CN108614045A - The detection method of formaldehyde in the preparation method and surrounding air of a kind of formaldehyde sampling pipe - Google Patents
The detection method of formaldehyde in the preparation method and surrounding air of a kind of formaldehyde sampling pipe Download PDFInfo
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- CN108614045A CN108614045A CN201810388266.6A CN201810388266A CN108614045A CN 108614045 A CN108614045 A CN 108614045A CN 201810388266 A CN201810388266 A CN 201810388266A CN 108614045 A CN108614045 A CN 108614045A
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- formaldehyde
- pfbha
- carbon fiber
- activated carbon
- bacteria cellulose
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 370
- 238000005070 sampling Methods 0.000 title claims abstract description 72
- 238000001514 detection method Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- UOISMTPJFYEVBW-UHFFFAOYSA-N o-[(2,3,4,5,6-pentafluorophenyl)methyl]hydroxylamine Chemical compound NOCC1=C(F)C(F)=C(F)C(F)=C1F UOISMTPJFYEVBW-UHFFFAOYSA-N 0.000 claims abstract description 67
- 241000894006 Bacteria Species 0.000 claims abstract description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003463 adsorbent Substances 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 229920002678 cellulose Polymers 0.000 claims abstract description 49
- 239000001913 cellulose Substances 0.000 claims abstract description 49
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000003795 desorption Methods 0.000 claims abstract description 5
- 239000000523 sample Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 238000004817 gas chromatography Methods 0.000 claims description 20
- 238000004458 analytical method Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 9
- 238000004587 chromatography analysis Methods 0.000 claims description 8
- 238000004445 quantitative analysis Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012496 blank sample Substances 0.000 claims description 4
- 238000011088 calibration curve Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012491 analyte Substances 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims 2
- 238000001212 derivatisation Methods 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 5
- 239000003570 air Substances 0.000 description 62
- 239000000243 solution Substances 0.000 description 23
- 238000005259 measurement Methods 0.000 description 14
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007812 deficiency Effects 0.000 description 5
- 238000012417 linear regression Methods 0.000 description 5
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000012080 ambient air Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 238000003965 capillary gas chromatography Methods 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- -1 aldehyde ketone Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 230000003902 lesion Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 206010064571 Gene mutation Diseases 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000013566 allergen Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000005096 hematological system Anatomy 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 150000004031 phenylhydrazines Chemical class 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/30—Control of physical parameters of the fluid carrier of temperature
-
- G01N30/48—
-
- G01N30/482—
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
-
- G01N2030/484—
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention provides a kind of preparation method of formaldehyde sampling pipe and the detection method of formaldehyde in surrounding air, the preparation method of the formaldehyde sampling pipe include：It learns from else's experience the PFBHA derivating agents of purifying；Bacteria cellulose-base nanometer activated carbon fiber adsorbent is taken, the impurity wherein adsorbed is removed, and be modified to it, to obtain modified bacteria cellulose base nanometer activated carbon fiber adsorbent；Purified PFBHA derivating agents are added in modified bacteria cellulose base nanometer activated carbon fiber adsorbent, persistently stir the predetermined time, PFBHA derivating agents are carried on modified bacteria cellulose base nanometer activated carbon fiber adsorbent；There is the modified bacteria cellulose base nanometer activated carbon fiber adsorbent of PFBHA derivating agents to be packed into sample cell load.Formaldehyde in the preparation method and surrounding air of formaldehyde sampling pipe provided by the invention in the detection method On-chip derivatization of formaldehyde, absorption, acquisition surrounding air, so as to detect the formaldehyde in surrounding air by direct Thermal desorption capillary gas chromatograph.
Description
Technical field
The present invention relates to the sampling technique of formaldehyde in surrounding air and its detection techniques, and in particular, to a kind of formaldehyde is adopted
The detection method of formaldehyde in the preparation method and surrounding air of sample pipe.
Background technology
Formaldehyde is pollutant important in surrounding air, especially in various indoor environments, public place, industrial operations field
Institute, the formaldehyde pollution generally existing in surrounding air.When human body long-term low dose is after respiratory tract and skin inhaled formaldehyde, can draw
It sends out respiratory system, hematological system, nervous system, reproductive system and internal organs damage and lesion.The World Health Organization is
Confirmed formaldehyde is teratogenesis, carcinogenic, cause gene mutation substance, and formaldehyde is that human body generates lesion and allergen, it is in China
It is in second on toxic chemical priority acccess control list.Therefore, the monitoring Yu control of Formaldehyde in Environment is one and is related to full society
The important process of meeting.
In recent years, China formulates《Indoor Air Quality standards》、《Civil building engineering indoor environmental pollution control rule
Model》、《Indoor decorating and refurnishing materials limits of harmful substances standard》Etc. series of standards, formaldehyde in indoor environment is monitored and
Control.In these monitoring standards, formaldehyde mainly uses two class detection method of spectrophotometry and gas-chromatography.In phenol reagent point
When light Photometric Determination of Formaldehyde, the presence of acetaldehyde, propionic aldehyde, which can generate result, just to be interfered, and there are can make when sulfur dioxide in environment
Lower result is needed using manganese sulfate filter paper filtration method come exclusive PCR, in sampling to have inconvenience more.In acetylacetone,2,4-pentanedione spectrophotometric
When method measures formaldehyde in air, though testing cost is relatively low, stability is good, when content of formaldehyde is relatively low, nothing due to sensitivity is low
Method normally measures, and all needs to take during sample collection, transport and storage and be protected from light, be stored refrigerated, and need to analyze in time,
Practical operation has inconvenience more.
In gas-chromatography detection method, since formaldehyde is the stronger molecule of polarity, capillary gas phase cannot be directly used
Chromatographic determination formaldehyde in indoor air, otherwise will appear chromatography broad peak, drag peak and it is bimodal phenomena such as, cause it is linear it is poor, measure spirit
The low restriction with detectable limit of sensitivity.Therefore, Environmental Protection Agency USA (USEPA) is in TO-11, IP-6A, IP-6B, IP-6C
Aldehyde and ketone in surrounding air are detected with 2,4 dinitrophenyl hydrazine derivatization method；Equally, also by 2,4- dinitros in China's national standard
Phenylhydrazine derivative, carbon disulfide elution, chromatography post separation, flame ionization ditector gas chromatography measure formaldehyde in air row
For important assay method.Though this method have it is easy to operate, measure it is linear it is wider, separating degree is good, high sensitivity, reproducible etc.
Advantage, but chromatographic column specially must be used, instrument utilization ratio is relatively low；With 2,4-dinitrophenylhydrazine derivatization, efficient liquid phase is used
Operating process is complicated when aldehyde ketone in chromatographic determination air, instrument price is expensive, is difficult to popularize.
When surrounding air is directly sampled due to being influenced by environment temperature, humidity, sampling rate, adsorption capacity imitates sampling
The influence of rate is notable, easily causes measurement result severe deviations.Due to not pre-processed also no pair to the air of pollution
Checking matter is concentrated, and cannot eliminate the influence of chaff interferent to the maximum extent, ineffective to the formaldehyde measurement of trace；Sample is adopted
After collection, in analysis, still needs to be eluted with a large amount of organic solvent, the 5~15% of total amount is only accounted for for detecting, environment is produced
Raw secondary pollution, does not meet the demand for development of environment friend's type analysis trend.
Therefore, studying quick, easy, efficient, environmental-friendly novel environmental formaldehyde in air detection method becomes one
Important research topic.
Invention content
A series of concept of reduced forms is introduced in Summary, this will in the detailed description section into
One step is described in detail.The Summary of the present invention is not meant to attempt to limit technical solution claimed
Key feature and essential features do not mean that the protection domain for attempting to determine technical solution claimed more.
In view of the deficiencies of the prior art, the present invention provides a kind of preparation methods of formaldehyde sampling pipe, including：
It learns from else's experience the PFBHA derivating agents of purifying；
Bacteria cellulose-base nanometer activated carbon fiber adsorbent is taken, removes the impurity adsorbed in the adsorbent, and to it
It is modified, to obtain modified bacteria cellulose base nanometer activated carbon fiber adsorbent；
The purified PFBHA is added in the modified bacteria cellulose base nanometer activated carbon fiber adsorbent to derive
The predetermined time is persistently stirred in agent, and the PFBHA derivating agents are carried on the modified bacteria cellulose base nano active carbon fiber
It ties up on adsorbent；And
There is the modified bacteria cellulose base nanometer activated carbon fiber adsorbent of PFBHA derivating agents to be packed into sample load
In quality control.
Illustratively, the step of being purified to the PFBHA derivating agents include：Using normal hexane to PFBHA solution into
Row extracts three times, discards first and second extract liquor extracted, and reservation third time extracts the extract liquor of gained, required with acquisition
PFBHA hexane solutions.
Illustratively, the concentration of PFBHA is more than 2mg/mL in the PFBHA normal hexanes solution.
Illustratively, the method being modified to the bacteria cellulose-base nanometer activated carbon fiber adsorbent is：By institute
State bacteria cellulose-base nanometer activated carbon fiber adsorbent and impregnate 8 hours or more in concentrated sulfuric acid, then use distilled water flushing 3~
5 times, and remove moisture and impurity therein.
Illustratively, the PFBHA derivating agents modified bacteria cellulose base nanometer activated carbon fiber is carried on to inhale
Step on attached dose includes：It is added in the modified bacteria cellulose base nanometer activated carbon fiber adsorbent described purified
PFBHA derives impregnate 1 hour or more in agent solution, and continues to stir 30 minutes or more.
Illustratively, the modified bacteria cellulose base nanometer activated carbon fiber adsorbent dress for having derivating agent will loaded
It inserts after the step in sample cell, further includes under nitrogen purge to the modified bacteria cellulose base nanometer activated carbon fiber
Adsorbent is heated, to remove solvent and impurity therein.
The present invention also provides a kind of detection method of formaldehyde in surrounding air, the detection method includes：
Gas sampler is connected on sampling pipe, air sample is acquired, being filled with load in the sampling pipe has PFBHA
The modified bacteria cellulose base nanometer activated carbon fiber adsorbent of derivating agent；
The sampling pipe for being collected sample is placed into pyrolysis analyzer, connection gas chromatograph carries out Thermal desorption-gas phase color
Spectrum analysis；
Quantitative analysis is carried out to the concentration of formaldehyde in surrounding air according to the result of the analysis.
Illustratively, the sample time for acquiring ambient air sampling is 10min~20min, sampling velocity 0.2L/min
~0.5L/min, sampling amount are 5L~10L.
Illustratively, the initial temperature of the pyrolysis analyzer is set as 45 DEG C, after sample loads, opens gas chromatograph
Afterwards, using the pattern of being rapidly heated, the pyrolysis analyzer is warming up to 300 DEG C~350 DEG C of pyrolysis temperature.
Illustratively, the temperature-rise period of the gas chromatograph is：50 DEG C of initial temperature keeps 10min, with the speed of 5 DEG C/min
Rate is warming up to 180 DEG C, then is warming up to 250 DEG C with the rate of 10 DEG C/min, and keeps 5min.
Illustratively, it is 300 DEG C, hydrogen flowing quantity 40mL/min by fid detector temperature setting, air mass flow is
350mL/min, chromatograph carrier gas column flow are 1mL/min.
Illustratively, the method for the quantitative analysis is：Addition is quantified with formaldehyde standard sample, it is dense with peak area-formaldehyde
Angle value draws standard curve, and compareing the standard curve according to the result of the Thermal desorption-gas chromatographic analysis is quantitatively divided
Analysis.
Illustratively, the computational methods of concentration of formaldehyde are：
First, sampling volume is converted into standard state down-sampling volume as the following formula：
Wherein, V0Sampling volume under standard state
VtSampling volume, Lt=sampling flows (L/min) × sampling time (min)
The temperature of t- sampled points, DEG C
T0Absolute temperature under standard state, T0=373K
The atmospheric pressure of p- sampled points, kPa
p0Atmospheric pressure under standard state, P0=101kPa
Then, air formaldehyde concentration is calculated as follows：
C=(A-A0)×X/V0
Wherein, C- Formaldehyde Concentration of Indoor Air (mg/m3)
A- analyte derivative gas-chromatography peak areas
A0Blank sample derives gas-chromatography peak area
X- is calculated out by standards calibration curve：X=(Y-758)/33238
V0The sampling volume being converted under standard state, L.
The detection method of formaldehyde is by modified bacteria in the preparation method and surrounding air of formaldehyde sampling pipe provided by the invention
The activated carbon fiber loaded derivating agent of cellulose based nano, the formaldehyde in On-chip derivatization, absorption, acquisition surrounding air, so as to logical
Direct Thermal desorption-capillary gas chromatograph is crossed to detect the formaldehyde in surrounding air, compensates for other sample-pretreating methods
And Thermal desorption-gas chromatography cannot direct determination of the environment formaldehyde in air deficiency.
Description of the drawings
The following drawings of the present invention is used to understand the present invention in this as the part of the present invention.Shown in the drawings of this hair
Bright embodiment and its description, device used to explain the present invention and principle.In the accompanying drawings,
Fig. 1 shows the process flow chart of the preparation method for the formaldehyde sampling pipe that one embodiment of the invention provides；
Fig. 2 shows the relation curves of PFBHA solution concentrations and formaldehyde collection efficiency in one embodiment of the invention；
Fig. 3 shows that modified bacteria cellulose base nanometer activated carbon fiber is in PFBHA solution in one embodiment of the invention
The relation curve of the time and formaldehyde collection efficiency of dipping；
Fig. 4 shows the formaldehyde sampling that the preparation method of the formaldehyde sampling pipe provided according to one embodiment of the invention is obtained
The structural schematic diagram of pipe；
Fig. 5 shows the process flow chart of the detection method for the formaldehyde that one embodiment of the invention provides；
Fig. 6 shows that Thermal desorption-gas chromatography in the detection method of the formaldehyde that one embodiment of the invention provides obtains
Sample detection chromatogram；
Fig. 7 shows that the formaldehyde-PFBHA-HCHO oximates in the detection method for the formaldehyde that one embodiment of the invention provides are closed
Object standard curve.
Specific implementation mode
In the following description, a large amount of concrete details are given in order to provide more thorough understanding of the invention.So
And it is obvious to the skilled person that the present invention may not need one or more of these details and be able to
Implement.In other examples, in order to avoid with the present invention obscure, for some technical characteristics well known in the art not into
Row description.
In order to thoroughly understand the present invention, detailed step will be proposed in following description, to illustrate proposition of the present invention
Preparation method.Obviously, execution of the invention is not limited to the specific details that those skilled in the art is familiar with.The present invention
Preferred embodiment be described in detail as follows, however in addition to these detailed description other than, the present invention can also have other embodiment.
It should be understood that when the term " comprising " and/or " including " is used in this specification, indicating described in presence
Feature, entirety, step, operation, element and/or component, but do not preclude the presence or addition of other one or more features, entirety,
Step, operation, element, component and/or combination thereof.
Current Analysis Methods for Formaldehyde includes mainly two class detection method of spectrophotometry and gas-chromatography.In gas-chromatography
In detection method, since formaldehyde is the stronger molecule of polarity, cannot directly it use in capillary gas chromatography room air
Formaldehyde, otherwise will appear chromatography broad peak, drag peak and it is bimodal phenomena such as, cause the linear poor, measurement sensitivity low and detectable limit
It restricts.Therefore, in China's national standard by 2,4 dinitrophenyl hydrazine derivative, carbon disulfide elution, chromatography post separation, hydrogen flame from
Sonization detector gas chromatography measures the important assay method that formaldehyde in air is classified as.However, this method must use it is special
Chromatographic column, instrument utilization ratio are relatively low；With 2,4-dinitrophenylhydrazine derivatization, when measuring aldehyde ketone in air with high performance liquid chromatography
Operating process is complicated, instrument price is expensive, is difficult to popularize.
When surrounding air directly samples, due to being influenced by environment temperature, humidity, sampling rate, adsorption capacity is to sampling
The influence of efficiency is notable, easily causes measurement result severe deviations.Do not have due to not pre-processed to the air of pollution yet
Checking matter is concentrated, the influence of chaff interferent cannot be eliminated to the maximum extent, it is ineffective to the formaldehyde measurement of trace；Sample
After acquisition, in analysis, still needs to be eluted with a large amount of organic solvent, the 5~15% of total amount is only accounted for for detecting, to environment
Secondary pollution is generated, the demand for development of environment friend's type analysis trend is not met.
For above-mentioned at least one technical problem, the present invention provides a kind of preparation methods of formaldehyde sampling pipe, including：It takes
Purified PFBHA derivating agents；It takes bacteria cellulose-base nanometer activated carbon fiber adsorbent, removes and adsorbed in the adsorbent
Impurity, and it is modified, to obtain modified bacteria cellulose base nanometer activated carbon fiber adsorbent；In the modified bacteria
The purified PFBHA derivating agents are added in cellulose based nano activated carbon fiber adsorbent, persistently stir the predetermined time, with
The PFBHA derivating agents are carried on the modified bacteria cellulose base nanometer activated carbon fiber adsorbent；And it will load
There is the modified bacteria cellulose base nanometer activated carbon fiber adsorbent of PFBHA derivating agents to be packed into sample cell.
The present invention also provides a kind of detection methods of formaldehyde, including：Gas sampler is connected on sampling pipe, acquisition is empty
Gas sample product, load is filled in the sampling pipe has the modified bacteria cellulose base nanometer activated carbon fiber of PFBHA derivating agents to inhale
Attached dose；The sampling pipe for being collected sample is placed into pyrolysis analyzer, connection gas chromatograph carries out Thermal desorption-gas-chromatography
Analysis；Quantitative analysis is carried out to the concentration of formaldehyde in air according to the result of the analysis.
The preparation method of formaldehyde sampling pipe provided by the invention and the detection method of formaldehyde are by modified bacteria cellulose Ji Na
The activated carbon fiber loaded derivating agent of rice, the formaldehyde in On-chip derivatization, absorption, acquisition air, so as to pass through direct Thermal desorption-hair
Capillary gas chromatography instrument detects the formaldehyde in surrounding air, compensates for other sample-pretreating methods and Thermal desorption-gas phase color
Spectrometry cannot directly measure the deficiency of formaldehyde in air.
In order to thoroughly understand the present invention, detailed structure and/or step will be proposed in following description, to illustrate this
Invent the technical solution proposed.Presently preferred embodiments of the present invention is described in detail as follows, however other than these detailed descriptions, this hair
It is bright to have other embodiment.[exemplary embodiment one]
Below with reference to Fig. 1, the preparation method of the formaldehyde sampling pipe of an embodiment of the present invention is described in detail.
First, step 101, PFBHA (the o- Wu Fu Benzyl bases azanol) derivating agent for purifying of learning from else's experience are executed.PFBHA derivating agents with
Formaldehyde reaction is very fast, and the On-chip derivatization of formaldehyde may be implemented.When PFBHA molecules encounter the gaseous formaldehyde in air, it may occur that
Carbonyl addition generates PFBHA-HCHO oxime compounds, and oxime is adsorbed and be enriched with by the nanoaperture of nanofiber surface, and with
Air matrix detaches, to achieve the purpose that sample collection.
Wherein, the chemical reaction of formaldehyde and PFBHA derivating agents is：
In order to obtain the derivative reagent of relatively low background, need to purify the PFBHA derivating agents.In the present embodiment, it takes
After PFBHA derivating agents, the PFBHA derivating agents are purified using normal hexane.Illustratively, the purifying of PFBHA derivating agents
Step includes：By the PFBHA solution of 5mL2mg/mL, 2mL normal hexanes are added, are extracted three times, discards first and second extraction
Liquid, retains third time extract liquor, and third time extract liquor is that the concentration of PFBHA is more than the PFBHA normal hexane solution of 2mg/mL.One
In a embodiment, a concentration of 6.8 μm of ol/mL of PFBHA in the third time extract liquor.
Then, step 102 is executed, bacteria cellulose-base nanometer activated carbon fiber adsorbent, heating is taken to remove the absorption
The impurity adsorbed in agent, and it is modified, to obtain modified bacteria cellulose base nanometer activated carbon fiber.
Wherein, bacteria cellulose-base activated carbon nano fiber is a kind of adsorptivity Nanowire of the surface with nanoaperture
Dimension, with good spacial framework, high-specific surface area, splendid adsorption capacity and the rate of adsorption, than common activity
Carbon fibe is more suitable for the adsorbent of formaldehyde sampling pipe.Being modified to bacteria cellulose-base activated carbon nano fiber can carry
Its high surface-active.
Since nanofiber has adsorbed organic impurities in manufacture, transport and storage carry out, to bacteria cellulose
Base nanometer activated carbon fiber is modified before processing, the impurity for needing heating removal wherein to adsorb first.Specifically, warm in stove
Under 280 DEG C of degree, the protection of 0.4Mpa nitrogen, heating removal nanofiber adsorbs organic in manufacture, transport and storage carry out
It is spare after impurity.
Then, processing is modified to bacteria cellulose-base nanometer activated carbon fiber adsorbent using the concentrated sulfuric acid, to obtain
Modified bacteria cellulose base nanometer activated carbon fiber adsorbent.Specifically, bacteria cellulose-base nanometer activated carbon fiber is adsorbed
Agent is impregnated 8 hours or more in concentrated sulfuric acid, then uses distilled water flushing 3-5 times, and solution is downloaded in the protection of flow 0.4Mpa nitrogen
It analyses and is heated in stove to remove the impurity adsorbed in moisture removal and various preparation process, the modified bacteria cellulose base that will then be obtained
Nanometer activated carbon fiber adsorbent is placed in air-tight bottle and preserves.
Then, step 103 is executed, is added through pure in the modified bacteria cellulose base nanometer activated carbon fiber adsorbent
The PFBHA changed derives in agent solution, persistently stirs the predetermined time, it is thin that the PFBHA derivating agents are carried on the modification
On fungin base nanometer activated carbon fiber adsorbent.
During lasting stirring, PFBHA derivating agents are supported on the modified bacteria cellulose with nanoaperture
On base nanometer activated carbon fiber adsorbent.During sample collection, when the formaldehyde in ambient air passes through sampling pipe, born
The modified bacteria cellulose base nanometer activated carbon fiber with nanoaperture for being loaded with derivating agent intercepts, and is quickly sent out with derivating agent
There is specificity and specificity, reaction product can be detached with other matrix in air for raw derivatization reaction, the derivatization reaction, reach point
From the purpose with enrichment.The product of derivatization reaction be modified bacteria cellulose-base nanometer activated carbon fiber surface nanoaperture inhale
It is attached, and detach and be enriched with air matrix, to achieve the purpose that sample collection.
Illustratively, add in batches in the modified bacteria cellulose base nanometer activated carbon fiber adsorbent that 800mg is handled well
Enter the above-mentioned PFBHA hexane solutions purified, persistently stirs 30min or more, PFBHA derivating agents are carried on modified bacteria
On cellulose based nano activated carbon fiber adsorbent.
When being sampled to the formaldehyde in surrounding air, enough PFBHA derivative reagent load capacity are expected to have, environment is made
Formaldehyde in air converts completely, meets the requirement that quantitative analysis measures formaldehyde.In the present embodiment, in order to determine that best PFBHA is negative
Carrying capacity and carried out PFBHA load capacity optimize test.The arithmetic that the collection efficiency value of formaldehyde recycles measurement data with formaldehyde is flat
Mean value is assessed.In the present embodiment, PFBHA solution concentrations and formaldehyde collection efficiency are tested, drawn by test data
In Fig. 2.As shown in Figure 2, when PFBHA solution concentrations are more than 2.0mg/mL, formaldehyde has higher collection efficiency.Therefore, this reality
The concentration for applying the PFBHA solution employed in example is more than 2.0mg/mL.
In order to which adsorbent is immersed in the time in PFBHA solution by determination, to modified bacteria cellulose base nano active carbon
Fiber adsorbing substance is immersed in the time in the PFBHA solution of a concentration of 2.0mg/mL and the relationship of the collection efficiency of formaldehyde carries out
Experiment, experimental result is shown in Fig. 3.From the figure 3, it may be seen that in the dip time of 1h or more, the formaldehyde collection efficiency more than 90% can get.
Therefore, in the present embodiment, modified bacteria cellulose base nanometer activated carbon fiber adsorbent is immersed in a concentration of 2.0mg/mL
PFBHA solution in time be more than 1 hour.
Then, step 104 is executed, load is had to the modified bacteria cellulose base nanometer activated carbon fiber of PFBHA derivating agents
Adsorbent is packed into sample cell.
Specifically, by load have the modified bacteria cellulose base nanometer activated carbon fiber adsorbents of PFBHA derivating agents from
It is packed into sample cell after being taken out in PFBHA solution, the blowback under 80 DEG C, 0.4Mpa nitrogen, to remove normal hexane solvent, distilled water
Equal impurity.Then fixed with stainless steel cloth at modified bacteria cellulose base nanometer activated carbon fiber both ends, make its it is closely knit stopper,
Both ends sealing is stored in hermetic bag.Modified bacteria cellulose base nanometer activated carbon fiber adsorbent can repeat coating, bear
It carries, it, can be reusable after thermal desorption after sampling pipe samples use.Container used is cleaned with normal hexane, and it is molten to dry removal
Agent.It is modified according to the structure chart of the formaldehyde sampling pipe of the method for the present embodiment manufacture as shown in figure 4, specifically including sample cell 401
Bacteria cellulose-base nanometer activated carbon fiber adsorbent 402 and be set to modified bacteria cellulose base nanometer activated carbon fiber suction
The stainless steel cloth 403 of attached dose of 402 both sides.
So far, the introduction of the correlation step of the preparation method of the formaldehyde sampling pipe of the embodiment of the present invention is completed.It can manage
Solution, the present embodiment formaldehyde sampling tube preparation method not only include above-mentioned steps, before above-mentioned steps, among or later
It may also include other desired step, be included in the range of this implementation preparation method.
The preparation method for the formaldehyde sampling pipe that the present embodiment is provided is by modified bacteria cellulose base nanometer activated carbon fiber
Load derivating agent, the formaldehyde in On-chip derivatization, absorption, acquisition air, so as to pass through direct Thermal desorption-capillary gas chromatography
Instrument detects the formaldehyde in surrounding air, compensates for other sample-pretreating methods and Thermal desorption-gas chromatography cannot be direct
Measure the deficiency of formaldehyde in air.
[exemplary embodiment two]
Below with reference to Fig. 5, the detection method of the formaldehyde of an embodiment of the present invention is described in detail.
First, execution step 501, gas sampler is connected on sampling pipe, acquisition air sample, in the sampling pipe
There is the modified bacteria cellulose base nanometer activated carbon fiber adsorbent of PFBHA derivating agents with load.
Specifically, the connection rubber tube on the air inlet of the constant current air sampler with electronics controlling timer is inserted into have and bear
It is loaded with the sampling pipe of the modified bacteria cellulose base nanometer activated carbon fiber adsorbent of PFBHA derivating agents, controls sampling instrument flow
For 0.5mL, 2~10L of air sample is acquired, and record sample volume, sample time, environment temperature, atmospheric pressure data.
Wherein, the air sample acquired is the formaldehyde in indoor environment, is defended according to the public places GBT18204.2-2014
Part 2 in the raw method of inspection：The acquisition of chemical pollutant, ambient air sampling is with reference to HJ/T194-2005 ambient air qualities
Manual Specifications of Monitoring Technology executes.
In order to determine the flow velocity of air sample to obtain preferable formaldehyde collection efficiency, sample flow has been carried out in the present embodiment
Speed and formaldehyde collection efficiency test, experimental result are as shown in Figure 6.It will be appreciated from fig. 6 that under the conditions of smaller sampling velocity, can obtain
Obtain preferable formaldehyde collection efficiency.Therefore in sampling process, low flow velocity, the method for extension sample time is taken to be sampled.
In a preferred embodiment, the best sampling amount range of formaldehyde in air is 5~10L, sample time is 10~
20min.And according to experimental result, sample is carried out using the sampling velocity of 0.2~0.5L/min, to obtain preferably inspection
Survey effect.
Then, step 502 is executed, the sampling pipe for being collected sample is placed into pyrolysis analyzer, connection gas chromatograph,
Carry out Thermal desorption-gas chromatographic analysis.
Illustratively, the instrument condition of the gas chromatograph is：Thermal desorption initial temperature is set as 45 DEG C, when sample fills
After filling out, after opening chromatograph, using the pattern of being rapidly heated, the pyrolysis temperature to 300~350 DEG C can be brought rapidly up inside.Chromatography
Instrument temperature programming：50 DEG C of holding 10min of initial temperature, are raised to 180 DEG C with 5 DEG C/min, then rise to 250 DEG C with 10 DEG C/min, keep
5min.Fid detector temperature is 300 DEG C, hydrogen flowing quantity 40mL/min, air mass flow 350mL/min, chromatograph carrier gas column
Flow is 1mL/min.Fig. 6 is Thermal desorption-gas chromatography sample detection chromatogram of the formaldehyde obtained in the present embodiment.
Then, step 503 is executed, the concentration of formaldehyde in surrounding air is quantitatively divided according to the result of the analysis
Analysis.
Specifically, first draw formaldehyde-PFBHA-HCHO oxime compound standard curves, with calculate its equation of linear regression and
Linear regression coeffficient.In the present embodiment, according to above-mentioned optimum analysis condition, by blank modified bacteria cellulose base nano active
Carbon fiber impregnates 1h in the PFBHA solution of 2.0mg/mL, and the formaldehyde standard that various concentration value is quantitatively adding in sample cell is molten
Liquid carries out Thermal desorption-gas-chromatography temperature programming in the case where optimum solvent purges parameter, Thermal desorption, chromatographic condition, measures 30.50
~31.40min period PFBHA-HCHO oxime compound chromatographic peak area (A) data.Each concentration carries out 6 horizontal surveies, surveys
It is as shown in the table to measure average data：
It is molten with formaldehyde standard with PFBHA-HCHO oxime compound chromatographic peak area average values and formaldehyde concentration of standard solution value
Liquid concentration value is abscissa, PFBHA-HCHO oxime compound chromatographic peak area average values are ordinate, draws formaldehyde-PFBHA-
HCHO oxime compound standard curves calculate the linear regression coeffficient R of linear function with least square method2.According to above-mentioned measured value
(concentration of formaldehyde is from 0.0375 μ as shown in fig. 7, in measurement range for the formaldehyde-PFBHA-HCHO oxime compounds standard curve of drafting
The μ g of g~1.875, it is 0.00818mg/m to be converted into formaldehyde content values under 25.0 DEG C/101kPa standard state3~0.409mg/m3),
Standards calibration curve linear relationship is good, and equation of linear regression and linear regression coeffficient are respectively：Y=33238X+758R2=
0.9998。
Then, it is calculated according to concentration of formaldehyde in above-mentioned surrounding air：
First, sampling volume is converted into standard state down-sampling volume as the following formula：
Wherein, V0Sampling volume under standard state
VtSampling volume, Lt=sampling flows (L/min) × sampling time (min)
The temperature of t- sampled points, DEG C
T0Absolute temperature under standard state, T0=373K
The atmospheric pressure of p- sampled points, kPa
p0Atmospheric pressure under standard state, P0=101kPa
Then, air formaldehyde concentration is calculated as follows：
C=(A-A0)×X/V0
Wherein, C- Formaldehyde Concentration of Indoor Air (mg/m3)
A- analyte derivative gas-chromatography peak areas
A0Blank sample derives gas-chromatography peak area
X- is calculated out by standards calibration curve：X=(Y-758)/33238
V0The sampling volume being converted under standard state, L.
The present embodiment also measures the detection precision of the detection method, and measurement method is：In blank sample
Guan Zhong is quantitatively adding 0.3750 μ g of formaldehyde standard solution with microsyringe, carries out 6 duplicate measurements, measurement and statistical data
As shown in the table：
It is calculated by 6 duplicate measurements of above-mentioned standard sample：Formaldehyde chromatographic peak area average value is 13110.34, phase
It is 0.70% to standard deviation；Content of formaldehyde average value is 0.3718, RSD 0.72%.Above-mentioned repeated measurement data shows：This
The detection method for the formaldehyde that embodiment is provided has higher detection accuracy.
Within the scope of curved measurement, the minimum detectable level (MDL) of formaldehyde is 0.0018 μ g in sample.It is converted into first in air
Aldehyde value is 0.000368mg/m3；It is 1.8750 μ g that sample, which measures peak, be converted under standard state (25 DEG C,
101kPa) formaldehyde in air content value is 0.409mg/m3.Measurement data shows：Method provided by the present invention exists
0.000368mg/m3~0.409mg/m3In measurement range, formaldehyde in indoor air content value can be accurately measured, state of China is met
Family standard GB/T18883-2002《Indoor Air Quality standards》With GB50325-2010 (2013 editions)《In civil building engineering room
Environment pollution control specification》In the requirement in relation to formaldehyde examination range defined in formaldehyde in indoor air detection method.
The detection method for the formaldehyde that the present embodiment is provided is spread out by the load of modified bacteria cellulose base nanometer activated carbon fiber
Agent, the formaldehyde in On-chip derivatization, absorption, acquisition air are given birth to, and ring is detected by direct Thermal desorption-capillary gas chromatograph
Formaldehyde in the air of border, compensating for other sample-pretreating methods and Thermal desorption-gas chromatography cannot directly measure in air
The deficiency of formaldehyde.
Unless otherwise defined, those skilled in the art of technical and scientific term used herein and the present invention
Normally understood meaning is identical.Term used herein is intended merely to describe specifically to implement purpose, it is not intended that limitation is originally
Invention.Terms such as herein presented " settings " can both indicate that a component was attached directly to another component, also may be used
To indicate that a component is attached to another component by middleware.The feature described in one embodiment herein can be single
Solely or with other feature in combination be applied to another embodiment, unless this feature in another embodiment be not suitable for or
It is to be otherwise noted.
The present invention is illustrated by above-described embodiment, but it is to be understood that, above-described embodiment is only intended to
The purpose of citing and explanation, and be not intended to limit the invention within the scope of described embodiment.In addition people in the art
It is understood that the invention is not limited in above-described embodiment, introduction according to the present invention can also be made more kinds of member
Variants and modifications, these variants and modifications are all fallen within scope of the present invention.Protection scope of the present invention by
The appended claims and its equivalent scope are defined.
Claims (13)
1. a kind of preparation method of formaldehyde sampling pipe, which is characterized in that the preparation method includes：
It learns from else's experience the PFBHA derivating agents of purifying；
Bacteria cellulose-base nanometer activated carbon fiber adsorbent is taken, removes the impurity adsorbed in the adsorbent, and carry out to it
It is modified, to obtain modified bacteria cellulose base nanometer activated carbon fiber adsorbent；
The purified PFBHA derivating agents are added in the modified bacteria cellulose base nanometer activated carbon fiber adsorbent,
The predetermined time is persistently stirred, the PFBHA derivating agents are carried on the modified bacteria cellulose base nanometer activated carbon fiber
On adsorbent；And
There is the modified bacteria cellulose base nanometer activated carbon fiber adsorbent of PFBHA derivating agents to be packed into sample cell load
It is interior.
2. preparation method according to claim 1, which is characterized in that the step of being purified to the PFBHA derivating agents
Including：PFBHA solution is extracted three times using normal hexane, discards the extract liquor of first and second extraction, retains third time and extracts
The extract liquor for taking gained, to obtain required PFBHA hexane solutions.
3. preparation method according to claim 2, which is characterized in that the concentration of PFBHA in the PFBHA normal hexanes solution
More than 2mg/mL.
4. preparation method according to claim 1, which is characterized in that the bacteria cellulose-base nanometer activated carbon fiber
The method that adsorbent is modified is：The bacteria cellulose-base nanometer activated carbon fiber adsorbent is impregnated 8 in concentrated sulfuric acid
Hour or more, then use distilled water flushing 3~5 times, and remove moisture and impurity therein.
5. preparation method according to claim 1, which is characterized in that the PFBHA derivating agents are carried on the modification
Step on bacteria cellulose-base nanometer activated carbon fiber adsorbent includes：In the modified bacteria cellulose base nano active carbon
The purified PFBHA be added in fiber adsorbing substance derive and impregnate 1 hour or more in agent solution, and continue to stir 30 minutes with
On.
6. preparation method according to claim 1, which is characterized in that the modified bacteria fibre for having derivating agent will loaded
The plain base nanometer activated carbon fiber adsorbent of dimension is packed into after the step in sample cell, further includes：Under nitrogen purge to described
Modified bacteria cellulose base nanometer activated carbon fiber adsorbent is heated, to remove solvent and impurity therein.
7. the detection method of formaldehyde in a kind of surrounding air, which is characterized in that the detection method includes：
Gas sampler is connected on sampling pipe, air sample is acquired, being filled with load in the sampling pipe there are PFBHA derivatives
The modified bacteria cellulose base nanometer activated carbon fiber adsorbent of agent；
The sampling pipe for being collected sample is placed into pyrolysis analyzer, connection gas chromatograph carries out Thermal desorption-gas-chromatography point
Analysis；
Quantitative analysis is carried out to the concentration of formaldehyde in surrounding air according to the result of the analysis.
8. the detection method of formaldehyde in surrounding air according to claim 7, which is characterized in that acquire taking for air sample
The sample time is 10min~20min, and sampling velocity is 0.2L/min~0.5L/min, and sampling amount is 5L~10L.
9. the detection method of formaldehyde in surrounding air according to claim 7, which is characterized in that described to be pyrolyzed the first of analyzer
Beginning temperature setting is 45 DEG C, after sample loads, after opening gas chromatograph, using the pattern of being rapidly heated, by the Thermal desorption
Instrument is warming up to 300 DEG C~350 DEG C of pyrolysis temperature.
10. the detection method of formaldehyde in surrounding air according to claim 7, which is characterized in that the gas chromatograph
Temperature-rise period be：50 DEG C of initial temperature keeps 10min, is warming up to 180 DEG C with the rate of 5 DEG C/min, then with the rate of 10 DEG C/min
250 DEG C are warming up to, and keeps 5min.
11. the detection method of formaldehyde in surrounding air according to claim 7, which is characterized in that by fid detector temperature
300 DEG C, hydrogen flowing quantity 40mL/min, air mass flow 350mL/min are set as, chromatograph carrier gas column flow is 1mL/min.
12. the detection method of formaldehyde in surrounding air according to claim 7, which is characterized in that the quantitative analysis
Method is：Addition is quantified with formaldehyde standard sample, standard curve is drawn with peak area-concentration of formaldehyde value, according to the Thermal desorption-
The result of gas chromatographic analysis compares the standard curve and carries out quantitative analysis.
13. the detection method of formaldehyde in surrounding air according to claim 12, which is characterized in that the calculating of concentration of formaldehyde
Method is：
First, sampling volume is converted into standard state down-sampling volume as the following formula：
Wherein, V0Sampling volume under standard state
VtSampling volume, Lt=sampling flows (L/min) × sampling time (min)
The temperature of t- sampled points, DEG C
T0Absolute temperature under standard state, T0=373K
The atmospheric pressure of p- sampled points, kPa
p0Atmospheric pressure under standard state, P0=101kPa
Then, air formaldehyde concentration is calculated as follows：
C=(A-A0)×X/V0
Wherein, C- Formaldehyde Concentration of Indoor Air (mg/m3)
A- analyte derivative gas-chromatography peak areas
A0Blank sample derives gas-chromatography peak area
X- is calculated out by standards calibration curve：X=(Y-758)/33238
V0The sampling volume being converted under standard state, L.
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| CN109632402A (en) * | 2019-01-23 | 2019-04-16 | 大连理工大学 | A kind of novel thermal desorption adsorption tube |
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