodiethylamine solution with a certain concentration for the same time to obtain the removal effect of different groups of modified activated carbon on the nitrosodiethylamine, and screening out the activated carbon modification condition with the best adsorption effect on the nitrosodiethylamine through a three-factor three-level orthogonal experiment.
Preferably, before the above technical scheme S2, the method further comprises screening adsorption reaction conditions, and the specific steps are as follows: adding different amounts of the modified activated carbon obtained in S1 into water bodies containing nitrosodiethylamine with the same concentration and different pH values respectively, reacting for different time, obtaining the removal effect of different groups of modified activated carbon on the nitrosodiethylamine, and screening out the adsorption reaction condition with the best adsorption effect on the nitrosodiethylamine through a three-factor three-level orthogonal test.
According to the method, the three-factor single-level orthogonal test is used for screening the modification conditions of the activated carbon and the nitrosodiethylamine adsorption conditions of the modified activated carbon, so that the workload is reduced, the optimal modification conditions and adsorption reaction conditions can be screened out, the investment of manpower and material resources for groping the modification conditions is reduced, and the working efficiency can be improved.
Preferably, in the technical solution S1, the activated carbon is any one of biological activated carbon, powdered activated carbon, and granular activated carbon.
Preferably, in the technical scheme S1, the concentration of the permanganate solution is 0.1-0.8 mol/L.
Preferably, in the above technical solution, the concentration of the permanganate solution is 0.8 mol/L.
Preferably, in the technical scheme S1, the volume-to-mass ratio mL/g of the permanganate solution to the activated carbon is 1-10: 1.
Preferably, in the above technical solution S1, the high-temperature calcination temperature is 400-800 ℃, and preferably 400 ℃. According to the technical scheme, the specific surface area, pore volume, pore diameter and the like of the activated carbon can be changed through high-temperature roasting, so that the activated carbon is developed towards the direction beneficial to pollutant adsorption, and the adsorption performance is improved.
Preferably, in the above technical scheme S2, the pH of the water body containing nitrosodiethylamine is controlled to 6 to 9, preferably 6.
Preferably, in the technical scheme S2, the adding amount of the modified activated carbon is 0.6-1g/L, and preferably 0.8 g/L.
Compared with the prior art, the method has the beneficial effects that:
1. the method comprises the steps of cleaning and drying the original activated carbon, pre-soaking the original activated carbon by using a permanganate solution, then roasting the pre-soaked activated carbon at a high temperature, forming more adsorption sites and surface functional groups on the surface of the modified activated carbon by a composite method, increasing the specific surface area, the pore volume and the pore diameter, and remarkably improving the adsorption performance.
2. The invention optimizes the adsorption condition by combining physical adsorption and chemical adsorption, has high adsorption efficiency, is used in water containing nitrosodiethylamine, has the adsorption rate of 78.66 percent and good adsorption effect on the nitrosodiethylamine.
3. The method of the invention respectively screens the modification condition and the adsorption reaction condition by using a three-factor three-level orthogonal test, can save subsequent work, has high efficiency, simultaneously uses materials without toxic and side effects, has high adsorption efficiency on nitrosodiethylamine, and is suitable for removing the nitrosodiethylamine in a drinking water source.
Drawings
FIG. 1 is a 500nm scanning electron micrograph of a virgin activated carbon (a) and a modified activated carbon (b) according to the present invention;
FIG. 2 is a 1 μm scanning electron micrograph of a virgin activated carbon (a) and a modified activated carbon (b) of the present invention;
FIG. 3 is a 5 μm scanning electron micrograph of a virgin activated carbon (a) and a modified activated carbon (b) according to the present invention;
FIG. 4 is a scanning electron micrograph of 10 μm of a virgin activated carbon (a) and a modified activated carbon (b) according to the present invention;
fig. 5 is XRD analysis patterns of the original activated carbon (a) and the modified activated carbon (b) of the present invention.
Detailed Description
The technical features of the present invention described above and those described in detail below (as an embodiment) can be combined with each other to form a new or preferred technical solution, but the present invention is not limited to these embodiments, and the embodiments also do not limit the present invention in any way.
The experimental procedures in the following examples are conventional unless otherwise specified. The formulations according to the following examples are all commercially available products and are commercially available, unless otherwise specified.
The materials and instruments used in the present invention are as follows:
materials: unless otherwise indicated, the chemicals were premium grade pure. Chlorine dioxide (CH)2Cl2) Pesticide residue grade, methanol (CH)3OH): pesticide residue grade, acetone (C)3H6O) pesticide residue grade, diethyl ether [ (C)2H5)2O]: pesticide residueGrade, sodium thiosulfate (Na)2S2O3) Anhydrous sodium sulfate (Na)2SO4) Sodium chloride (NaCl), sulfuric acid (H)2SO4) Rho 1.84g/mL, sodium hydroxide (NaOH), nitrosodiethylamine (C)4H10N2O, 99.9%), potassium permanganate (KMnO)4) Basic Alumina (Alumina): 100 meshes, nitrogen (purity > 99.999%), hydrogen (purity > 99.99%) and powdered activated carbon.
Instruments and devices: a gas chromatograph (GC9790 II), a rotary evaporator (XDSY-3000A), a nitrogen-blowing concentrator (NAI-DCY-12Z), a muffle furnace (SX2-20-10B), a scanning electron microscope (FlexSEM1000), a specific surface area tester (BSD-PS1/2/4), a quartz capillary chromatographic column (column length 30m multiplied by inner diameter 0.25mm, film thickness 0.25 mu m), a chromatographic column (300mm long multiplied by 10mm inner diameter), a 500mL separating funnel, and common instruments and equipment in a common laboratory.
The invention is described in further detail below with reference to the figures and examples:
example 1: activated carbon modification condition screening
A certain amount of active carbon which is cleaned and dried by deionized water is weighed, and the influence of three factors of permanganate concentration, roasting temperature and roasting time on the adsorption performance is mainly considered. The method comprises the steps of carrying out 18 groups of experiments on the modified activated carbon conditions, setting three groups of single-factor horizontal experiments by a single-factor control method when the pH value is 7, wherein the activated carbon is presoaked by permanganate of 0.05, 0.1, 0.2, 0.3, 0.5 and 0.8mol/L, six groups of experiments of 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ and 800 ℃ are respectively set at the roasting temperature, 1h, 2h, 3h, 4h, 5h and 7h are set at the roasting time, and the 18 groups of modified activated carbon are prepared by the steps.
0.5g of the 18 kinds of modified activated carbon and the original Powdered Activated Carbon (PAC) prepared above were weighed respectively, 500mL of NDEA with an initial concentration of 50mg/L was treated, shaking was performed at a constant temperature for 24 hours, and after the complete reaction reached equilibrium, the concentration of the remaining NDEA was measured.
According to the results of the test, the original activated carbon is found to have better NDEA adsorption effect when being presoaked by 0.1mol/L,0.5mol/L and 0.8mol/L of permanganate, the calcination temperatures are respectively 400 ℃, 500 ℃ and 800 ℃, and the calcination times are respectively 2h, 5h and 7 h. Therefore, three-factor three-level orthogonal analysis is carried out according to the test results, so as to screen out the condition combination of the activated carbon with the optimal NDEA adsorption effect. The factors and levels of the orthogonal test are shown in table 1, the results of the orthogonal test design and the removal rate of the activated carbon to the nitrosodiethylamine under the corresponding modification conditions are shown in table 2, and the results of the range analysis are shown in table 3.
TABLE 1 orthogonal test factors and levels
TABLE 2 orthogonal experimental design and corresponding removal rate of nitrosodiethylamine by activated carbon under modified conditions
| Numbering | Permanganate concentration | Calcination time | Calcination temperature | Removal Rate (%) |
| 1 | 1 | 1 | 1 | 22.4758 |
| 2 | 1 | 2 | 3 | 27.7094 |
| 3 | 1 | 3 | 2 | 29.3448 |
| 4 | 2 | 1 | 3 | 35.0854 |
| 5 | 2 | 2 | 2 | 23.5472 |
| 6 | 2 | 3 | 1 | 43.0922 |
| 7 | 3 | 1 | 2 | 32.6552 |
| 8 | 3 | 2 | 1 | 47.4124 |
| 9 | 3 | 3 | 3 | 36.3572 |
TABLE 3 range analysis
Test results show that the optimal combination of the modified activated carbon with the best adsorption effect on the nitrosodiethylamine is screened by a three-factor three-level orthogonal test and range analysis, and the optimal combination is as follows: the concentration of the permanganate solution is 0.8mol/L, the roasting temperature is 400 ℃, and the roasting time is 7 hours.
Example 2: screening of adsorption reaction conditions
The present example mainly considers the influence of adsorption time, pH and dosage on the adsorption effect. Different amounts of modified activated carbon are respectively added into 500mL of water containing nitrosodiethylamine with the same concentration (50mg/L) and pH values of 3, 4, 5, 6, 7, 8 and 9 in amounts of 0.2g/L, 0.4g/L, 0.6g/L, 0.8g/L, 1g/L and 1.2g/L, and after reaction for 0.5h, 1h, 2h, 3h, 4h, 5h and 6h, the adsorption effect on NDEA is calculated.
The results show that the NDEA adsorption effect is better when the adding amount of the modified activated carbon is 0.6g/L, 0.8g/L and 1g/L, the reaction time is 2h, 5h and 6h, and the pH value of the solution is 6, 8 and 9. Therefore, the adsorption reaction conditions having the best effect on the adsorption of nitrosodiethylamine were screened by performing a three-factor three-level orthogonal test based on the above results. Wherein, the orthogonal test factors and levels are shown in table 4, the orthogonal test design and the result of the removal rate of the modified activated carbon to the nitrosodiethylamine under the reaction conditions of the corresponding combination are shown in table 5, and the worst analysis result is shown in table 6.
TABLE 4 orthogonal test factors and levels
TABLE 5 Quadrature test design and removal of nitrosodiethylamine by modified activated carbon under reaction conditions of corresponding combinations
| Numbering | Adding amount of modified active carbon | Reaction time | pH of water body | Removal Rate (%) |
| 1 | 1 | 1 | 1 | 59.6254 |
| 2 | 1 | 2 | 3 | 54.8322 |
| 3 | 1 | 3 | 2 | 61.7283 |
| 4 | 2 | 1 | 3 | 70.3246 |
| 5 | 2 | 2 | 2 | 62.4395 |
| 6 | 2 | 3 | 1 | 78.6600 |
| 7 | 3 | 1 | 2 | 71.2327 |
| 8 | 3 | 2 | 1 | 76.7015 |
| 9 | 3 | 3 | 3 | 62.5417 |
TABLE 6 range analysis
Test results show that the optimal combination of the modified activated carbon screened by the three-factor three-level orthogonal test and the range analysis is as follows: the adding amount of the modified activated carbon is 0.8g/L, the pH value of the solution is 6, and the reaction is carried out for 6 hours. The merit of the three factors is ranked as the addition > pH > reaction time.
Example 3
A method for adsorbing nitrosyldiethylamine in water based on modified activated carbon comprises the following specific steps:
s1, modification of activated carbon: washing original activated carbon with deionized water, filtering, then baking in an oven at 80 ℃ for 8h, taking 100g of the dried activated carbon, pre-soaking in 1L of 0.8mol/L permanganate solution for 24h, and then placing the pre-soaked activated carbon in a muffle furnace at 400 ℃ for high-temperature roasting for 7h to obtain modified activated carbon;
s2, adsorbing nitrosodiethylamine: adding the modified activated carbon obtained in the step S1 into a water body containing nitrosodiethylamine in an adding amount of 0.8g/L, controlling the pH value of the water body to be 6, measuring the content of the nitrosodiethylamine in the water body after reacting for 6h, and calculating the adsorption rate of the modified activated carbon to the nitrosodiethylamine under the reaction condition.
Example 4
A method for adsorbing nitrosyldiethylamine in water based on modified activated carbon comprises the following specific steps:
s1, modification of activated carbon: washing original activated carbon with deionized water, filtering, then baking in an oven at 80 ℃ for 6h, taking 100g of the dried activated carbon, pre-soaking in 100mL of 0.1mol/L permanganate solution for 22h, and then placing the pre-soaked activated carbon in a muffle furnace at 500 ℃ for high-temperature roasting for 5h to obtain modified activated carbon;
s2, adsorbing nitrosodiethylamine: adding the modified activated carbon obtained in the step S1 into a water body containing nitrosodiethylamine in an adding amount of 0.6g/L, controlling the pH value of the water body to be 8, measuring the content of the nitrosodiethylamine in the water body after reacting for 2h, and calculating the adsorption rate of the modified activated carbon to the nitrosodiethylamine under the reaction condition.
Example 5
A method for adsorbing nitrosyldiethylamine in water based on modified activated carbon comprises the following specific steps:
s1, modification of activated carbon: washing original activated carbon with deionized water, filtering, then baking in an oven at 80 ℃ for 10h, taking 100g of the dried activated carbon, pre-soaking in 500mL of 0.5mol/L permanganate solution for 26h, and then placing the pre-soaked activated carbon in a resistance furnace at 800 ℃ for high-temperature roasting for 2h to obtain modified activated carbon;
s2, adsorbing nitrosodiethylamine: adding the modified activated carbon obtained in the step S1 into a water body containing nitrosodiethylamine in an adding amount of 1g/L, controlling the pH value of the water body to be 9, reacting for 5 hours, measuring the content of the nitrosodiethylamine in the water body, and calculating to obtain the adsorption rate of the modified activated carbon to the nitrosodiethylamine under the reaction condition.
Comparative example 1
A process for the adsorption of nitrosodiethylamine in water based on activated carbon, which is largely the same as in example 1, except that the original activated carbon used has not been subjected to a modification step.
Comparative example 2
A method for the adsorption of nitrosodiethylamine in water based on modified activated carbon, which is largely the same as in example 1, except that the activated carbon modification was not pre-soaked with a permanganate solution.
Comparative example 3
A method for adsorbing nitrosodiethylamine in water based on modified activated carbon, which is largely the same as in example 1, except that the modified activated carbon is charged in an amount of 0.4 g/L.
Comparative example 4
A method for adsorbing nitrosodiethylamine in water based on modified activated carbon, which is largely the same as in example 1 except that the pH of the adsorption reaction water body is 3.
Comparative example 5
A modified activated carbon-based method for adsorbing nitrosodiethylamine in water, which is largely the same as example 1 except that the adsorption reaction time is 1 h.
The structures of the original activated carbon and the modified activated carbon of example 3 were subjected to SEM test, specific surface area test, and XRD test using an X-ray diffractometer. Wherein, SEM test is carried out through an emission scanning electron microscope, a specific surface area tester detects the specific surface area, an X-ray diffractometer carries out XRD test, and the SEM structure is shown in figures 1-4; specific surface area data are shown in table 7; the XRD pattern analysis is shown in FIG. 5.
TABLE 7 specific surface area test results
As can be seen from FIGS. 1-4, the surface morphology of the activated carbon before and after modification changed significantly. Before modification, the surface of the activated carbon is large in stacking particles, and the surface of the activated carbon has no obvious pore structure; the modified active carbon has rough surface, irregular convex thorn-shaped particle structure and developed pore structure. Therefore, the activated carbon modified by the method has more adsorption sites formed on the surface, can greatly improve the adsorption performance of the activated carbon, increases the adsorption capacity of the nitrosodiethylamine, and can improve the adsorption effect.
As can be seen from the XRD pattern of fig. 5, the peaks of the activated carbon before and after modification are similar, but some peaks appear and some peaks disappear, and a characteristic diffraction peak of the activated carbon appears at 28.3 ° 2 θ, and in contrast to JCPDS card PDF21-44-0268, the XRD pattern of the modified activated carbon is found to cover a characteristic peak in the β -Mn range, and a characteristic peak at 22.8 ° 2 θ is significantly enhanced, which is found in comparison with PDF21-44-0268 standard card, and these peaks are characteristic peaks of manganese oxide. Therefore, the activated carbon modified by the method has the advantages of new phase generation, increased content of manganese oxide attached to the surface, larger crystallization degree of the modified material and more stable crystal form.
As can be seen from the results in Table 7, the specific surface area of the modified activated carbon was 2 times that of the activated carbon before modification, and the cumulative total adsorption volume (pore diameter of 1.7-300nm) of BJH was 1.72 times that of the activated carbon before modification, and the pore diameters were all mesopores. The active carbon modified by the method of the invention has increased specific surface area and pore volume and improved adsorption performance.
The adsorption effect of the methods of examples 3 to 5 and comparative examples 1 to 5 on nitrosyldiethylamine in the same water body was examined, and the results are shown in table 8.
TABLE 8 adsorption Effect
| Group of | Adsorption Rate (%) |
| Example 3 | 78.66 |
| Example 4 | 69.27 |
| Example 5 | 63.14 |
| Comparative example 1 | 36.1 |
| Comparative example 2 | 53.7 |
| Comparative example 3 | 49.32 |
| Comparative example 4 | 41.15 |
| Comparative example 5 | 39.71 |
From the results in table 8, it can be seen that the modified activated carbon prepared by the method of the present invention has an effect of adsorbing nitrosodiethylamine in water, which is 2.18 times of the adsorption effect of the original activated carbon, and 1.46 times of the adsorption effect of the modified activated carbon not presoaked with permanganate solution, and the effect is significant; the input amount, pH and reaction time of the active carbon in the adsorption condition have influence on the adsorption, and the adsorption effect is obviously improved by adopting the adsorption condition. The modified active carbon has high adsorption efficiency on the nitrosyl diethylamine in the water body, the adsorption performance of the active carbon can be effectively improved by a composite modification method combining presoaking and high-temperature roasting, the two have the synergistic effect, and the adsorption effect reaches the optimal level by optimizing the adsorption condition.
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.
Claims (10)
1. A method for adsorbing nitrosyldiethylamine in water based on modified activated carbon is characterized by comprising the following specific steps:
s1, modification of activated carbon: washing original activated carbon with deionized water, filtering, baking in an oven at 80 ℃ for 6-10h, presoaking the dried activated carbon in a permanganate solution for 22-26h, and then baking the presoaked activated carbon in a muffle furnace at high temperature for 2-7h to obtain modified activated carbon;
s2, adsorbing nitrosodiethylamine: and adding the modified activated carbon obtained in the step S1 into a water body containing nitrosodiethylamine, reacting for 2-6h, measuring the content of nitrosodiethylamine in the water body, and calculating to obtain the adsorption rate of the modified activated carbon on the nitrosodiethylamine.
2. The method for adsorbing nitrosyldiethylamine in water based on modified activated carbon as claimed in claim 1, wherein after S1, the method further comprises screening modified activated carbon, and the specific steps are as follows: and respectively adding the same amount of modified activated carbon obtained from S1 into a nitrosodiethylamine solution with a certain concentration for the same time to obtain the removal effect of different groups of modified activated carbon on the nitrosodiethylamine, and screening out the activated carbon modification condition with the best adsorption effect on the nitrosodiethylamine through a three-factor three-level orthogonal experiment.
3. The method for adsorbing nitrodiethylamine in water based on modified activated carbon as claimed in claim 1, characterized in that before S2, the method further comprises screening of adsorption reaction conditions, and the specific steps are as follows: adding different amounts of the modified activated carbon obtained in S1 into water bodies containing nitrosodiethylamine with the same concentration and different pH values respectively, reacting for different time, obtaining the removal effect of different groups of modified activated carbon on the nitrosodiethylamine, and screening out the adsorption reaction condition with the best adsorption effect on the nitrosodiethylamine through a three-factor three-level orthogonal test.
4. The method for adsorbing nitrodiethylamine in water based on modified activated carbon as claimed in claim 1, wherein in S1, the activated carbon is any one of biological activated carbon, powdered activated carbon and granular activated carbon.
5. The method for adsorbing nitrodiethylamine in water based on modified activated carbon as claimed in claim 1, wherein the concentration of said permanganate solution in S1 is 0.1-0.8 mol/L.
6. The method for adsorbing nitrodiethylamine in water based on modified activated carbon as claimed in claim 5, characterized in that the concentration of the permanganate solution is 0.8 mol/L.
7. The method for adsorbing nitrodiethylamine in water based on modified activated carbon as claimed in claim 1, wherein in S1, the volume-to-mass ratio mL/g of the permanganate solution to activated carbon is 1-10: 1.
8. The method for adsorbing nitrosyldiethylamine in water based on modified activated carbon as claimed in claim 1, wherein in S1, the high-temperature roasting temperature is 400-800 ℃, preferably 400 ℃.
9. The method for adsorbing nitrosodiethylamine in water based on modified activated carbon as claimed in claim 1, wherein in S2, the pH of the water body containing nitrosodiethylamine is controlled to 6-9, preferably 6.
10. The method for adsorbing nitrosyldiethylamine in water based on modified activated carbon as claimed in claim 1, wherein in S2, the addition amount of the modified activated carbon is 0.6-1g/L, preferably 0.8 g/L.
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