CN114073936B - Adsorbent for enriching nitrosamine in air and preparation method thereof - Google Patents

Adsorbent for enriching nitrosamine in air and preparation method thereof Download PDF

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CN114073936B
CN114073936B CN202110934475.8A CN202110934475A CN114073936B CN 114073936 B CN114073936 B CN 114073936B CN 202110934475 A CN202110934475 A CN 202110934475A CN 114073936 B CN114073936 B CN 114073936B
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adsorbent
metal salt
enriching
inorganic material
nitrosamine
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CN114073936A (en
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杨振
何婷婷
陈武炼
徐晨
张凯
徐增睿
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Shanghai Anpu Experimental Technology Co ltd
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Abstract

The invention discloses an adsorbent for enriching nitrosamine in air and a preparation method thereof, wherein the adsorbent is formed by mixing inorganic materials and antioxidants, and the inorganic materials are inorganic materials modified by metal oxides or metal salts. The invention takes cheap inorganic materials as raw materials, modifies metal oxide or metal salt providing a positive charge field on a filler in a physical load mode, and mixes an antioxidant and the filler to form an adsorbent for enriching nitrosamine in air; the method has the advantages of simple synthesis steps and low cost, and can effectively prevent the false positive phenomenon in the trapping process; the method is suitable for enrichment of nitrosamines in the air by inspection institutions, scientific research and environmental monitoring units.

Description

Adsorbent for enriching nitrosamine in air and preparation method thereof
Technical Field
The invention relates to an adsorption material and a preparation method thereof, in particular to an adsorbent for enriching nitrosamine in air and a preparation method thereof.
Background
Nitrosamines are a strong carcinogen, have the properties of low boiling point and easy volatilization, and easily cause the nitrosamines contained in cigarette smoke, cosmetics and industrial products to volatilize into the air, thereby threatening the health of people. Therefore, the detection of nitrosamines in the air is of great importance for the monitoring of environmental health.
At present, nitrosamine in the air is mainly enriched by an adsorption method. The method is simple and efficient, firstly, the nitrosamine in the air is captured by the adsorbent, and then the nitrosamine is desorbed by the desorption liquid and enters an instrument for analysis. Among them, the adsorbent plays an important role as a core of the method. Among the commonly used adsorbents are modified molecular sieves or zeolite materials such as NaY, SBA-15 and MCM-41, for example: the three-stage copolymer was formed as a templating agent by ZhouCF et Al, SBA-15 was prepared by prepolymerization, standing, heating and calcination, and modified with CuO for nitrosamine removal (Zhou C F, xu J H, zhuang T T, et Al New efficiency Al-containing SBA-15materials for removing nitrosamines in mild conditions[J ]. Studies in Surface Science & Catalysis,2005, 156:907-916.). The chinese patent application No. CN202011568692.1 discloses that a carbon-containing polymer is prepared by mixing monomers and an initiator for polymerization reaction, and activated with a mixture of water vapor/inert gas (e.g., nitrogen) to prepare spherical carbon for adsorption of nitrosamines in flue gas. The Chinese patent document with publication number CN 101053446B uses molecular sieves such as SBA-15, MCM-41, etc., modified by high viscosity liquid such as glycerol, ethylene glycol, polyethylene glycol, etc., as adsorbents for removing nitrosamines in flue gas.
Although the adsorbents have good adsorption effect on nitrosamine, the preparation process of materials or material precursors is complex, and the adsorbents have the defects of long time consumption, high cost and the like, and are difficult to realize large-scale production. Meanwhile, the air matrix is complex, and in the trapping process of nitrosamine, nitrogen-oxygen compounds in the air are easy to be converted into nitrosamine, so that false positive is caused, and the accuracy of a detection result is influenced. Therefore, aiming at the defects of long time consumption, high cost and easy generation of false positive phenomenon in the trapping process of the existing nitrosamine adsorption material preparation process, the preparation process is complex and needs to be improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing the adsorbent for enriching the nitrosamine in the air and the preparation method thereof, which have low raw material cost and simple preparation process and can prevent false positive phenomenon in the trapping process.
The technical scheme adopted by the invention for solving the technical problems is to provide the adsorbent for enriching the nitrosamine in the air, which is formed by mixing an inorganic material and an antioxidant, wherein the inorganic material is an inorganic material modified by metal oxide or metal salt.
Further, the inorganic material and the antioxidant are mixed according to the mass ratio of 1-5:0.01-0.1.
Further, the inorganic material is diatomaceous earth, silica, zeolite or molecular sieve.
Further, the metal salt is magnesium sulfate, magnesium acetate, calcium chloride, calcium carbonate, sodium sulfate or basic copper carbonate, and the metal oxide is magnesium oxide, calcium oxide or copper oxide.
Further, the antioxidant is metabisulfite, sulfamic acid or ascorbic acid.
The invention also provides a preparation method of the adsorbent for enriching nitrosamine in air, which comprises the following steps: s1, preparing a metal oxide or metal salt solution by a mechanical stirring mode; s2, placing the inorganic material into a metal oxide or metal salt solution to prepare a metal oxide or metal salt loaded inorganic material; s3, mixing the inorganic material modified by the metal oxide or the metal salt with the antioxidant in a physical mixing mode to obtain the nitrosamine adsorption material.
Further, the step S1 is to take metal oxide or metal salt, add solvent, and mechanically stir for 20-120 min at a stirring speed of 250-400 r/min to obtain metal oxide or metal salt solution; step S2, adding inorganic materials into the metal oxide or metal salt solution, and mechanically stirring for 12-24 hours at a stirring speed of 250-400 r/min; removing the solvent by suction filtration, and drying at 60 ℃ for 12 hours to obtain the metal oxide or metal salt modified inorganic material.
Further, for the inorganic material loaded by the metal salt, the step S3 further comprises calcining the inorganic material modified by the metal salt in a muffle furnace at 400-1000 ℃ for 2-12 hours to obtain the inorganic material modified by the metal oxide.
Further, the solvent: metal salt: the inorganic material is 1-5 mL, 0.04-0.6 g, 0.2-1 g, and the solvent is deionized water, methanol or ethanol.
Further, the mixing mode adopted in the step S3 is grinding, ultrasonic vibration or mechanical stirring.
Compared with the prior art, the invention has the following beneficial effects: the adsorbent for enriching the nitrosamine in the air provided by the invention takes the cheap inorganic material as a raw material, modifies the metal salt providing a positive charge field or the metal oxide having better adsorption performance on the nitrosamine on the filler in a physical load mode, and mixes the antioxidant with the filler; the method has the advantages of simple synthesis steps and low cost, and can effectively prevent the false positive phenomenon in the trapping process; the method is suitable for enrichment of nitrosamines in the air by inspection institutions, scientific research and environmental monitoring units.
Drawings
FIG. 1 is a representation of the EDS of example 1 of the present invention;
FIG. 2 is a representation of BET and BJH for example 1 of the present invention;
FIG. 3 is a gas chromatogram of an eluent of the target material of the present invention;
FIG. 4 is a gas chromatogram of the material eluent in example 1 of the present invention;
FIG. 5 is a gas chromatogram of the material eluent in example 3 of the present invention;
FIG. 6 is a gas chromatogram of the material eluent in example 5 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred experimental methods and materials described herein are for illustrative purposes only.
The invention provides a material capable of enriching nitrosamines in air, which is a mixture of a metal oxide or metal salt modified inorganic material and an antioxidant. The invention loads the metal oxide or metal salt on the inorganic material by a physical modification mode, and mixes the antioxidant with the inorganic material. The positive charge field formed by the metal salt or the metal oxide loaded on the inorganic material enables the nitrosamine to enable the nitroso head with stronger electronegativity to enter the aperture, and the 'embedded' adsorption of the nitrosamine target object specificity is realized based on the positive charge field formed by the metal salt or the metal oxide; because the metal oxide can provide a stronger positive charge field, the modified inorganic material has better adsorption performance on nitrosamine; in addition, the pore diameter of the selected inorganic material is smaller, so that the specific adsorption of the adsorbent to nitrosamine in the air matrix can be realized by forming an exclusion effect on macromolecular interferents in the complex air matrix.
According to the invention, the antioxidant is doped in the material in a physical mixing mode, so that the oxynitride in the air can be effectively prevented from being converted into nitrosamine in the trapping process, and the interference of false positive on the detection result is avoided.
Example 1 preparation of magnesium acetate modified nitrosamine adsorption Material
8g of magnesium acetate was taken and stirred mechanically for 20min at 300 r/min. 20g of silica was added and stirring was continued for 8h. Suction filtration and drying at 60 ℃ for 12 hours. 0.08g of sulfamic acid was added to prepare a magnesium acetate modified nitrosamine adsorption material. The EDS characterization diagram is shown in fig. 1, and the BET and BJH characterization diagrams are shown in fig. 2.
Example 2 preparation of magnesium sulfate-modified nitrosamine adsorption Material
120g of magnesium sulfate was taken and stirred mechanically at 300r/min for 120min. 200g of celite was added and stirring was continued for 8h. Suction filtration and drying at 60 ℃ for 12 hours. 12g of sulfamic acid was added to prepare a magnesium sulfate modified nitrosamine adsorption material.
EXAMPLE 3 preparation of sodium sulfate modified nitrosamine adsorption Material
8g of sodium sulfate was taken and stirred mechanically for 20min at 300 r/min. 20g zeolite was added and stirring was continued for 8h. Suction filtration and drying at 60 ℃ for 12 hours. Sodium metabisulfite (0.08 g) was added to prepare a sodium sulfate modified nitrosamine adsorption material.
EXAMPLE 4 preparation of copper chloride-modified nitrosamine adsorption Material
120g of copper chloride was taken and stirred mechanically for 120min at 350 r/min. 200g of molecular sieve are added and stirring is continued for 24h. Suction filtration and drying at 60 ℃ for 12 hours. 12g of sodium metabisulfite is added to prepare the copper chloride modified nitrosamine adsorption material.
EXAMPLE 5 preparation of copper oxide-modified nitrosamine adsorption Material
150g of basic copper carbonate is taken and mechanically stirred for 120min at 350 r/min. 200g of silica were added and stirring was continued for 24h. Suction filtration and drying at 60 ℃ for 12 hours. 15g of ascorbic acid is added, and the material is calcined in a muffle furnace at 300 ℃ for 4 hours to prepare the copper oxide modified nitrosamine adsorption material.
EXAMPLE 6 preparation of magnesia modified nitrosamine adsorption Material
150g of magnesium acetate are taken and mechanically stirred at 350r/min for 120min. 200g of celite was added and stirring was continued for 24h. Suction filtration and drying at 60 ℃ for 12 hours. 15g of ascorbic acid is added, and the material is calcined in a muffle furnace at 500 ℃ for 4 hours to prepare the magnesium oxide modified nitrosamine adsorption material.
Example 7 application of magnesium acetate modified nitrosamine adsorption Material in enrichment of nitrosamines
Taking a nitrosamine enrichment column of a certain international brand as a standard matching material, and injecting 4 mu L of nine nitrosamine mixed standard solutions (500 ppm) into an air inlet hole of a sampling tube according to a pretreatment mode (Doi: 10.1021/ac50052a 014) in a literature; air was purged at a flow rate of 500ml/min for 8 hours, after which the purge was completed with methylene chloride: acetone (1:1, V/V) eluted from the sampling tube and then entered into GC-MS for analysis, the chromatogram is shown in FIG. 3.
The prepared material was packed in a small column (1 g from example 1) and the eluate was subjected to the same pretreatment step and subjected to gas chromatography, the chromatogram being shown in fig. 4, and the results being shown in table 1.
Example 8 use of sodium sulfate modified nitrosamine adsorption Material for enrichment of nitrosamines
The prepared material was packed in a small column (1 g from example 3) and the eluate was subjected to gas chromatography (chromatogram see fig. 5) by the pretreatment procedure in example 7, and the results are shown in table 1.
Example 9 use of copper oxide modified nitrosamine adsorption Material for enrichment of nitrosamines
The prepared material was packed in a small column (1 g from example 5) and the eluate was subjected to gas chromatography (chromatogram see fig. 6) by the pretreatment procedure in example 7, and the results are shown in table 1.
TABLE 1
Example 10 verification of false positives of materials
To verify whether the packing was able to prevent false positives, examples 1', 3' and 5' were prepared with reference to the above-described steps of examples 1, 3 and 5, respectively, without the addition of an antioxidant, and the eluate was subjected to gas chromatography analysis by the same pretreatment step of example 7, and the results are shown in table 2.
TABLE 2
As can be seen from the combination of Table 1, when no antioxidant is added to the material, there is an abnormal recovery rate of the nine nitrosamines, which may be the conversion of the nitrogen oxide compounds in the air to nitrosamines. The material prepared by the method can effectively adsorb nine kinds of nitrosamines, can avoid the condition that nitrogen oxides are converted into nitrosamines to cause false positive in the process of trapping the nitrosamines, and is suitable for enriching the nitrosamines in the air.
While the invention has been described with reference to the preferred embodiments, it is not intended to limit the invention thereto, and it is to be understood that other modifications and improvements may be made by those skilled in the art without departing from the spirit and scope of the invention, which is therefore defined by the appended claims.

Claims (7)

1. The preparation method of the adsorbent for enriching the nitrosamine in the air is characterized in that the adsorbent is formed by mixing an inorganic material and an antioxidant, and the inorganic material is a metal oxide modified inorganic material;
the preparation method comprises the following steps:
s1, preparing a metal salt solution by a mechanical stirring mode;
s2, placing the inorganic material into a metal salt solution to prepare a metal salt loaded inorganic material;
s3, mixing the inorganic material modified by the metal oxide with an antioxidant in a physical mixing mode to obtain a nitrosamine adsorption material;
for inorganic materials loaded by metal salt, the step S3 further comprises the steps of taking the inorganic materials modified by metal salt and calcining 2-12 h in a muffle furnace at 400-1000 ℃ to obtain the inorganic materials modified by metal oxide;
the antioxidant is metabisulfite, sulfamic acid or ascorbic acid.
2. The method for preparing an adsorbent for enriching nitrosamines in air according to claim 1, wherein the inorganic material and the antioxidant are mixed according to a mass ratio of 1-5:0.01-0.1.
3. The method for preparing an adsorbent for enriching nitrosamines in air according to claim 1, wherein the inorganic material is diatomaceous earth, silica or molecular sieve.
4. The method for preparing an adsorbent for enriching nitrosamines in air according to claim 1, wherein the metal salt is magnesium sulfate, magnesium acetate, calcium carbonate or basic copper carbonate, and the metal oxide obtained after calcination is magnesium oxide, calcium oxide or copper oxide.
5. The method for preparing an adsorbent for enriching nitrosamines in air according to claim 1, wherein the step S1 is to take metal salt, add solvent, mechanically stir for 20-120 min at a stirring speed of 250-400 r/min and then put into metal salt solution; step S2, adding inorganic materials into the metal salt solution, and mechanically stirring at a stirring speed of 250-400 r/min for 12-24 h; the solvent is removed by suction filtration, and the inorganic material modified by metal salt is obtained by drying 12h at 60 ℃.
6. The method for preparing an adsorbent for enriching nitrosamines in air according to claim 5, wherein the solvent: metal salt: the inorganic material is 1-5 mL, 0.04-0.6 g and 0.2-1 g, and the solvent is deionized water, methanol or ethanol.
7. The method for preparing an adsorbent for enriching nitrosamines in air according to claim 1, wherein the mixing mode adopted in the step S3 is grinding, ultrasonic vibration or mechanical stirring.
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