CN114394642A - Method for adsorbing nitrosodiethylamine in water based on modified zeolite - Google Patents
Method for adsorbing nitrosodiethylamine in water based on modified zeolite Download PDFInfo
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- CN114394642A CN114394642A CN202210097487.4A CN202210097487A CN114394642A CN 114394642 A CN114394642 A CN 114394642A CN 202210097487 A CN202210097487 A CN 202210097487A CN 114394642 A CN114394642 A CN 114394642A
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 171
- WBNQDOYYEUMPFS-UHFFFAOYSA-N N-nitrosodiethylamine Chemical compound CCN(CC)N=O WBNQDOYYEUMPFS-UHFFFAOYSA-N 0.000 title claims abstract description 84
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- 238000013461 design Methods 0.000 description 3
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 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
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
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- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical class ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
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- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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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
- C02F1/281—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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
Abstract
The invention specifically relates to a method for adsorbing nitrosodiethylamine in water based on modified zeolite, which comprises the following specific steps: modification of zeolite: washing original zeolite with deionized water, filtering, baking in an oven at 80 ℃ for 6-10h, taking the dried zeolite, pre-soaking in a ferrous sulfate solution for 22-26h, and then placing the pre-soaked zeolite in a muffle furnace for high-temperature baking for 2-7h to obtain modified zeolite; adsorption of nitrosodiethylamine: adding the obtained modified zeolite into a water body containing nitrosodiethylamine, reacting for 3-6h, and calculating to obtain the adsorption rate of the modified zeolite to the nitrosodiethylamine. The invention firstly uses ferrous sulfate solution to presoak zeolite, and carries out high-temperature roasting, more adsorption sites and larger pore volume/aperture value are formed on the surface of the zeolite after composite modification, and the adsorption capacity is improved.
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 zeolite.
Background
Although many harmful substances are removed from drinking water after chlorination and disinfection, the disinfection by-products generated by the reaction of chlorine disinfectants and organic matters in water gradually become a new problem affecting human health. Nitrosodimethylamine (NDMA) was first discovered in drinking water from the ontario lake, canada in 1989. The China has repeatedly detected N-nitrosamine compounds in drinking water, and the concentration level is higher than that of Europe and America countries. 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 remove N-DBPs directly through an adsorption material or a filter membrane, and the adsorption method is mainly to remove pollutants by utilizing the chemical reaction between the adsorption material and the adhesion force and the surface chemical property formed by the huge specific surface area of the adsorbent, so that the aim of removing the pollutants is fulfilled. The adsorbent is of various types, and typically, activated carbon, silica gel, zeolite, and the like are used. The zeolite has a good adsorption effect on pollutants due to various types, low price and easy obtainment, and is widely applied in the field of environmental management. The adsorption capacity of unmodified zeolite to nitrosodiethylamine is relatively weak, but the adsorption capacity of modified zeolite to nitrosodiethylamine is obviously improved. At present, the modification methods of zeolite mainly comprise high-temperature modification, acid modification and load modification. In the prior art, a single method is adopted to study the removal effect of N-DBPs, but the research on the coupling use of a plurality of methods is less. Therefore, it is one of the important research directions in the future to research the new modified zeolite to improve the adsorption performance to nitrosodiethylamine.
Disclosure of Invention
The invention aims to provide a method for adsorbing nitrosodiethylamine in water based on modified zeolite, which comprises the steps of pre-soaking zeolite with ferrous sulfate solution, then carrying out high-temperature roasting, carrying out composite modification, forming more adsorption sites and larger pore volume/pore diameter value on the surface of the modified zeolite, and simultaneously optimizing adsorption reaction conditions by combining physical adsorption and chemical adsorption, thereby effectively improving the adsorption rate of the nitrosodiethylamine and having obvious effect.
The invention provides a method for adsorbing Nitrosyldiethylamine (NDEA) in water based on modified zeolite, which comprises the following specific steps:
s1, modification of zeolite: washing original zeolite with deionized water, filtering, baking in an oven at 80 ℃ for 6-10h, taking the dried zeolite, pre-soaking in a ferrous sulfate solution for 22-26h, and then placing the pre-soaked zeolite in a muffle furnace for high-temperature baking for 2-7h to obtain modified zeolite;
s2, adsorbing nitrosodiethylamine: and adding the modified zeolite obtained in the step S1 into a water body containing nitrosodiethylamine, reacting for 3-6h, and measuring the content of the nitrosodiethylamine in the water body to obtain the adsorption rate of the modified zeolite to the nitrosodiethylamine.
The zeolite is formed by connecting stereo silicon-oxygen tetrahedron and stereo aluminum-oxygen tetrahedron by common oxygen atoms, and has a plurality of nanometer-scale pore canals with uniform pore diameter and pores with large internal specific surface area, so that the zeolite has strong adsorbability.
Adsorption principle of modified zeolite: the porosity of the original zeolite is obviously increased after the original zeolite is calcined at high temperature, so that the number of micropores of the zeolite is increased, and the adsorption quantity of the zeolite to NDEA is increased. According to the invention, physical adsorption and chemical adsorption are combined, and in the physical adsorption process, Van der Waals attraction exists between zeolite and NDEA molecules, so that the NDEA molecules can be adsorbed on the surface of the zeolite until adsorption balance is achieved; the chemical adsorption of the modified zeolite on NDEA is mainly monolayer chemical adsorption, and accords with the Langmuir equation, because the surface catalytic performance of the zeolite is obviously improved after the zeolite is impregnated with ferrous sulfate. In addition, the iron compound is loaded on the surface of the zeolite, so that the surface property of the zeolite is changed, the structure is more complex, the porous structure is more obvious, and the adsorption sites are more, thereby improving the adsorption effect on NDEA.
Preferably, after the above technical scheme S1, the method further comprises screening zeolite modification conditions, and the specific steps are: and respectively adding the same amount of modified zeolite 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 zeolite on the nitrosodiethylamine, and screening out the zeolite modification conditions with the best adsorption effect on the nitrosodiethylamine through a three-factor three-level orthogonal test. According to the invention, the three-factor single-level orthogonal test is used for screening the zeolite modification conditions, so that the workload is reduced, the optimal modification conditions can be screened out, the investment of manpower and material resources for exploring the modification conditions is reduced, and the efficiency can be improved.
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 modified zeolite obtained from S1 into water bodies containing nitrosodiethylamine with the same concentration and different pH values respectively, reacting for different time to obtain the removal effect of different groups of modified zeolite on the nitrosodiethylamine, and screening out the adsorption reaction condition with the best adsorption effect on the nitrosodiethylamine by a three-factor three-level orthogonal test. According to the invention, the adsorption reaction conditions of the modified zeolite are screened by using the three-factor single-level orthogonal test, so that the workload is reduced, the optimal adsorption reaction conditions can be screened out, and the working efficiency is improved.
Preferably, in the above technical solution S1, the concentration of the ferrous sulfate solution is 0.2-0.5mol/L, and preferably 0.3 mol/L. In the technical scheme, the ferrous sulfate is used for pretreatment, so that a large number of new micropores are generated on the surface of the zeolite, the existing micropores are converted into mesopores, the number of acid functional groups on the surface of the zeolite is increased, and the adsorption capacity of the zeolite on the nitrosodiethylamine is promoted by the chemical action of the acid functional groups and the nitrosodiethylamine.
Preferably, in the technical scheme S1, the volume-to-mass ratio mL/g of the catalyst to the zeolite is 1-10: 1.
Preferably, in the above technical solution S1, the calcination temperature is 400-800 ℃, preferably 800 ℃. According to the technical scheme, the zeolite is roasted at high temperature, so that the specific surface area, the pore volume, the pore diameter and the like of the zeolite can be changed, the zeolite 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 6-9, preferably pH 7.
Preferably, in the technical scheme S2, the adding amount of the modified zeolite 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 invention firstly cleans and dries the original zeolite, and uses ferrous sulfate acid solution to presoak, then carries on high temperature baking, the surface of the modified zeolite forms more adsorption sites and surface functional groups, the specific surface area, pore volume/aperture value are increased, the adsorption performance is improved obviously.
2. The method respectively screens the modification conditions and the adsorption reaction conditions by using a three-factor three-level orthogonal test to obtain the optimal reaction conditions, combines physical adsorption and chemical adsorption, has high adsorption efficiency, is used in water containing nitrosodiethylamine, has the adsorption rate of 75.42 percent on the nitrosodiethylamine, and has good adsorption effect.
3. The method can save later work by pre-screening the optimal conditions, has high efficiency, simultaneously has no toxic or side effect on the used materials, has high adsorption efficiency on the nitrosodiethylamine, and is suitable for removing the nitrosodiethylamine in a drinking water source.
Drawings
FIG. 1 is a 500nm scanning electron micrograph of a modified zeolite (a) and an original zeolite (b) according to the present invention;
FIG. 2 is a 1 μm scanning electron micrograph of a modified zeolite (a) and an original zeolite (b) according to the present invention;
FIG. 3 is a scanning electron micrograph at 5 μm of a modified zeolite (a) and an original zeolite (b) according to the present invention;
FIG. 4 is a 10 μm scanning electron micrograph of a modified zeolite (a) and an original zeolite (b) according to the present invention;
FIG. 5 is an XRD analysis pattern of the modified zeolite (a) and the original zeolite (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 test methods in the following examples are conventional methods 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 residue grade, 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 200 meshes, nitrogen (purity > 99.999%), hydrogen (purity > 99.99%), and powdered zeolite.
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: screening of Zeolite modification conditions
Weighing a certain amount of zeolite which is cleaned and dried by deionized water, and mainly considering the influence of three factors of ferrous sulfate concentration, roasting temperature and roasting time on the adsorption performance. The zeolite modification condition screening tests are carried out for 18 groups in total, three groups of single-factor horizontal tests are set by a single-factor control method when the pH is 7, the zeolite is presoaked by ferrous sulfate of 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.5mol/L and 0.8mol/L respectively, six groups of tests of 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ and 800 ℃ are set at the roasting temperature, six groups of tests of 1h, 2h, 3h, 4h, 5h and 7h are set at the roasting time, and 18 groups of modified zeolites are prepared by the steps in total. The factors and levels of the orthogonality test are shown in Table 1.
Respectively weighing 0.5g of the 18 prepared modified zeolites and the original zeolite, treating 500mL of NDEA with the initial concentration of 50mg/L, oscillating at constant temperature for 24h, and determining the concentration of the residual NDEA after the full reaction reaches equilibrium.
The test results show that the original zeolite has better NDEA adsorption effect when subjected to ferrous sulfate solutions of 0.2mol/L, 0.3mol/L and 0.5mol/L at the calcining temperatures of 400 ℃, 600 ℃ and 800 ℃ for 2h, 5h and 7h respectively. Therefore, a three-factor three-level orthogonal analysis is performed according to the results of the above experimental determination, and a condition combination of zeolite having an optimum NDEA adsorption effect is selected. 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 zeolite to 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 removal of nitrosodiethylamine by zeolite under corresponding modified conditions
| Numbering | FeSO4Concentration of | Calcination time | Calcination temperature | Removal Rate (%) |
| 1 | 1 | 1 | 1 | 26.1292 |
| 2 | 1 | 2 | 3 | 27.2558 |
| 3 | 1 | 3 | 2 | 25.245 |
| 4 | 2 | 1 | 3 | 36.8148 |
| 5 | 2 | 2 | 2 | 35.1284 |
| 6 | 2 | 3 | 1 | 29.4166 |
| 7 | 3 | 1 | 2 | 26.2496 |
| 8 | 3 | 2 | 1 | 34.7564 |
| 9 | 3 | 3 | 3 | 37.12852 |
TABLE 3 range analysis
Test results show that the optimal combination of zeolite modification 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 ferrous sulfate solution is 0.3mol/L, the roasting temperature is 800 ℃, and the roasting time is 5 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 zeolite 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, 1.0g/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 test results show that the NDEA adsorption effect is better when the addition amount of the modified zeolite is 0.6g/L, 0.8g/L and 1.0g/L, the reaction time is 3h, 5h and 6h, and the pH of the solution is 6, 7 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 zeolite 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 zeolites under reaction conditions of corresponding combinations
| Numbering | Amount of modified zeolite added | Reaction time | pH of water body | Removal Rate (%) |
| 1 | 1 | 1 | 1 | 59.2754 |
| 2 | 1 | 2 | 3 | 62.1378 |
| 3 | 1 | 3 | 2 | 61.2657 |
| 4 | 2 | 1 | 2 | 68.2174 |
| 5 | 2 | 2 | 2 | 75.4200 |
| 6 | 2 | 3 | 1 | 68.1247 |
| 7 | 3 | 1 | 2 | 73.2679 |
| 8 | 3 | 2 | 1 | 72.1386 |
| 9 | 3 | 3 | 3 | 64.2137 |
TABLE 6 range analysis
Test results show that the optimal combination of the modified zeolite screened by the three-factor three-level orthogonal test and range analysis is as follows: the addition amount of the modified zeolite was 0.8g/L, the pH of the solution was 7, and the reaction was carried out for 5 hours. The merit of the three factors is ranked as the charge > reaction time > pH.
Example 3
A method for adsorbing nitrosodiethylamine in water based on modified zeolite comprises the following specific steps:
s1, modification of zeolite: washing original zeolite with deionized water, filtering, baking in an oven at 80 ℃ for 8h, taking 100g of the dried zeolite, pre-soaking in 1L of ferrous sulfate solution with the concentration of 0.3mol/L for 24h, and roasting the pre-soaked zeolite in a muffle furnace at 800 ℃ for 5h to obtain modified zeolite;
s2, adsorbing nitrosodiethylamine: adding the modified zeolite obtained in S1 into a water body containing nitrosodiethylamine in an adding amount of 0.8g/L, controlling the pH of the water body to be 7, reacting for 5h, and measuring the content of the nitrosodiethylamine in the water body to obtain the adsorption rate of the modified zeolite to the nitrosodiethylamine.
Example 4
A method for adsorbing nitrosodiethylamine in water based on modified zeolite comprises the following specific steps:
s1, modification of zeolite: washing original zeolite with deionized water, filtering, baking in an oven at 80 ℃ for 6h, taking 100g of the dried zeolite, pre-soaking in 100mL of ferrous sulfate solution with the concentration of 0.5mol/L for 22h, and roasting the pre-soaked zeolite in a muffle furnace at 400 ℃ for 7h to obtain modified zeolite;
s2, adsorbing nitrosodiethylamine: adding the modified zeolite obtained in S1 into a water body containing nitrosodiethylamine in an adding amount of 0.6g/L, controlling the pH of the water body to be 6, reacting for 6h, and measuring the content of the nitrosodiethylamine in the water body to obtain the adsorption rate of the modified zeolite to the nitrosodiethylamine.
Example 5
A method for adsorbing nitrosodiethylamine in water based on modified zeolite comprises the following specific steps:
s1, modification of zeolite: washing original zeolite with deionized water, filtering, baking in an oven at 80 ℃ for 10h, taking 100g of the dried zeolite, pre-soaking in 500mL of ferrous sulfate solution with the concentration of 0.2mol/L for 26h, and roasting the pre-soaked zeolite in a muffle furnace at 600 ℃ for 2h to obtain modified zeolite;
s2, adsorbing nitrosodiethylamine: adding the modified zeolite obtained in S1 into a water body containing nitrosodiethylamine in an adding amount of 1.0g/L, controlling the pH of the water body to be 9, reacting for 3h, and measuring the content of the nitrosodiethylamine in the water body to obtain the adsorption rate of the modified zeolite to the nitrosodiethylamine.
Comparative example 1
A zeolite-based process for the adsorption of nitrosodiethylamine in water which is largely the same as that of example 3, except that the original zeolite used has not been subjected to a modification step.
Comparative example 2
A process for the adsorption of nitrosodiethylamine in water based on a modified zeolite, which is largely the same as example 3, except that the zeolite modification was not pre-impregnated with a ferrous sulfate solution.
Comparative example 3
A process for the adsorption of nitrosodiethylamine in water based on a modified zeolite, which is largely the same as in example 3, except that the amount of modified zeolite added is 0.4 g/L.
Comparative example 4
A modified zeolite-based process for the adsorption of nitrosodiethylamine in water which is largely the same as that of example 3 except that the pH of the adsorption reaction water is 3.
Comparative example 5
A process for the adsorption of nitrosodiethylamine in water based on modified zeolite, which is largely the same as example 3, except that the adsorption reaction time is 1 h.
The structures of the original zeolite and the modified zeolite 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 fig. 1-4, the surface morphology of the zeolite before and after modification changed significantly. Before modification, the zeolite surface has larger stacking particles and no obvious pore structure on the surface; the modified zeolite has rough surface, irregular raised thorn-shaped particle structure and developed pore structure. The modified zeolite has the advantages that the pore diameter is reduced to a certain extent, but the pore volume is obviously increased, the ratio of the pore volume to the pore diameter is also obviously increased, the porous structure is more obvious, and the adsorption sites are more. In conclusion, the zeolite modified by the method can greatly improve the adsorption performance of the zeolite and increase the adsorption capacity of the nitrosodiethylamine, thereby improving the adsorption effect of NDEA and obviously improving the surface catalytic performance of the zeolite. In addition, the iron compound is loaded on the surface of the zeolite, so that the condition that the surface of the zeolite is the same, the structure is more complex, the porous structure is more obvious, and the adsorption sites are more, thereby improving the adsorption effect on NDEA.
As can be seen from the XRD pattern of fig. 5, the peaks before and after modification of the zeolite are similar, but some peaks appear and some peaks disappear, and characteristic diffraction peaks of the zeolite appear at 69.37 °, and compared with JCPDS card PDF21-44-0268, the XRD pattern of the modified zeolite covers characteristic peaks of sulfur and iron elements, and characteristic peaks at 23.98 ° 2 θ are significantly enhanced, and compared with PDF21-44-0268 standard card, the peaks are characteristic peaks of sulfur and iron elements. Therefore, the zeolite modified by the method of the invention has new phase generation, the content of oxide with iron attached to the surface is increased, the crystallization degree of the modified material is larger, and the crystal form is more stable.
From the results in Table 7, it can be seen that the specific surface area after modification of the zeolite was 4.66 times that before modification, and the cumulative total adsorption volume (pore diameter 1.7 to 300nm) of BJH was 22.69 times that before modification, but the pore diameter was reduced by 2.57 times. It is demonstrated that the zeolite modified by the method of the present invention has increased specific surface area and pore volume, increased pore volume/pore diameter value and improved adsorption performance.
The adsorption effect of the methods of examples 1 to 3 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 | 75.42 |
| Example 4 | 65.27 |
| Example 5 | 68.21 |
| Comparative example 1 | 18.23 |
| Comparative example 2 | 23.17 |
| Comparative example 3 | 58.72 |
| Comparative example 4 | 52.41 |
| Comparative example 5 | 54.92 |
From the results in table 8, it can be seen that the modified zeolite obtained by the method of the present invention has an effect of adsorbing nitrosodiethylamine in water under specific adsorption conditions, which is 4.14 times of the adsorption effect of the original zeolite and 3.26 times of the adsorption effect of the modified zeolite which is not presoaked with ferrous sulfate solution, and the effect is significant; the input amount, pH and reaction time of zeolite in the adsorption condition have influence on adsorption, and the adsorption effect is obviously improved by adopting the adsorption condition. The zeolite modified by the method has high adsorption efficiency on the nitrosodiethylamine in the water body, the adsorption performance of the zeolite can be effectively improved by a composite modification method combining presoaking and high-temperature roasting, the zeolite and the zeolite have a synergistic effect, and the adsorption effect can reach the optimal level by optimizing the adsorption conditions.
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 nitrosodiethylamine in water based on modified zeolite is characterized by comprising the following specific steps:
s1, modification of zeolite: washing original zeolite with deionized water, filtering, baking in an oven at 80 ℃ for 6-10h, taking the dried zeolite, pre-soaking in a ferrous sulfate solution for 22-26h, and then placing the pre-soaked zeolite in a muffle furnace for high-temperature baking for 2-7h to obtain modified zeolite;
s2, adsorbing nitrosodiethylamine: and adding the modified zeolite obtained in the step S1 into a water body containing nitrosodiethylamine, reacting for 3-6h, and measuring the content of the nitrosodiethylamine in the water body to obtain the adsorption rate of the modified zeolite to the nitrosodiethylamine.
2. The method for adsorbing nitrosodiethylamine in water based on modified zeolite as claimed in claim 1, further comprising screening of zeolite modification conditions after S1, the specific steps are: and respectively adding the same amount of modified zeolite 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 zeolite on the nitrosodiethylamine, and screening out the zeolite modification conditions with the best adsorption effect on the nitrosodiethylamine through a three-factor three-level orthogonal test.
3. The method for adsorbing nitrosodiethylamine in water based on modified zeolite as claimed in claim 1, further comprising screening the adsorption reaction conditions before S2, the specific steps are: adding different amounts of modified zeolite obtained from S1 into water bodies containing nitrosodiethylamine with the same concentration and different pH values respectively, reacting for different time to obtain the removal effect of different groups of modified zeolite on the nitrosodiethylamine, and screening out the adsorption reaction condition with the best adsorption effect on the nitrosodiethylamine by a three-factor three-level orthogonal test.
4. The method for adsorbing nitrosodiethylamine in water based on modified zeolite as claimed in claim 1, wherein the concentration of the ferrous sulfate solution in S1 is 0.2-0.5 mol/L.
5. The method for adsorbing nitrosodiethylamine in water based on modified zeolite as claimed in claim 4, wherein the concentration of the ferrous sulfate solution is 0.3 mol/L.
6. The method for adsorbing nitrosodiethylamine in water based on modified zeolite as claimed in claim 1, wherein in S1, the volume-to-mass ratio mL/g of ferrous sulfate solution and zeolite is 1-10: 1.
7. The method for adsorbing nitrosodiethylamine in water based on modified zeolite as claimed in claim 1, wherein in S1, the high temperature calcination temperature is 400-800 ℃.
8. The method for adsorbing nitrosodiethylamine in water based on modified zeolite as claimed in claim 7, wherein the high temperature calcination temperature is 800 ℃.
9. The method for adsorbing nitrosodiethylamine in water based on modified zeolite as claimed in claim 1, wherein in S2, the pH of the water containing nitrosodiethylamine is controlled to 6-9, preferably 7.
10. The method for adsorbing nitrosodiethylamine in water based on modified zeolite as claimed in claim 1, wherein the modified zeolite is added in an amount of 0.6-1g/L, preferably 0.8g/L in S2.
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| US20180079660A1 (en) * | 2016-09-20 | 2018-03-22 | University Of Kentucky Research Foundation | Process and material for removal of nitrosamines from aqueous systems |
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