CN104634619A - Sampling tube for acquiring formaldehyde in air - Google Patents
Sampling tube for acquiring formaldehyde in air Download PDFInfo
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- CN104634619A CN104634619A CN201310442213.5A CN201310442213A CN104634619A CN 104634619 A CN104634619 A CN 104634619A CN 201310442213 A CN201310442213 A CN 201310442213A CN 104634619 A CN104634619 A CN 104634619A
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Abstract
The invention discloses a sampling tube for acquiring formaldehyde in air. The sampling tube is a hollow glass tube 2 with two open ends, the tube is filled with a solid adsorption silica gel 1, the solid adsorption silica gel 1 is fixed in the glass tube through glass cotton 4, and the surface of the solid adsorption silica gel is coated with a derivating agent pentafluorophenyl hydrazine (PFPH). The glass tube is filled with silica gel particles in two segments, and the glass tube is sealed to make the sampling tube; and the sampling tube is connected with a sampler to acquire formaldehyde in air, and formaldehyde reacts with the PFPH on the silica gel in order to realize online derivation. The sampling tube has the advantages of making convenience, small size, long preservation time, high sampling efficiency, convenience for subsequent detection, and very high practical popularization application values.
Description
Technical field
The invention belongs to the monitoring field of surrounding air, particularly a kind of sampling pipe for gathering formaldehyde in air.
Background technology
Formaldehyde is the simplest, common, that content is high aldehyde material, one of indoor major pollutants.At normal temperatures colourless, there is the gas that intense stimulus smells taste, relative density is 1.067, fusing point-92 DEG C, boiling point-19.5 DEG C, can be miscible in any proportion with water, ethanol, acetone and other organic solvent.
Formaldehyde extensively exists with environment, formaldehyde in room air is mainly derived from the artificial board of finishing material and the use of new composite furniture, the product such as coating, chemical fibre carpet, cosmetics, floor glue of antiseptic is made of formaldehyde, also can slow releasing formaldehyde, also have a small amount of formaldehyde from the industrial gaseous waste of outdoor, vehicle exhaust and photochemistry cigarette etc. simultaneously.The healthy generation of formaldehyde to the mankind is many unfavorable, main manifestations is spread effect, sensitization and mutagenesis, that outstanding behaviours has headache, dizziness, weak, Nausea and vomiting, uncomfortable in chest, ophthalmodynia, has a throat-ache, stomach is received is poor, palpitaition, have a sleepless night, lose weight, failure of memory and vegetative nervous disorder etc.; Pregnant woman sucks for a long time and may cause fetal anomaly, and even dead, man sucks for a long time and can cause man's teratospermia, death etc.Formaldehyde has been listed in an important indicator in air ambient pollutant monitoring.
The collection of formaldehyde in indoor air mainly contains solution absorption method and solid phase absorption process.AHMT(4-amino-3-hydrazine-5-sulfydryl-1,2, the 4-triazole that GB adopts) and phenol reagent method; The alcoholic solution absorption process of DNPH, formaldehyde and its reaction afterproduct are through liquid chromatographic detection.There is following problem in what use said method: the acidity that the process for preparation of chemical solution is loaded down with trivial details, chemical reagent consumption amount greatly, repeatedly measures or alkali condition are difficult to be consistent; Need larger bubbles absorption tube during sampling, bring restriction to transport and preservation; Generate substance that show color and need longer induction period, developing time is difficult to strict control, and color product is difficult to long preservation; Spectrophotometry sensitivity is low, poor repeatability, and error is larger.
Solid absorption method mainly contains: ACF-derives collection-Thermal desorption-vapor-phase chromatography, and with activated carbon fiber (ACF) for absorption carrier, adjacent PFBBR azanol (PFBHA) derivating agent of load carries out formaldehyde sampling; Adopt silica gel or the florisil silica particle of DNPH coating; The absorption layer of hydrosulfite dipping; The synthetic fibre tows etc. of the surface modification of coating formaldehyde absorbent.But said method exists or preparation process is complicated, expensive, or sampling efficiency is low, sensitivity is low, or is unfavorable for the problems such as subsequent analysis monitoring.
Summary of the invention
The object of the present invention is to provide a kind of sampling pipe for gathering formaldehyde in air.
Realizing technical scheme of the present invention is:
A kind of sampling pipe for gathering formaldehyde in air, described sampling pipe is that the glass tube 2(of the both ends open of hollow is convenient to fill wherein or take out silica gel absorber, glass tube can be reused), solid absorption silica gel 1 is filled with in pipe, solid absorption silica gel 1 glass wool 4 is fixed in glass tube, described solid absorption Silica Surface coating derivating agent phenyl-pentafluoride hydrazine (PFPH).
Wherein, solid absorption silica gel divides two sections to be filled in glass tube, and middle and two ends glass wool is fixed, and wherein the glass wool of one end is fixing (when sampling with U-shaped little iron wire 3, the sampling pipe of air sampler is connected with one end of U-shaped iron wire, can guarantee that any vibration does not occur adsorbent during sampling).
The inner rubber cap 6 being coated with vacuum grease 5 in advance in glass tube opening two ends carries out sealing (vacuum grease sealing is good, is not subject to external environment influence, stable in properties).Sampling pipe can be prepared in batches, preserves with room temperature or refrigerator.
The method of sampling of above-mentioned sampling pipe, comprises the following steps:
Step one, connects air sampler by sampling pipe near one end of U-shaped little iron wire, and the other end exposes in atmosphere;
Step 2, sets different sampling rates, sampling time according to the concentration of formaldehyde in air, samples;
Step 3, after sampling terminates, takes out sampling pipe, rubber cap on coating vacuum grease bonnet, and sampling pipe is placed in room temperature or refrigerator and preserves;
Step 4, pours out the silica gel in sampling pipe, detects after acetonitrile, analyzes its elution efficiency.
Wherein, in step one, at least one sampling pipe connects air sampler.
In step 2, the setting in sampling rate and sampling time must meet sampling efficiency and reaches more than 90%.
Need in step 4 to carry out secondary acetonitrile, by concentrated after eluent mixing, then measure.
Solid absorption silica gel divides two sections of objects be filled in glass tube to be: fill two sections of silica gel and both made full use of glass tube, be beneficial to again and analyze the sampling efficiency of each sampling process.The content that the formaldehyde analyzed in back segment sampling pipe accounts for leading portion formaldehyde can obtain the sampling efficiency of this sampling, thus judges the validity of sampling.Series connection two single hop sampling pipes can be avoided like this, simplify experimental procedure.
The present invention compared with prior art its remarkable advantage is: (1) have developed a kind of novel sampling pipe for active acquisition formaldehyde in air, can be used in detecting the formaldehyde in air; (2) PFPH during sampling on formaldehyde and silica gel carries out On-chip derivatization reaction, and generation phenyl-pentafluoride hydrazone, can be directly used in subsequent detection analysis, easy and simple to handle; (3) choose novel derivating agent PFPH, fast, product stable, is easy to subsequent measurements analysis for PFPH and formaldehyde reaction; (4) choose cheap and easy to get, the adsorbent silica gel (60-80 order) that absorption property is high, silica gel specific surface area is large, is easy to be coated with absorbing liquid, is easy to wash-out; (5) vacuum grease sealing of sampling replaces traditional sealing glass Sealing Method, makes that sampling pipe is easy to make, volume is little, and the holding time is long, is applicable to batch synchronization and samples, have very high practical extending application value.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of formaldehyde sampling pipe.
The sampling efficiency of sampling pipe when Fig. 2 is different PFPH coating weight.
The sampling efficiency of sampling pipe when Fig. 3 is different sampling rate.
The sampling efficiency of sampling pipe when Fig. 4 is different sampling stages under 3 kinds of concentration.
Fig. 5 is the retention of sampling pipe at 3 kinds of temperature.
Embodiment
A kind of sampling pipe for gathering formaldehyde in air, described sampling pipe is that the glass tube 2(of the both ends open of hollow is convenient to fill wherein or take out silica gel absorber, glass tube can be reused), solid absorption silica gel 1 is filled with in pipe, solid absorption silica gel 1 glass wool 4 is fixed in glass tube, described solid absorption Silica Surface coating derivating agent phenyl-pentafluoride hydrazine.
Wherein, solid absorption silica gel divides two sections to be filled in glass tube, and middle and two ends glass wool is fixed, and wherein the glass wool of one end is fixing (when sampling with U-shaped little iron wire 3, the sampling pipe of air sampler is connected with one end of U-shaped iron wire, can guarantee that any vibration does not occur adsorbent during sampling).
The inner rubber cap 6 being coated with vacuum grease 5 in advance in glass tube opening two ends carries out sealing (vacuum grease sealing is good, is not subject to external environment influence, stable in properties).Sampling pipe can be prepared in batches, preserves with room temperature or refrigerator.
A kind of sampling pipe for gathering formaldehyde in air is prepared and the method for sampling:
1), material prepares: the acetonitrile solution of preparation derivating agent phenyl-pentafluoride hydrazine (PFPH); Silica gel particle is after tap water cleaning, and be placed on through sulfuric acid soaked overnight in beaker, be repeatedly washed to neutrality, be positioned over 300 DEG C of activation 4h in muffle furnace after oven dry, the sealing bag putting into cleaning after cooling saves backup, the same silica gel treatment of glass wool.Glass tube (8cm*6mm*8mm) is put into supersonic wave cleaning machine and is cleaned, deionized water rinsing, dries at 110 DEG C;
2), the dipping of absorbing liquid: be soaked in by 2g silica gel in 3mLPFPH solution, after High Purity Nitrogen dries up solvent, obtain the silica gel of even spread PFPH, coating weight is 0.5mgPFPH/200mg silica gel.Silica gel particle absorption property is high, Heat stability is good, stable chemical nature, has higher physical strength;
3), silica gel filling: will insert in glass tube after the silica gel precise in step b, divide two sections and insert, leading portion be 150mg, and back segment is 50mg, and it is fixing that appropriate cleaned glass cotton is filled at middle and two ends, and inserts the vibration of silica gel when U-shaped little iron wire prevents from sampling.Silica gel particle specific surface area is large, and absorption property is high, and the formaldehyde in air is easily absorbed by the derivating agent of its surface coating;
4), by the sampling pipe silica gel back segment prepared be connected with sampling thief, first leading portion silica gel gather formaldehyde.Reasonable set sampling time and sampling rate, in virtual space, (containing formaldehyde) samples, after sample collection completes, rubber cap beyond the Great Wall after sampling pipe end coating vacuum grease again, sealing preservation more than 5 hours, ensures that formaldehyde and derivating agent react completely;
5), by section silica gel of two in sampling pipe pour into respectively in ampoule bottle, successively add two parts of 2mL acetonitriles and carry out wash-out, be concentrated into 2mL by after two parts of eluent mixing, now elution efficiency reaches more than 98%, and absorption is not residual on silica gel for derivating agent and product;
6), gas chromatography-electron capture detector (ECD) (GC/ECD) detect, calculate concentration of formaldehyde;
7) sampling efficiency of sampling pipe, is measured.
In order to determine that the best of sampling pipe uses and sampling condition, in analog sampling space, carry out a series of Optimum Experiment.By capacitive equipments, measure the coating weight of PFPH on silica gel in sampling pipe respectively, the sampling time, sampling rate on the impact of sampling efficiency, the retention of analytical sampling pipe simultaneously.
Each influence factor experimental technique as follows:
Embodiment 1
PFPH coating weight: the acetonitrile solution of the PFPH of preparation variable concentrations, be coated with the silica gel particle of equivalent respectively, after High Purity Nitrogen dries up solvent acetonitrile, obtain the silica gel particle that coating weight is 0.2 ~ 0.5 mg/200mg silica gel, sample after filling sampling pipe, after wash-out, GC/ECD analyzes.Find the increase along with coating weight, sampling efficiency increases, and when coating weight reaches 0.4mg/200mg silica gel, sampling efficiency has reached 100%(Fig. 2).
Embodiment 2
Sampling rate: after determining best coating weight, prepare sampling pipe is the condition down-sampling of 200 ~ 800 mL/min in the sampling rate of sampling pump, and after wash-out, GC/ECD analyzes.Find the increase along with sampling rate, sampling efficiency can decline, and when ensureing that sampling efficiency is high while, sampling volume is large, select the speed of 300mL/min, sampling efficiency now, still higher than 98%, reaches requirement of experiment.
Embodiment 3
In the sampling time: after determining coating weight and sampling rate, prepare sampling pipe, in virtual space, inject inequality formaldehyde, make its concentration be respectively 1 μ g/L, 5 μ g/L, 10 μ g/L.Sample 20 min respectively, 30 min, 60 min, 90 min, 120min, and after wash-out, GC/ECD analyzes.When finding that the sampling time is long, have part propylene aldehyde to penetrate sampling pipe, sampling efficiency declines, the concentration of this and formaldehyde also has relation, the 90min that can sample when concentration is low still keeps the efficiency of 100%, and then sample during concentration height 60min, can reach the sampling efficiency (Fig. 4) of 97%.
Embodiment 4
Sampling pipe retention: prepare sampling pipe, is divided into 4 groups, and wherein one group as blank, injects the formaldehyde standard solution of equivalent respectively, sealed by sampling pipe in its excess-three group sampling pipe.Blank group preserved at room temperature, all the other three components are not kept at 25 DEG C, 4 DEG C, and at-20 DEG C, sampling pipe is taken out in timing, and after eluting silica gel, GC/ECD analyzes.Find that blank sampling pipe at room temperature preserves 10 days, sealing property is still good, for detecting formaldehyde.And the recovery is still more than 90% in the sampling pipe of collected specimens at room temperature 10 days, during Cord blood, the recovery is then higher.
Claims (8)
1. one kind for gathering the sampling pipe of formaldehyde in air, it is characterized in that: described sampling pipe is the glass tube (2) of the both ends open of hollow, solid absorption silica gel (1) is filled with in pipe, solid absorption silica gel (1) glass wool (4) is fixed in glass tube, described solid absorption Silica Surface coating derivating agent phenyl-pentafluoride hydrazine.
2. sampling pipe according to claim 1, is characterized in that: solid absorption silica gel divides two sections to be filled in glass tube, and middle and two ends glass wool is fixed, and wherein the glass wool of one end is fixed with U-shaped little iron wire (3).
3. sampling pipe according to claim 1, is characterized in that; The rubber cap (6) that inside, glass tube opening two ends is coated with vacuum grease (5) in advance seals.
4. sampling pipe according to claim 1, is characterized in that: sampling pipe can be prepared in batches, preserves with room temperature or refrigerator.
5. a method of sampling for sampling pipe as claimed in claim 1, is characterized in that, comprise the following steps:
Step one, connects air sampler by sampling pipe near one end of U-shaped little iron wire, and the other end exposes in atmosphere;
Step 2, sets different sampling rates, sampling time according to the concentration of formaldehyde in air, samples;
Step 3, after sampling terminates, takes out sampling pipe, rubber cap on coating vacuum grease bonnet, and sampling pipe is placed in room temperature or refrigerator and preserves;
Step 4, pours out the silica gel in sampling pipe, detects after acetonitrile, analyzes its elution efficiency.
6. the method for sampling according to claim 5, is characterized in that, in step one, at least one sampling pipe connects air sampler.
7. the method for sampling according to claim 5, is characterized in that, in step 2, the setting in sampling rate and sampling time must meet sampling efficiency and reaches more than 90%.
8. the method for sampling according to claim 5, is characterized in that, needs to carry out secondary acetonitrile in step 4, by concentrated after eluent mixing, then measures.
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| CN201310442213.5A CN104634619A (en) | 2013-11-12 | 2013-11-12 | Sampling tube for acquiring formaldehyde in air |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105115785A (en) * | 2015-08-26 | 2015-12-02 | 杭州普洛赛斯检测科技有限公司 | Preparation method of sampling tube of dimethylamine and trimethylamine in air and waste gas |
| CN105435412A (en) * | 2015-12-10 | 2016-03-30 | 刘智懿 | Hydrogel for rapidly removing aldehydes and ketones compounds and preparing method of hydrogel |
| CN106769243A (en) * | 2016-12-19 | 2017-05-31 | 广电计量检测（成都）有限公司 | A kind of amine sampling pipe and preparation method thereof and its application method |
| CN107983138A (en) * | 2017-11-15 | 2018-05-04 | 王军 | Load inorganic silica gel of aldehyde remover and preparation method thereof |
| CN109164099A (en) * | 2018-10-29 | 2019-01-08 | 张垚 | A method of detection indoor formaldehyde content |
| CN113600136A (en) * | 2021-08-04 | 2021-11-05 | 北京市劳动保护科学研究所 | Preparation method of solid adsorbent for collecting ammonia in air and sampling pipe |
| CN114199639A (en) * | 2021-11-03 | 2022-03-18 | 广东省职业病防治院(广东省职业卫生检测中心) | Air sampling detection method for nitrobenzene compounds |
| CN116793773A (en) * | 2023-08-25 | 2023-09-22 | 安徽农业大学 | Malodorous gas sampling device for livestock farm |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105115785A (en) * | 2015-08-26 | 2015-12-02 | 杭州普洛赛斯检测科技有限公司 | Preparation method of sampling tube of dimethylamine and trimethylamine in air and waste gas |
| CN105115785B (en) * | 2015-08-26 | 2017-10-10 | 杭州普洛赛斯检测科技有限公司 | The preparation method of dimethylamine and trimethylamine sampling pipe in a kind of air and waste gas |
| CN105435412A (en) * | 2015-12-10 | 2016-03-30 | 刘智懿 | Hydrogel for rapidly removing aldehydes and ketones compounds and preparing method of hydrogel |
| CN106769243A (en) * | 2016-12-19 | 2017-05-31 | 广电计量检测（成都）有限公司 | A kind of amine sampling pipe and preparation method thereof and its application method |
| CN107983138A (en) * | 2017-11-15 | 2018-05-04 | 王军 | Load inorganic silica gel of aldehyde remover and preparation method thereof |
| CN109164099A (en) * | 2018-10-29 | 2019-01-08 | 张垚 | A method of detection indoor formaldehyde content |
| CN113600136A (en) * | 2021-08-04 | 2021-11-05 | 北京市劳动保护科学研究所 | Preparation method of solid adsorbent for collecting ammonia in air and sampling pipe |
| CN114199639A (en) * | 2021-11-03 | 2022-03-18 | 广东省职业病防治院(广东省职业卫生检测中心) | Air sampling detection method for nitrobenzene compounds |
| CN116793773A (en) * | 2023-08-25 | 2023-09-22 | 安徽农业大学 | Malodorous gas sampling device for livestock farm |
| CN116793773B (en) * | 2023-08-25 | 2023-11-07 | 安徽农业大学 | Malodorous gas sampling device for livestock farm |
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Application publication date: 20150520 |