CN109030654A - The method and application of low molecule chlorinatedorganic in a kind of quick detection mthod of white water from paper making - Google Patents
The method and application of low molecule chlorinatedorganic in a kind of quick detection mthod of white water from paper making Download PDFInfo
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- CN109030654A CN109030654A CN201810939356.XA CN201810939356A CN109030654A CN 109030654 A CN109030654 A CN 109030654A CN 201810939356 A CN201810939356 A CN 201810939356A CN 109030654 A CN109030654 A CN 109030654A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000001514 detection method Methods 0.000 title claims abstract description 34
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical class ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012086 standard solution Substances 0.000 claims abstract description 19
- -1 chloro- 2- propyl Chemical group 0.000 claims abstract description 17
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 12
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000007790 solid phase Substances 0.000 claims abstract description 9
- 238000002347 injection Methods 0.000 claims abstract description 8
- 239000007924 injection Substances 0.000 claims abstract description 8
- 238000003780 insertion Methods 0.000 claims abstract description 5
- 230000037431 insertion Effects 0.000 claims abstract description 5
- 238000001319 headspace solid-phase micro-extraction Methods 0.000 claims abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 238000002470 solid-phase micro-extraction Methods 0.000 claims description 19
- 238000000605 extraction Methods 0.000 claims description 13
- 238000001819 mass spectrum Methods 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 9
- 238000004817 gas chromatography Methods 0.000 claims description 9
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000000611 regression analysis Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 9
- 238000004458 analytical method Methods 0.000 abstract description 7
- 239000000523 sample Substances 0.000 description 27
- 239000000835 fiber Substances 0.000 description 11
- 230000032683 aging Effects 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 238000010009 beating Methods 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004853 microextraction Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001785 headspace extraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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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
Abstract
The invention discloses the methods and application of low molecule chlorinatedorganic in a kind of quickly detection mthod of white water from paper making.Method includes the following steps: (1) sample to be tested pre-processes: water sample mthod of white water from paper making to be measured being filtered, chlorate is added, obtains sample to be tested；(2) configuration standard solution: by the chloro- 2- propyl alcohol of 1,3- bis- and 1,2,3- trichloropropanes are added in mthod of white water from paper making, configure the standard solution of at least five concentration；(3) solid phase microextraction-gas-chromatography-Mass Spectrometer Method: sample to be tested and step standard solution are extracted by the way of headspace solid-phase microextraction respectively, the extracting head insertion mass spectrographic injection port of gas-chromatography-is desorbed again, and carry out Gas Chromatography-Mass Spectrometry, it calculates 1 in sample, the chloro- 2- propyl alcohol of 3- bis- and 1, the content of 2,3- trichloropropanes.Method of the invention is easy to operate, efficient, sensitive, the rate of recovery is high, at low cost, the analysis of volatility chlorinatedorganic suitable for mthod of white water from paper making.
Description
Technical field
The invention belongs to noxious material detection field in papermaking chemical product, in particular in a kind of quickly detection mthod of white water from paper making
The method and application of low molecule chlorinatedorganic.
Background technique
Polyamine epichlorohydrin resin (abbreviation PAE resin) have as wet strength agent the potent fruit of being humidified it is good, it is formaldehydeless,
Dosage is few, is suitble to the advantages that neutral and alkali copy paper and is widely used in paper industry.As the improvement of people's living standards, high
The demand of wet strength paper is more more and more intense, therefore PAE resin is widely used in paper-making process.But current existing technology, it is raw
Some by-products can be generated during producing PAE, these by-products are organic by epoxychloropropane hydrolysis generation small molecule chloro
Object.When using PAE in paper-making process, these chlorinatedorganics can pollute page and white-water system.
Low molecule chlorinatedorganic is fat-soluble good, and metabolism slowly, can be concentrated, accumulates and make in vivo in vivo
The chronic toxicity effect of growth stage.Especially there is very strong toxicity to liver, some even have carcinogenicity.Mthod of white water from paper making is by multiple
Reuse, low molecule chlorinatedorganic can accumulate in plain boiled water, and the plain boiled water of reuse is used to produce paper, and can be by these low molecules
Chlorinatedorganic is transferred in paper.Paper is used for the every aspect of daily life, contacts with human skin zero distance, therein
Chlorinatedorganic can cause harm to the human body.The plain boiled water of multiple reuse is through emission treatment, wherein the low molecule chloro contained is organic
Object can also cause damages to aqueous bio.
Conventional method measures the content of low molecule chlorinatedorganic with titration.Examined by silver nitrate precipitation titration
It surveys, before titration, it is necessary first to it be extracted with organic solvent such as ethyl acetate, secondly with liquor potassic permanganate to object containing chlorine
Matter is ionized, so that it is oxidized to inorganic chloride ion from organochlorine.The detection of this conventional titration method limits higher, trace
The chlorinatedorganic of amount cannot be measured accurately by this method.
In addition to above-mentioned chemical titration, there are also some instrument analytical methods.Since low molecule chloro has in mthod of white water from paper making
Machine object content is generally lower, and plain boiled water matrix interference is big, and the methods of traditional liquid-liquid extraction, solid phase extraction need to use large volume
Plain boiled water (500~1000ml) enrichment concentration to guarantee to reach detection limit, there are big (the liquid liquid extractions of solvent-oil ratio for pretreatment process
To take need 100~300ml organic reagent), it is cumbersome that time-consuming (through extraction, enrichment, concentration, time-consuming is about each sample
8h) etc. greatly constrain the development of coherent detection and research work.
Therefore, a kind of method for efficiently, quickly detecting chlorinatedorganic in mthod of white water from paper making is established, for environmental protection and paper
Quality is of great significance safely.
Summary of the invention
The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, provide a kind of quickly detection mthod of white water from paper making
The method of middle low molecule chlorinatedorganic.
Another object of the present invention is to provide the applications of low molecule chlorinatedorganic in the quick detection mthod of white water from paper making.
The purpose of the invention is achieved by the following technical solution: it is organic that one kind quickly detecting low molecule chloro in mthod of white water from paper making
The method of object, comprising the following steps:
(1) sample to be tested pre-processes
Water sample mthod of white water from paper making to be measured is filtered, filtered mthod of white water from paper making sample is obtained；Mthod of white water from paper making sample is packed into again
In ml headspace bottle and chlorate is added, 10~60min is balanced under the conditions of 35 DEG C~70 DEG C, obtains sample to be tested；
(2) configuration standard solution
By the chloro- 2- propyl alcohol (DCP) of 1,3- bis- and 1,2,3- trichloropropanes are added in mthod of white water from paper making, and configuration at least five is dense
The chloro- 2- propyl alcohol of 1,3- bis- of degree and the mixed liquor of 1,2,3- trichloropropane are as standard solution；
(3) solid phase microextraction-gas-chromatography-Mass Spectrometer Method (SPME-GC/MS)
Standard solution obtained in sample to be tested and step (2) will be obtained in step (1) respectively using the micro- extraction of head space solid phase
The mode taken extracts 10~60min under the conditions of 35~70 DEG C；Then the extracting head of the standard solution obtained after extraction is inserted into
The injection port of gas-chromatography-mass spectrum (GC/MS) is desorbed, and carries out gas-chromatography-Mass Spectrometer Method, then with the color of standard solution
Spectral peak area corresponds to its concentration and carries out regression analysis, obtains standard working curve；Then it will be obtained after extraction under the same conditions
The injection port of extracting head insertion gas-chromatography-mass spectrum (GC/MS) of sample to be tested desorbed, and carry out gas-chromatography-matter
Spectrum measurement, then result is compareed with standard working curve, calculate the chloro- 2- propyl alcohol of 1,3- bis- and 1,2,3- trichloropropanes in sample
Content.
Chlorate described in step (1) is preferably NaCl.
The mass ratio of the NaCl and the mthod of white water from paper making sample are 0.3~2.1:1~10；Preferably 0.3~2.1:
5；More preferably 2.1:5.
Ml headspace bottle described in step (1) is preferably the ml headspace bottle of 20ml.
The condition of balance described in step (1) is preferred are as follows: balances 60min under the conditions of 40 DEG C.
Mthod of white water from paper making described in step (2) does not add wet strength agent to generate mthod of white water from paper making when being paper making.
The mass ratio of the paper making duration fibre and short fibre is 2:3, and long fibre beating degree is 20 ° of SR, short fibre beating degree
For 22 ° of SR, sizing concentration 0.9wt%.
The chloro- 2- propyl alcohol (DCP) of 1,3- bis- and 1, the concentration model of 2,3- trichloropropanes in standard solution described in step (2)
Enclosing is 0.1~10 μ g/L.
The chloro- 2- propyl alcohol (DCP) of 1,3- bis- and 1 in standard solution described in step (2), the concentration of 2,3- trichloropropanes is matched
To as follows: 0.1 μ g/L/0.1 μ g/L, 0.5 μ g/L/0.5 μ g, 1 μ g/L/1 μ g/L, 2 μ g/L/2 μ g, 3 μ g/L/3 μ g, 4 μ g/L/4 μ
g、5μg/L/5μg/L、10μg/L/10μg/L。
The extracting head of solid phase microextraction described in step (3) is 85 μm of Carboxen/PDMS extracting heads, 85 μm poly- third
Olefin(e) acid ester (Polyacrylate) extracting head or 65 μm of PDMS/DVB extracting heads；Preferably 85 μm of polyacrylate
(Polyacrylate) extracting head；85 μm of polyacrylate (Polyacrylate) extracting heads more preferably after aging.
The condition of the aging are as follows: aging 15min in GC injection port under the conditions of 250 DEG C.
The condition of solid phase microextraction described in step (3) are as follows: extract 40min under the conditions of 35~70 DEG C；It is preferred that are as follows:
40min is extracted under the conditions of 40 DEG C；More preferably: extracting 40min under the conditions of 800r/min, 40 DEG C.
The condition of desorption described in step (3) are as follows: 2~10min is desorbed under the conditions of 240~280 DEG C；It is preferred that are as follows:
6min is desorbed under the conditions of 240 DEG C.
Chromatographic column used in gas-chromatography is DB-WAX chromatographic column in gas-chromatography-mass spectrum described in step (3), long
30m, internal diameter 0.25mm.
The condition of gas-chromatography in gas-chromatography-mass spectrum described in step (3) are as follows:
Temperature program are as follows: 35 DEG C of heat preservation 1min, 10 DEG C/min are warming up to 180 DEG C of heat preservations 3min, 15 DEG C/min and are warming up to 240
DEG C heat preservation 1min；
Injector temperature: 240 DEG C.
Mass spectrographic condition in gas-chromatography-mass spectrum described in step (3) are as follows: EI+Ion source；Single level four bars mass spectrum inspection
It surveys；Energy is 70eV；Full scan ion monitoring (full scan).
The method of low molecule chlorinatedorganic low molecule in detection mthod of white water from paper making in the quick detection mthod of white water from paper making
Application in chlorinatedorganic.
The low molecule chlorinatedorganic is the chloro- 2- propyl alcohol (DCP) of 1,3- bis- and 1,2,3- trichloropropane.
The present invention has the following advantages and effects with respect to the prior art:
1, in mthod of white water from paper making of the present invention low molecule chlorinatedorganic pre-treatment analyzing detecting method and conventional method
Comparing, it is rapidly and efficiently environmentally friendly to have the characteristics that, the pre-treatment time that conventional method needs is long, cumbersome, and expends a large amount of
Organic reagent, determinand easily lose or pollute.
2, the present invention is using low molecule chlorinatedorganic in solid phase micro-extraction technique separation and concentration mthod of white water from paper making, and passes through gas
Phase hydrolysis and condensation tests and analyzes sample, realize in mthod of white water from paper making low molecule chlorinatedorganic it is quick
Detection.Solid phase micro-extraction technique of the invention has many advantages, such as quick, efficient, simplicity, especially has in the detection of contaminant trace species
Have wide practical use.
3, method of the invention keeps the analysis detection in mthod of white water from paper making real by Chemical Measurement policy optimization Parameter Conditions
Now from sampling pre-treatment-sample introduction integration, quickly, required sample size is few for analysis, and detection process organic solvent-free uses, operation
Effect easy and that detection limit is low, reproducibility is high.
4, method of the invention integrates extraction, concentration and separation and sampling technique, and analysis is quick, efficient, sensitive, ring
Guarantor, the rate of recovery are high, at low cost, suitable for handling the separation and concentration technology of trace samplings, and the volatility suitable for mthod of white water from paper making
The analysis of chlorinatedorganic.
Detailed description of the invention
Fig. 1 is the chromatogram of low molecule chlorinatedorganic in mthod of white water from paper making.
Fig. 2 is the canonical plotting of the chloro- 2- propyl alcohol (DCP) of 1,3- bis-.
Fig. 3 is the canonical plotting of 1,2,3- trichloropropane.
Fig. 4 is influence diagram of the extraction time to DCP and 1,2,3- trichloropropane detection sensitivity.
Influence diagram of the additive amount to DCP and 1,2,3- trichloropropane detection sensitivity that Fig. 5 is NaCl.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Experimental method used in following embodiments, if being the existing conventional method of the art, being used without specified otherwise
Ingredient or material be unless otherwise specified by the available ingredient of commercial sources or material.
Embodiment 1
The rapid assay methods of low molecule chlorinatedorganic in a kind of mthod of white water from paper making, comprising the following steps:
(1) sample to be tested pre-processes
Oil removal is filtered with middling speed qualitative filter paper to water sample mthod of white water from paper making to be measured, 5 grams is then accurately weighed and makes
Paper plain boiled water and 2.1 grams of NaCl balance 1h at 40 DEG C in 20ml ml headspace bottle.
(2) solid phase microextraction (SPME)
Aging process is carried out to solid-phase micro-extraction fibre head: 85 μm of polyacrylate (Polyacrylate) extracting heads are set
The aging 15min in GC (gas-chromatography) injection port, 250 DEG C of temperature is to remove the residue on surface；It will then be put down in step (1)
In solid-phase micro-extraction fibre head (polyacrylate extracting head) insertion ml headspace bottle after the sample aging weighed, it is micro- to release solid phase
Extracting fiber head headspace extraction sample, extraction temperature are 40 DEG C, and extraction time is 40min (magnetic stirrer extraction, revolving speed
For 800r/min)；Solid phase microextraction sample introduction needle after the completion of adsorption sample is inserted into solid phase microextraction-gas chromatography combined with mass spectrometry
(GC/MS) interface releases solid-phase micro-extraction fibre head, fastens fixing buckle；Starting GC/MS solves solid phase micro-extracting head
It inhales, so that the compound of enrichment is desorbed at high temperature and is entered chromatography with mobile phase and desorbed and detected, desorption temperature is
240 DEG C, desorption time 6min.Desorption terminates, and opens fixing buckle, and solid phase microextraction of pulling back handle push rod keeps solid phase microextraction fine
Dimension head, which is retracted to, to be punctured in dottle pin needle, is removed solid phase microextraction handle, is carried out extracting operation next time.The chromatography of mthod of white water from paper making
Figure is as shown in Figure 1.
(3) gas-chromatography-mass spectrometry (GC/MS)
Using Agilent 7890A-5977B gas chromatograph-mass spectrometer (GC-MS):
1. chromatographic condition:
Temperature program are as follows: 35 DEG C of heat preservation 1min, 10 DEG C/min are warming up to 180 DEG C of heat preservations 3min, 15 DEG C/min and are warming up to 240
DEG C heat preservation 1min；
Chromatographic column: DB-WAX (Agilent company), long 30m, internal diameter 0.25mm；Injector temperature is 240 DEG C.
2. Mass Spectrometry Conditions:
With the EI for pulling out lens+Ion source；Single level four bars Mass Spectrometer Method；Energy: 70eV；Scanning of the mass spectrum mode: it sweeps entirely
Retouch ion monitoring (full scan).
(4) standard curve is drawn, the content of low molecule chlorinatedorganic is measured
1. drawing standard curve: accurate measuring 1, the chloro- 2- propyl alcohol (DCP) of 3- bis- and 1,2,3- trichloropropane standard items, so
After be added to self-control plus wet strength agent mthod of white water from paper making (plain boiled water generates plain boiled water when being paper making, long fine with short fibre in paper-making process
Mass ratio be 2:3, fiber is all from certain purchased market pulp board of paper for daily use factory, and long fibre beating degree is 20 ° of SR, short fine beating degree
To configure the chloro- 2- propyl alcohol (DCP) of 1,3- bis- and 1, the mixing of 2,3- trichloropropanes is molten in 22 ° of SR, sizing concentration 0.9wt%)
Liquid, concentration are 0.1 μ g/L/0.1 μ g/L, 0.5 μ g/L/0.5 μ g, 1 μ g/L/1 μ g/L, 2 μ g/L/2 μ g, 3 μ g/L/3 μ g, 4 μ g/
The standard solution of L/4 μ g, 5 μ g/L/5 μ g/L, 10 μ g/L/10 μ g/L；Standard solution is subjected to solid phase by the method for step (2) again
Solid phase microextraction sample introduction needle is inserted into solid phase microextraction-gas chromatography combined with mass spectrometry (GC/MS) after the completion by micro-extraction, adsorption sample
Interface desorbed (desorption temperature be 240 DEG C, desorption time 6min), then carry out gas-chromatography-Mass Spectrometer Method analysis, obtain
To the corresponding chromatographic peak area of each concentration gradient sample, obtained peak area concentration gradient corresponding with its is subjected to Linear Quasi
It closes, obtains calibration curve equation and linearly dependent coefficient.The standard curve that the data of obtained concentration and response are depicted as is such as
Shown in Fig. 2 and 3.
2. measuring the content of low molecule chlorinatedorganic: the method that sample to be tested obtained in step (3) is pressed step (2)
Solid phase microextraction is carried out, the extracting head insertion GC/MS injection port of the sample to be tested obtained after extraction is then desorbed into (desorption
240 DEG C of temperature, desorption time 6min), then gas-chromatography-mass spectroscopy is carried out, and it is qualitative with retention time, to measure target peak
Area value substitutes into calibration curve equation, acquires the content of low molecule chlorinatedorganic in sample.
(5) rate of recovery and precision
Under the determination condition of this method, to this method linear correlation, detection limit (3 times of signal-to-noise ratio, reach ng rank), add
(recovery of standard addition is that standard addition method measures to obtain to the mark rate of recovery, i.e., the determinand of known quantity is added in blank sample, according to step
Rapid processing sample is detected obtained determinand content and known content ratio is the rate of recovery) and relative standard deviation carry out
It investigates.Test result shows that extracting head still keeps good thermal stability at 70 DEG C.Using the method for the invention to papermaking
The range of linearity of low molecule chlorinatedorganic is 0.1~10 μ g/L in plain boiled water, and linear good, linearly dependent coefficient R2For
0.9960~0.9991, recovery of standard addition is 80.1%~102.4%, and relative standard deviation is 2.55%~4.97%, detection
It is limited to 0.0136~0.0364 μ g/L, above data explanation, this method has preferable precision, stability and reproducibility, can
With the Accurate Determining for low molecule chlorinatedorganic in mthod of white water from paper making.The recovery of standard addition of detection method of the invention such as table 1
It is shown.
1 rate of recovery test result of table
Embodiment 2
Detected according to the method for embodiment 1, the difference is that: in step (2) solid phase microextraction (SPME) when
Between be 10,20,30,40,50,60min.It is as shown in Figure 4 that it detects signal.During SPME generally by increase extraction time come
Guarantee that volatile materials is maximumlly evaporate into improve detection sensitivity in head space, but as seen from Figure 4, in 40min
The sensitivity of 1,2,3- trichloropropanes is significantly lowered afterwards, and DCP is then gradually increased, this is the performance of absorption competition, in order to guarantee two
Kind substance accurately detects, and extraction Best Times are 40min.
Embodiment 3
It is detected according to the method for embodiment 1, the difference is that: it is added when sample to be tested pre-processes in step (1)
The quality of NaCl is 0.3,0.6,0.9,1.2,1.5,1.8,2.1 gram.It is as shown in Figure 5 that it detects signal.Ionic effect can reduce
The solubility of substance in water, the salt containing chlorine, which is added, will increase the volatility of chlorinated organics.It can be seen from Fig. 5 that NaCl is added
The sensitivity of two kinds of objects to be checked is significantly increased, it therefore, can be organic to improve low molecule chloro in plain boiled water by the way that NaCl is added
The detection sensitivity of object.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method of low molecule chlorinatedorganic in quickly detection mthod of white water from paper making, which comprises the following steps:
(1) sample to be tested pre-processes
Water sample mthod of white water from paper making to be measured is filtered, filtered mthod of white water from paper making sample is obtained；Mthod of white water from paper making sample is packed into head space again
In bottle and chlorate is added, 10~60min is balanced under the conditions of 35 DEG C~70 DEG C, obtains sample to be tested；
(2) configuration standard solution
By the chloro- 2- propyl alcohol of 1,3- bis- and 1,2,3- trichloropropanes are added in mthod of white water from paper making, configure 1, the 3- bis- of at least five concentration
The mixed liquor of chloro- 2- propyl alcohol and 1,2,3- trichloropropane is as standard solution；
(3) solid phase microextraction-gas-chromatography-Mass Spectrometer Method
Standard solution obtained in sample to be tested and step (2) will be obtained in step (1) respectively using headspace solid-phase microextraction
Mode extracts 10~60min under the conditions of 35~70 DEG C；Then the extracting head of the standard solution obtained after extraction is inserted into gas phase
The mass spectrographic injection port of chromatography-is desorbed, and carries out gas-chromatography-Mass Spectrometer Method, then with the chromatographic peak area pair of standard solution
It answers its concentration to carry out regression analysis, obtains standard working curve；Then the sample to be tested that will be obtained after extraction under the same conditions
The extracting head insertion mass spectrographic injection port of gas-chromatography-desorbed, and carry out Gas Chromatography-Mass Spectrometry, then by result with
Standard working curve control, calculates the chloro- 2- propyl alcohol of 1,3- bis- and 1, the content of 2,3- trichloropropanes in sample.
2. the method for low molecule chlorinatedorganic in quick detection mthod of white water from paper making according to claim 1, it is characterised in that:
The condition of solid phase microextraction described in step (3) are as follows: extract 40min under the conditions of 40 DEG C.
3. the method for low molecule chlorinatedorganic in quick detection mthod of white water from paper making according to claim 1, it is characterised in that:
Chlorate described in step (1) is NaCl；
Mthod of white water from paper making described in step (2) does not add wet strength agent to generate mthod of white water from paper making when being paper making.
4. the method for low molecule chlorinatedorganic in quick detection mthod of white water from paper making according to claim 3, it is characterised in that:
The mass ratio of the NaCl and the mthod of white water from paper making sample are 0.3~2.1:1~10.
5. the method for low molecule chlorinatedorganic in quick detection mthod of white water from paper making according to claim 4, it is characterised in that:
The mass ratio of the NaCl and the mthod of white water from paper making sample are 0.3~2.1:5.
6. the method for low molecule chlorinatedorganic in quick detection mthod of white water from paper making according to claim 1, it is characterised in that:
The condition of gas-chromatography in gas-chromatography-mass spectrum described in step (3) are as follows:
Temperature program are as follows: 35 DEG C of heat preservation 1min, 10 DEG C/min are warming up to 180 DEG C of heat preservations 3min, 15 DEG C/min and are warming up to 240 DEG C of guarantors
Warm 1min；
Injector temperature: 240 DEG C；
Mass spectrographic condition in gas-chromatography-mass spectrum described in step (3) are as follows: EI+Ion source；Single level four bars Mass Spectrometer Method；Energy
For 70eV；Full scan ion monitoring.
7. the method for low molecule chlorinatedorganic in quick detection mthod of white water from paper making according to claim 1, it is characterised in that:
The chloro- 2- propyl alcohol (DCP) of 1,3- bis- and 1 in standard solution described in step (2), the concentration range of 2,3- trichloropropanes is equal
For 0.1~10 μ g/L.
8. the method for low molecule chlorinatedorganic in quick detection mthod of white water from paper making according to claim 7, it is characterised in that:
The chloro- 2- propyl alcohol (DCP) of 1,3- bis- and 1 in standard solution described in step (2), the concentration pairing of 2,3- trichloropropanes is such as
Under: 0.1 μ g/L/0.1 μ g/L, 0.5 μ g/L/0.5 μ g, 1 μ g/L/1 μ g/L, 2 μ g/L/2 μ g, 3 μ g/L/3 μ g, 4 μ g/L/4 μ g, 5 μ
g/L/5μg/L、10μg/L/10μg/L。
9. the method for low molecule chlorinatedorganic in quick detection mthod of white water from paper making according to claim 1, it is characterised in that:
The condition of balance described in step (1) are as follows: balance 60min under the conditions of 40 DEG C；
Extracting head described in step (3) is 85 μm of Carboxen/PDMS extracting heads, 85 μm of polyacrylate extracting heads or 65 μ
The extracting head of m PDMS/DVB；
The condition of desorption described in step (3) are as follows: 2~10min is desorbed under the conditions of 240~280 DEG C；
Chromatographic column used in gas-chromatography is DB-WAX chromatographic column in gas-chromatography-mass spectrum described in step (3).
10. the method for low molecule chlorinatedorganic is detecting in quick detection mthod of white water from paper making according to any one of claims 1 to 9
Application in mthod of white water from paper making in low molecule chlorinatedorganic, it is characterised in that: the low molecule chlorinatedorganic is 1,3- bis-
Chloro- 2- propyl alcohol and 1,2,3- trichloropropane.
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| CN110470756A (en) * | 2019-08-12 | 2019-11-19 | 华南理工大学 | The method and its application of the organic chloro thing DCP content of nocuousness of PAE wet strength agent in a kind of measurement paper for daily use |
| CN110988214A (en) * | 2019-12-27 | 2020-04-10 | 广东省药品检验所（广东省药品质量研究所、广东省口岸药品检验所） | Method for detecting chloropropanol in hydroxypropyl modified starch |
| CN110988214B (en) * | 2019-12-27 | 2022-09-27 | 广东省药品检验所（广东省药品质量研究所、广东省口岸药品检验所） | Method for detecting chloropropanol in hydroxypropyl modified starch |
| CN116106456A (en) * | 2023-04-13 | 2023-05-12 | 中轻纸品检验认证有限公司 | Method for detecting content of 3-chloro-1, 2-propanediol in polyamide epichlorohydrin wet strength agent |
| CN116106456B (en) * | 2023-04-13 | 2023-08-29 | 中轻纸品检验认证有限公司 | Method for detecting content of 3-chloro-1, 2-propanediol in polyamide epichlorohydrin wet strength agent |
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