CN103837628A - Method for detecting content of short-chain chlorinated paraffin in chlorinated paraffin product - Google Patents
Method for detecting content of short-chain chlorinated paraffin in chlorinated paraffin product Download PDFInfo
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Abstract
The invention provides a method for detecting the content of short-chain chlorinated paraffin in a chlorinated paraffin product. The quantitative analysis is carried out by adopting a method of combining a short-chain chlorinated paraffin online catalysis dechlorinating and hydrogenating device and a gas chromatograph. The method comprises the steps: reducing the short-chain chlorinated paraffin in the chlorinated paraffin product into alkane with corresponding carbon chain length by adopting the online catalysis dechlorinating and hydrogenating device, and completely transferring into the gas chromatograph with a carrier gas for performing online separation, wherein a separation column is a quartz capillary-column chromatography DB-5. According to the method, the online reduction of the short-chain chlorinated paraffin in the chlorinated paraffin product is realized by combining the short-chain chlorinated paraffin online catalysis dechlorinating and hydrogenating device and the gas chromatograph, and the content of the short-chain chlorinated paraffin in the chlorinated paraffin product is indirectly quantitatively analyzed through analyzing an alkane product with the corresponding carbon chain length. The method is capable of achieving rapid detection of the short-chain chlorinated paraffin in the chlorinated paraffin product, convenient to operate, simple in spectrum and quantization method, and accurate in detection result.
Description
Technical field
The present invention relates to a kind of detection method for chlorinated paraffin product short chain chlorinated paraffin content, adopt specifically the alkane that the online catalysis dechlorination hydrogenation plant of short chain chlorinated paraffin is corresponding carbon chain lengths by short chain chlorinated paraffin Efficient Conversion under high-temperature and high-pressure conditions, and by analyzing quantitative method with gas chromatograph on-line coupling.
Background technology
Chlorinated paraffin (chlorinated paraffins, CPs) be the synthetic n-alkane chlorinated derivative of lineup's work, be mainly used in the fire retardant of textile, rubber and plastic cement, leather treatment, plasticiser and the Metalworking fluid adjuvant of paint and other coating.Can be divided into short chain chlorinated paraffin (SCCPs, chain length is 10-13 carbon atom), medium chain chlorinated paraffin (MCCPs, chain length is 14-17 carbon atom) and long-chain chlorinated paraffin (LCCPs, chain length is 18-30 carbon atom) according to the difference of carbon chain lengths.Especially short chain chlorinated paraffin, receives the concern of International Environmental Protection tissue and national governments in recent years day by day.
Since the 1980's, developed country has carried out the toxicologic study of short chain chlorinated paraffin successively.The World Health Organization (WHO) (WHO/IPCS) has carried out the ecosystem and health assessment to chlorinated paraffin, and its result shows that short chain chlorinated paraffin has toxicity for algae, invertabrate and fish.Along with scientific research further deeply, short chain chlorinated paraffin can lastingly exist and can carry out long-distance migration in environment, is easy to enrichment in vivo and also passes through food chain biomagnification, has the toxicity such as carcinogenic, teratogenesis and mutagenesis.2000, EU Water Framework Directive banned use of short chain chlorinated paraffin, and was classified as one of primary dangerous substance in water; Multiple countries comprise that the U.S., Canada, Australia etc. put into effect production and the contents level of corresponding laws and regulations restriction short chain chlorinated paraffin subsequently.The new persistence organic pollutant of Convention of Stockholm (POPs) examination board in 2007 thinks that short chain chlorinated paraffin has reached POPs and related to screening criteria, is put into POPs candidate inventory.
Along with European Union and the U.S. etc. are for the production of short chain chlorinated paraffin and the restriction of use, domestic chlorinated paraffin is produced and outlet also will face the challenge.The chlorinated-paraffin producing process of domestic current mainly comprises two kinds, is respectively thermal chlorination and light chlorination process, is all the chlorination reaction based on alkane (being mainly n-alkane).Mass-produced middle long-chain chlorinated paraffin product comprises that (((chlorine wax) – 70, especially Lv La – 42 and Lv La – 52, account for the more than 80% of domestic chlorinated paraffin total production to chlorinated paraffin for chlorine wax) – 52 and chlorinated paraffin for chlorine wax) – 42, chlorinated paraffin.In the industrial processes of middle long-chain chlorinated paraffin, meeting association short chain chlorinated paraffin, once generate short chain chlorinated paraffin, is just difficult to separate from chlorinated paraffin product.
Have much for the analytical approach of short chain chlorinated paraffin at present, as high-resolution gas chromatography (HRGC) and high/low resolution mass spectrometric hyphenated technique, (GC × GC – electron capture is born chemical source (ECNI)-rapid scanning quadrupole rod mass spectrum (qTOF – MS) to comprehensive two dimensional gas chromatography, Gao Xiao Ye Xiang Se Pu – chlorine strengthens Atmosphere Pressure Chemical Ionization (APCI) (CI – APCI) ion trap mass spectrometry, but due to the interference of middle long-chain chlorinated paraffins a large amount of in chlorinated paraffin product, the analysis that makes these methods be applied to short chain chlorinated paraffin in chlorinated paraffin product also has certain limitation, be difficult to accurate quantitative analysis.The domestic relevant criterion of also not measuring short chain chlorinated paraffin content in chlorinated paraffin product at present, does not set up the analytical approach for short chain chlorinated paraffin content in chlorinated paraffin product yet.
Summary of the invention
The object of the present invention is to provide a kind of method based on the online catalysis dechlorination hydrogenation plant of short chain chlorinated paraffin and gas chromatograph coupling to carry out analyzing and testing to the content of short chain chlorinated paraffin in chlorinated paraffin product.The method is the alkane that the short chain chlorinated paraffin in chlorinated paraffin product is reduced to corresponding carbon chain lengths by online catalysis dechlorination hydrogenation plant, and all transfers in gas chromatograph and carry out ON-LINE SEPARATION with carrier gas, and flame ionization ditector is measured alkane.The content of the indirect quantitative test short chain of alkane product chlorinated paraffin by analyzing corresponding carbon chain lengths in product.The method spectrogram and quantivative approach are simple, and testing result is accurate.Simplify pre-treatment step, and solvent-oil ratio is little, reduces experimental cost.Can realize the fast detecting of short chain chlorinated paraffin in chlorinated paraffin product, easy to operate.Be applicable to Routine Test Lab analysis and the factory inspection in enormous quantities to chlorinated paraffin product of short chain chlorinated paraffin in chlorinated paraffin product.The limitation standard of China being carried out to short chain chlorinated paraffin content in chlorinated paraffin product provides foundation and technical guarantee with the production technology of researching and developing long-chain chlorinated paraffin product in high-purity, and significant.
The detection method of short chain chlorinated paraffin content in chlorinated paraffin product provided by the invention, comprises following steps:
1), the preparation of internal standard compound matter solution: using the manually synthetic chlorinated paraffin with branched structure as internal standard compound matter, and be made into certain density inner mark solution with normal hexane, deepfreeze is preserved.
2), the preparation of alkane standard solution: be the n-alkane that is 10-13 by carbon chain lengths is mixed with series concentration alkane standard solution with certain density internal standard compound matter hexane solution.
3), the preparation of chlorinated paraffin sample: weigh in the balance and get a certain amount of chlorinated paraffin sample, in employing and alkane standard solution, the interior mark hexane solution of internal standard compound matter same concentrations fully dissolves constant volume, and after shaking up, sealing is preserved.
4), sample introduction operation: open carrier gas, start online catalysis dechlorination hydrogenation plant and gas chromatograph.After catalyzer in catalysis dechlorination hydrogenation plant is activated, and catalysis dechlorination hydrogenation plant and gas chromatograph reach setting operating conditions and stable after, adopt 10 μ L micro syringes to draw 1 μ L sample and enter online catalysis dechlorination hydrogenation plant and measure.
5), online catalysis dechlorination hydrogenation plant condition;
6), gas chromatography-hydrogen flameionization testing conditions: adopt chromatographic work station to record the chromatographic peak area of different carbon chain lengths alkane, and carry out qualitative analysis according to retention time.
7), quantitative test.Adopt the concentration of four kinds of alkane in inner mark method ration calculation sample, then calculate the mass concentration of short chain chlorinated paraffin in sample according to chlorinity information.
Wherein the internal standard compound matter in step 1) is that 2 – Jia Ji – undecanes are reacted to side chain chlorinated paraffin that artificial anamorphic zone branched structure and carbon chain lengths are 12 as internal standard compound matter by chlorination, and its chlorinity is 58.7%.Be made into the inner mark solution of 120mg/L with normal hexane, deepfreeze is preserved.Step 2) in alkane standard solution be to obtain by the method for dilution alkane work mother liquor.Alkane mother liquor is to take respectively in each 0.2000g to the 10mL volumetric flask of n-decane, n-undecane, n-dodecane and n-tridecane with balance, adds normal hexane fully to dissolve and constant volume, shakes up, and obtains concentration and be respectively the hybrid working mother liquor of four kinds of alkane of 20g/L.Then pipette respectively in 0,25,50,100 and 150 μ L hybrid working mother liquor to a 5 10mL volumetric flask with liquid-transfering gun, the interior mark hexane solution that is 120mg/L by concentration is diluted to graticule, mixes.The concentration that obtains four kinds of alkane in alkane standard solution is respectively 0,50, and 100,200 and 300mg/L.Chlorinated paraffin sample in step 3) adopts balance to take 0.0050 – 0.0500g (being accurate to 0.001g) sample, puts into 10mL volumetric flask, and adding 10mL concentration is that the interior mark hexane solution of 120mg/L fully dissolves constant volume, and after shaking up, sealing is preserved.
The concrete steps of sample introduction operation are
1), the preparation of catalyzer: adopt 8mg PdCl
2, be dissolved in 5% acetic acid of 1mL heat, transfer to after surface plate, add 1.9g 50-70 order silanized glass microballon, and be placed under infrared lamp and dry.Add appropriate amount of deionized water, and with ammonia spirit (25% mass concentration) regulate pH to 9.After drying under infrared lamp, wash with 5mL cyclopentane, air-dry in fuming cupboard, obtain palladium content and be 0.42% Pd catalyzer.
2), the filling of catalysis dechlorination hydrogenation reaction pipe: silica wool, catalyzer, Carbon Dioxide calcium, catalyzer, Carbon Dioxide calcium, silica wool are loaded in the stainless steel reaction pipe of catalysis dechlorination hydrogenation plant successively according to order from top to bottom.
3), catalysis dechlorination hydrogenation plant is connected with gas chromatograph: catalysis dechlorination hydrogenation plant carries out on-line joining process by temperature-resistant heat insulating pad and the gas chromatograph of interface section, and leak detection.
4), the activation of catalyzer: if air tight, open the pressure regulator valve on catalysis dechlorination hydrogenation plant.Regulate nebulizer gas pressure at 0.07-0.20MPa, stainless steel reaction pipe is heated to 280 ° of C simultaneously, keep heating at least 5h, catalyzer is activated, and remove wherein possible organic interfering material.
5), sample analysis: chlorinated paraffin sample is entered to catalysis dechlorination hydrogenation plant by the injection port of sample introduction part with Splitless injecting samples pattern, carry and enter stainless steel reaction pipe by carrier gas, short chain chlorinated paraffin generation redox reaction, generates the alkane of corresponding carbon chain lengths.Then pass through the transmission pin of interface section with carrier gas, all transfer in gas chromatography and analyze.
Online catalysis dechlorination hydrogenation plant reference conditions are for to do carrier gas with hydrogen, and pressure is 0.07-0.20MPa, and temperature controller temperature is adjusted to 280 ° of C, sample size 1 μ L.
Gas chromatography-hydrogen flameionization testing conditions is employing DB-5 quartz capillary column, internal diameter 0.32mm, and thickness 0.25 μ m, column length 30m, fixing is 5% phenyl-95% methyl polysiloxane mutually.Heating schedule is that 50 ° of C of initial temperature keep 3min, then rises to 280 ° of C with 10 ° of C/min, keeps 14min.Injector temperature is 280 ° of C, Splitless injecting samples, and constant voltage mode, does carrier gas with hydrogen.Detecting device is flame ionization ditector, and temperature is 270 ° of C.
Quantivative approach adopts internal standard method quantitatively to calculate short chain chlorinated paraffin.Per sample, generate the relative peak area of alkane on chromatogram and calculate corresponding mass concentration by typical curve.Then the mass concentration of alkane that basis is calculated and the chlorinity information of chlorinated paraffin sample calculate the mass concentration of short chain chlorinated paraffin in sample.Concrete grammar is as follows:
Wherein, C
sCCPs, sample(mg/L) be the mass concentration of short chain chlorinated paraffin in sample, C
alkane i, sample(mg/L) be the mass concentration that in sample, short chain chlorinated paraffin transforms the alkane generating, calculate acquisition by typical curve, i represents respectively n-decane, n-undecane, n-dodecane and n-tridecane.E
cl, sampleit is the chlorinity of chlorinated paraffin in sample.
In chlorinated paraffin product, the mass concentration κ of short chain chlorinated paraffin (mg/kg) is:
Wherein, C
sample(g/L) be the mass concentration of chlorinated paraffin in sample.
In sample, the computing method of the conversion ratio of short chain chlorinated paraffin are as follows:
Wherein, ex
2-methyl-undecane(mg/L) be that in experiment, internal standard compound matter transforms the undecanoic mass concentration of 2 – Jia Ji – generating.C
interior markit is the mass concentration (mg/L) of internal standard compound matter.E
cl, interior markit is the chlorinity of internal standard compound matter.When low conversion rate is in 90%, need to consider more catalyst changeout.
A kind of and the online dechlorination hydrogenation plant of short chain chlorinated paraffin gas chromatograph coupling, comprise sample introduction part, carrier gas air feed and pressure control section, with the catalysis dechlorination hydrogenation reaction part of heating element, the temperature control part of catalysis dechlorination hydrogenation reaction part being carried out to temperature control and adjusting, and the interface section being connected with gas chromatograph;
Described catalysis dechlorination hydrogenation reaction part is a stainless steel reaction pipe;
Described sample introduction part comprises an injection port, stainless steel carrier gas transfer tube;
Described injection port is fixed in one end of reaction tube, on the sidewall of the reaction tube near injection port, offers through hole, and through hole is connected with one end of stainless steel carrier gas transfer tube;
Described carrier gas air feed and pressure control section comprise a hydrogen source gas, pressure regulator valve, tensimeter; Hydrogen source gas is connected with the other end of carrier gas transfer tube;
Described temperature control part comprises thermopair, heating tube, glass wool heat-insulation layer and temperature controller; Reaction tube cover is embedded in heating tube, on the circumference of heating tube side, be provided with glass wool heat-insulation layer, one end of thermopair is inserted in heating tube, and the other end is connected with temperature controller by wire, heating tube is connected with temperature controller by wire, by the temperature of temperature controller regulation and control heating tube;
Described interface section comprises an adapter, transmission pin; Transmission pin is fixed in the other end of reaction tube by adapter.
Described injection port be the Central of the parts of stainless steel or aluminum alloy material with the aperture of the diameter 0.5-2mm of conical entrance, its effect is to facilitate sample introduction needle to insert to carry out sample injection operation.
Between the docking end face of injection port and reaction tube, be provided with the first high temperature resistant dottle pin of a disk shape.
Described carrier gas air feed and pressure control section comprise a hydrogen source gas, pressure regulator valve, tensimeter; Pressure regulator valve and tensimeter setting are connected with carrier gas transfer tube, and hydrogen source gas is transported in reaction tube inner chamber by carrier gas transfer tube through pressure regulator valve, tensimeter.
Described catalysis dechlorination hydrogenation reaction part is a stainless steel reaction pipe, in this reaction tube from injection port to the direction of transmitting pin successively layering filling silica wool, catalyzer, Carbon Dioxide calcium, catalyzer, Carbon Dioxide calcium, silica wool;
Filling layer height is respectively: silica wool 1-5mm, catalyzer 1-10mm, Carbon Dioxide calcium 1-8mm, catalyzer 1-10mm, Carbon Dioxide calcium 1-8mm, silica wool 1-5mm.
Tube inner diameter is 3-8mm mm, and long 5-20cm adopts inertia good stainless steel material to make, inwall polishing, and 300 ° of heatproofs are more than C, more than withstand voltage 5Mpa.
The silica wool of described catalysis dechlorination hydrogenation reaction part adopts high temperature resistant silica wool, and Carbon Dioxide calcium is pure for analyzing.
The catalyzer of described catalysis dechlorination hydrogenation reaction part is taking silanized glass microballon as carrier, the Pd(palladium that quality percentage composition is 0.42%) catalyzer.
Described adapter be one end with reaction tube) be connected the screw thread coordinating, the other end is with the hickey that is connected cooperation with injection port of chromatograph;
Transmission pin and reaction tube intracavity inter-connection, for being connected with the injection port of gas chromatograph;
Between adapter and reaction tube, be provided with graphite pads, ensure reacting gas through reaction tube inner chamber to the gas circuit sealing of transmitting pin;
Between adapter and the port surface of reaction tube, be provided with the second high temperature resistant dottle pin;
Form by adapter and graphite pads and the second high temperature resistant dottle pin the gas circuit that is tightly connected, gas flow enters gas chromatograph through catalysis dechlorination hydrogenation reaction part, transmission pin.
Advantage of the present invention and good effect are:
The method that the present invention is based on the online catalysis dechlorination hydrogenation plant of short chain chlorinated paraffin and gas chromatograph coupling is carried out analyzing and testing to the content of short chain chlorinated paraffin in chlorinated paraffin product.Carry out the content of the indirectly quantitative short chain chlorinated paraffin of gas chromatographic analysis in product by short chain chlorinated paraffin being changed into the alkane of corresponding carbon chain length.The series of problems such as traditional employing mass spectroscopy spectrogram and quantivative approach complexity, interfering material are many, quantitatively reliability is relatively low are solved.The quantitative analysis method of having set up short chain chlorinated paraffin content in chlorinated paraffin product, has the advantages such as simple to operate, experimental cost is low, testing result is accurate.Be applicable to Routine Test Lab analysis and the factory inspection in enormous quantities to chlorinated paraffin product of short chain chlorinated paraffin in chlorinated paraffin product.The limitation standard of China being carried out to short chain chlorinated paraffin content in chlorinated paraffin product provides foundation and technical guarantee with the production technology of researching and developing long-chain chlorinated paraffin product in high-purity, and significant.
Brief description of the drawings
Fig. 1 is the standard colors spectrogram of alkane
Fig. 2 is the structural representation of catalyst loading pattern in online catalysis dechlorination hydrogenation plant stainless steel reaction pipe;
Fig. 3 is the structural representation of online catalysis dechlorination hydrogenation plant;
Fig. 4 is the gas chromatogram of short chain chlorinated paraffin standard solution;
Fig. 5 is the gas chromatogram of chlorinated paraffin product chlorine wax-52.
Embodiment
The present invention has mainly proposed the detection method of short chain chlorinated paraffin content in a kind of chlorinated paraffin product, coupling based on the online catalysis dechlorination hydrogenation plant of short chain chlorinated paraffin and gas chromatograph has realized the direct injection analysis of chlorinated paraffin product, generates the alkane of corresponding carbon chain lengths by online catalytic reduction.Adopt the concentration of four kinds of alkane in inner mark method ration calculation sample, and obtain the content of short chain chlorinated paraffin in sample by calculating.
Below in conjunction with accompanying drawing, method of the present invention is described in further detail.
The detection method of short chain chlorinated paraffin content in chlorinated paraffin product provided by the invention, comprises following steps:
1), the preparation of internal standard compound matter solution: using the manually synthetic chlorinated paraffin with branched structure as internal standard compound matter, and be made into certain density inner mark solution with normal hexane, deepfreeze is preserved.
2), the preparation of alkane standard solution: be the n-alkane that is 10-13 by carbon chain lengths is mixed with series concentration alkane standard solution with certain density internal standard compound matter hexane solution.
3), the preparation of chlorinated paraffin sample: weigh in the balance and get a certain amount of chlorinated paraffin sample, in employing and alkane standard solution, the interior mark hexane solution of internal standard compound matter same concentrations fully dissolves constant volume, and after shaking up, sealing is preserved.
4), sample introduction operation: open carrier gas, start online catalysis dechlorination hydrogenation plant and gas chromatograph.After catalyzer in catalysis dechlorination hydrogenation plant is activated, and catalysis dechlorination hydrogenation plant and gas chromatograph reach setting operating conditions and stable after, adopt 10 μ L micro syringes to draw 1 μ L sample and enter online catalysis dechlorination hydrogenation plant and measure.
5), online catalysis dechlorination hydrogenation plant condition;
6), gas chromatography-hydrogen flameionization testing conditions: adopt chromatographic work station to record the chromatographic peak area of different carbon chain lengths alkane, and carry out qualitative analysis according to retention time.
7), quantitative test.Adopt the concentration of four kinds of alkane in inner mark method ration calculation sample, then calculate the mass concentration of short chain chlorinated paraffin in sample according to chlorinity information.
Wherein the internal standard compound matter in step 1) is that 2 – Jia Ji – undecanes are reacted to side chain chlorinated paraffin that artificial anamorphic zone branched structure and carbon chain lengths are 12 as internal standard compound matter by chlorination, and its chlorinity is 58.7%.Be made into the inner mark solution of 120mg/L with normal hexane, deepfreeze is preserved.Step 2) in alkane standard solution be to obtain by the method for dilution alkane work mother liquor.Alkane mother liquor is to take respectively in each 0.2000g to the 10mL volumetric flask of n-decane, n-undecane, n-dodecane and n-tridecane with balance, adds normal hexane fully to dissolve and constant volume, shakes up, and obtains concentration and be respectively the hybrid working mother liquor of four kinds of alkane of 20g/L.Then pipette respectively in 0,25,50,100 and 150 μ L hybrid working mother liquor to a 5 10mL volumetric flask with liquid-transfering gun, the interior mark hexane solution that is 120mg/L by concentration is diluted to graticule, mixes.The concentration that obtains four kinds of alkane in alkane standard solution is respectively 0,50, and 100,200 and 300mg/L.Then from low concentration to high concentration, analyze successively according to reference color spectral condition.Taking the peak area with respect to internal standard compound matter as ordinate, mass concentration (mg/L) is horizontal ordinate, drawing standard curve, typical curve correlation coefficient r >=0.99.Four kinds of n-alkanes are n-decane, n-undecane, n-dodecane, n-tridecane, and the i.e. undecanoic reference color spectrogram of 2 – Jia Ji – of generation product after internal standard compound matter hydrogenation catalyst, as shown in Figure 1.
Chlorinated paraffin sample in step 3) adopts balance to take 0.0050 – 0.0500g(and is accurate to 0.001g) sample, put into 10mL volumetric flask, adding 10mL concentration is that the interior mark hexane solution of 120mg/L fully dissolves constant volume, after shaking up, sealing is preserved.
The concrete steps of sample introduction operation are
1), the preparation of catalyzer: adopt 8mg PdCl
2, be dissolved in 5% acetic acid of 1mL heat, transfer to after surface plate, add 1.9g 50-70 order silanized glass microballon, and be placed under infrared lamp and dry.Add appropriate amount of deionized water, and with ammonia spirit (25% mass concentration) regulate pH to 9.After drying under infrared lamp, wash with 5mL cyclopentane, air-dry in fuming cupboard, obtain palladium content and be 0.42% Pd catalyzer.
2), the filling of catalysis dechlorination hydrogenation reaction pipe: silica wool B, catalyzer C, Carbon Dioxide calcium A, catalyzer C, Carbon Dioxide calcium A, silica wool B are loaded in the stainless steel reaction pipe (301) of catalysis dechlorination hydrogenation plant successively according to order from top to bottom.As shown in Figure 2.
3), catalysis dechlorination hydrogenation plant is connected with gas chromatograph: catalysis dechlorination hydrogenation plant carries out on-line joining process by the temperature-resistant heat insulating pad (503) of interface section with gas chromatograph, and leak detection.As shown in Figure 3.
4), the activation of catalyzer: if air tight, open the pressure regulator valve (201) on catalysis dechlorination hydrogenation plant.Regulate nebulizer gas pressure at 0.07-0.20MPa, stainless steel reaction pipe (301) is heated to 280 ° of C simultaneously, keep heating at least 5h, catalyzer is activated, and remove wherein possible organic interfering material.
5), sample analysis: chlorinated paraffin sample is entered to catalysis dechlorination hydrogenation plant by the injection port (101) of sample introduction part (1) with Splitless injecting samples pattern, carry and enter stainless steel reaction pipe (301) by carrier gas, short chain chlorinated paraffin generation redox reaction, generates the alkane of corresponding carbon chain lengths.Then pass through the transmission pin (504) of interface section (5) with carrier gas, all transfer in gas chromatography and analyze.
Online catalysis dechlorination hydrogenation plant reference conditions are for to do carrier gas with hydrogen, and pressure is 0.07-0.20MPa, and temperature controller temperature is adjusted to 280 ° of C, sample size 1 μ L.
Gas chromatography-hydrogen flameionization testing conditions is employing DB-5 quartz capillary column, internal diameter 0.32mm, and thickness 0.25 μ m, column length 30m, fixing is 5% Ben Ji – 95% methyl polysiloxane mutually.Heating schedule is that 50 ° of C of initial temperature keep 3min, then rises to 280 ° of C with 10 ° of C/min, keeps 14min.Injector temperature is 280 ° of C, Splitless injecting samples, and constant voltage mode, does carrier gas with hydrogen.Detecting device is flame ionization ditector, and temperature is 270 ° of C.
Quantivative approach adopts internal standard method quantitatively to calculate short chain chlorinated paraffin.Per sample, generate the relative peak area of alkane on chromatogram and calculate corresponding mass concentration by typical curve.Then the mass concentration of alkane that basis is calculated and the chlorinity information of chlorinated paraffin sample calculate the mass concentration of short chain chlorinated paraffin in sample.Concrete grammar is as follows:
Wherein, C
sCCPs, sample(mg/L) be the mass concentration of short chain chlorinated paraffin in sample, C
alkane i, sample(mg/L) be the mass concentration that in sample, short chain chlorinated paraffin transforms the alkane generating, calculate acquisition by typical curve, i represents respectively n-decane, n-undecane, n-dodecane and n-tridecane.E
cl, sampleit is the chlorinity of chlorinated paraffin in sample.
In chlorinated paraffin product, the mass concentration κ of short chain chlorinated paraffin (mg/kg) is:
Wherein, C
sample(g/L) be the mass concentration of chlorinated paraffin in sample.
In sample, the computing method of the conversion ratio of short chain chlorinated paraffin are as follows:
Wherein, ex
2-methyl-undecane(mg/L) be that in experiment, internal standard compound matter transforms the undecanoic mass concentration of 2 – Jia Ji – generating.C
interior markit is the mass concentration (mg/L) of internal standard compound matter.E
cl, interior markit is the chlorinity of internal standard compound matter.When low conversion rate is in 90%, need to consider more catalyst changeout.
Embodiment 1 accuracy
Employing concentration is 100mg/L, and the short chain chlorinated paraffin standard solution that chlorinity is 63%, as sample, adds after internal standard compound matter, adopts the inventive method to carry out quantitative test to it.The chromatogram obtaining as shown in Figure 4.In figure, each component is respectively: 1, n-decane; 2, n-undecane; 3,2-methyl-undecane (internal standard compound matter); 4, n-dodecane; 5, n-tridecane.Adopt the concentration of four kinds of alkane in inner mark method ration calculation sample, the middle relative peak area of alkane on chromatogram that generate calculates corresponding alkane mass concentration on working curve per sample.Calculate the mass concentration of short chain chlorinated paraffin in sample according to above-mentioned quantivative approach (1).Calculate the conversion ratio of short chain chlorinated paraffin according to above-mentioned quantivative approach (3).Replication 6 times, obtains in sample short chain chlorinated paraffin concentration and conversion ratio as shown in table 1.Mean concentration is 99.4mg/L, and relative error is between-4.3% ~ 8.6%.Illustrate that this device has good transformation efficiency and accuracy to analyzing short chain chlorinated paraffin.
Table 1
Adopt the synthetic chlorinated paraffin product chlorine wax – 52 of experiment indoors artificial as analytic target, this product mainly synthesizes as raw material using carbon chain lengths as the paraffin of 20 – 26, and wherein the concentration of short chain chlorinated paraffin is lower.Be made into the interior mark hexane solution that mass concentration is 5g/L by weight method, carry out continuously replication 7 times, calculate the mass concentration κ of short chain chlorinated paraffin in sample according to above-mentioned quantivative approach (2), and calculate the standard deviation of measured value, the method that obtains short chain chlorinated paraffin detects and is limited to 88mg/kg.
Embodiment 3 precision
Using chlorinated paraffin product chlorine wax-52 as analytic target, be made into the interior mark hexane solution that mass concentration is 5g/L by weight method, the chromatogram obtaining is as shown in Figure 5.Replication 7 times, calculates the mass concentration κ of short chain chlorinated paraffin in sample according to above-mentioned quantivative approach (2), and calculates the relative standard deviation of measured value, and the mass concentration κ and the relative standard deviation that obtain short chain chlorinated paraffin in sample are as shown in table 2.Illustrate that this device can be applied to the analyzing and testing to short chain chlorinated paraffin content in chlorinated paraffin product, and method accuracy is high, reproducible.
Table 2
Claims (10)
1. a detection method for short chain chlorinated paraffin content in chlorinated paraffin product, is characterized in that: comprise the following steps:
1), the preparation of internal standard compound matter solution: using the manually synthetic chlorinated paraffin with branched structure as internal standard compound matter, and be made into inner mark solution with normal hexane, deepfreeze is preserved;
2), the preparation of alkane standard solution: be the alkane standard solution that the n-alkane internal standard compound matter hexane solution that is 10-13 by carbon chain lengths is mixed with series concentration;
3), the preparation of chlorinated paraffin sample: weigh in the balance and get chlorinated paraffin sample, in employing and alkane standard solution, the interior mark hexane solution of internal standard compound matter same concentrations fully dissolves constant volume, and after shaking up, sealing is preserved;
4), sample introduction operation: open carrier gas, start online catalysis dechlorination hydrogenation plant and gas chromatograph; After catalyzer in catalysis dechlorination hydrogenation plant is activated, and catalysis dechlorination hydrogenation plant and gas chromatograph reach setting operating conditions and stable after, adopt 10 μ L micro syringes to draw 1 μ L sample and enter online catalysis dechlorination hydrogenation plant and measure;
5), online catalysis dechlorination hydrogenation plant condition;
6), gas chromatography-hydrogen flameionization testing conditions: adopt chromatographic work station to record the chromatographic peak area of different carbon chain lengths alkane, and carry out qualitative analysis according to retention time;
7), quantitative test: adopt the concentration of four kinds of alkane in inner mark method ration calculation sample, then calculate the mass concentration of short chain chlorinated paraffin in sample according to chlorinity information.
2. according to detection method claimed in claim 1, it is characterized in that:
Described internal standard compound matter is that 2 – Jia Ji – undecanes are reacted to side chain chlorinated paraffin that artificial anamorphic zone branched structure and carbon chain lengths are 12 as internal standard compound matter by chlorination, and its chlorinity is 58.7%; Be made into the inner mark solution of 120mg/L with normal hexane, deepfreeze is preserved.
3. according to detection method claimed in claim 1, it is characterized in that:
Described alkane standard solution is to obtain by the method for dilution alkane work mother liquor;
Alkane mother liquor is to take respectively in each 0.2000g to the 10mL volumetric flask of n-decane, n-undecane, n-dodecane and n-tridecane with balance, adds normal hexane fully to dissolve and constant volume, shakes up, and obtains concentration and be respectively the hybrid working mother liquor of four kinds of alkane of 20g/L; Then pipette respectively in 0,25,50,100 and 150 μ L hybrid working mother liquor to a 5 10mL volumetric flask with liquid-transfering gun, the interior mark hexane solution that is 120mg/L by concentration is diluted to graticule, mixes; The concentration that obtains four kinds of alkane in alkane standard solution is respectively 0,50, and 100,200 and 300mg/L.
4. according to detection method claimed in claim 1, it is characterized in that:
Described chlorinated paraffin sample adopts balance to take 0.0050 – 0.0500g(and is accurate to 0.001g) sample, put into 10mL volumetric flask, adding 10mL concentration is that the interior mark hexane solution of 120mg/L fully dissolves constant volume, after shaking up, sealing is preserved.
5. according to detection method claimed in claim 1, it is characterized in that:
The concrete steps of described sample introduction operation are:
1), the preparation of catalyzer: adopt 8mg PdCl
2, be dissolved in mass concentration 5% acetic acid of 1mL heat, transfer to after surface plate, add 1.9g 50-70 order silanized glass microballon, and be placed under infrared lamp and dry; Add deionized water, and with ammonia spirit (25% mass concentration) regulate pH to 9; After drying under infrared lamp, wash with 5mL cyclopentane, air-dry in fuming cupboard, obtain palladium content and be 0.42% Pd catalyzer;
2), the filling of catalysis dechlorination hydrogenation reaction pipe: silica wool, catalyzer, Carbon Dioxide calcium, catalyzer, Carbon Dioxide calcium, silica wool are loaded into successively in the stainless steel reaction pipe (301) of catalysis dechlorination hydrogenation plant according to order from top to bottom;
3), catalysis dechlorination hydrogenation plant is connected with gas chromatograph: catalysis dechlorination hydrogenation plant carries out on-line joining process by the temperature-resistant heat insulating pad (503) of interface section with gas chromatograph, and leak detection;
4), the activation of catalyzer: if air tight, open the pressure regulator valve (201) on catalysis dechlorination hydrogenation plant, regulate nebulizer gas pressure at 0.07-0.20MPa, stainless steel reaction pipe (301) is heated to 280 ° of C simultaneously, keep heating at least 5h, catalyzer is activated, and remove wherein possible organic interfering material;
5), sample analysis: chlorinated paraffin sample is entered to catalysis dechlorination hydrogenation plant by the injection port (101) of sample introduction part (1) with Splitless injecting samples pattern, carry and enter stainless steel reaction pipe (301) by carrier gas, short chain chlorinated paraffin generation redox reaction, generates the alkane of corresponding carbon chain lengths.Then pass through the transmission pin (504) of interface section (5) with carrier gas, all transfer in gas chromatography and analyze.
6. according to detection method claimed in claim 1, it is characterized in that: described online catalysis dechlorination hydrogenation plant reference conditions are: do carrier gas with hydrogen, pressure is 0.07-0.20MPa, and temperature controller temperature is adjusted to 280 ° of C, sample size 1 μ L.
7. according to detection method claimed in claim 1, it is characterized in that:
Described gas chromatography-hydrogen flameionization testing conditions is employing DB-5 quartz capillary column, internal diameter 0.32mm, and thickness 0.25 μ m, column length 30m, fixing is 5% Ben Ji – 95% methyl polysiloxane mutually.Heating schedule is that 50 ° of C of initial temperature keep 3min, then rises to 280 ° of C with 10 ° of C/min, keeps 14min, and injector temperature is 280 ° of C, Splitless injecting samples, and constant voltage mode, does carrier gas with hydrogen.Detecting device is flame ionization ditector, and temperature is 270 ° of C.
8. according to detection method claimed in claim 1, it is characterized in that: described quantivative approach adopts internal standard method quantitatively to calculate short chain chlorinated paraffin; Per sample, generate the relative peak area of alkane on chromatogram and calculate corresponding mass concentration by typical curve; Then the mass concentration of alkane that basis is calculated and the chlorinity information of chlorinated paraffin sample calculate the mass concentration of short chain chlorinated paraffin in sample; Concrete grammar is as follows:
Wherein, C
sCCPs, sample(mg/L) be the mass concentration of short chain chlorinated paraffin in sample, C
alkane i, sample(mg/L) be the mass concentration that in sample, short chain chlorinated paraffin transforms the alkane generating, calculate acquisition by typical curve, i represents respectively n-decane, n-undecane, n-dodecane and n-tridecane; E
cl, sampleit is the chlorinity of chlorinated paraffin in sample;
In chlorinated paraffin product, the mass concentration κ of short chain chlorinated paraffin (mg/kg) is:
Wherein, C
sample(g/L) be the mass concentration of chlorinated paraffin in sample.
9. according to detection method claimed in claim 1, it is characterized in that: in described sample, the computing method of the conversion ratio of short chain chlorinated paraffin are as follows:
Wherein, ex
2-methyl-undecane(mg/L) be that in experiment, internal standard compound matter transforms the undecanoic mass concentration of 2 – Jia Ji – generating.C
interior markit is the mass concentration (mg/L) of internal standard compound matter; E
cl, interior markit is the chlorinity of internal standard compound matter.When low conversion rate is in 90%, need to consider more catalyst changeout.
10. according to detection method claimed in claim 1, it is characterized in that:
Described online catalysis dechlorination hydrogenation plant comprises sample introduction part, carrier gas air feed and pressure control section, be connected with carrier gas air feed part, with the catalysis dechlorination hydrogenation reaction part of heating element, the temperature control part of catalysis dechlorination hydrogenation reaction part being carried out to temperature control and adjusting, and the interface section being connected with gas chromatograph;
Described catalysis dechlorination hydrogenation reaction part is a stainless steel reaction pipe;
Described sample introduction part comprises an injection port, stainless steel carrier gas transfer tube;
Described injection port is fixed in one end of reaction tube, on the sidewall of the reaction tube near injection port, offers through hole, and through hole is connected with one end of stainless steel carrier gas transfer tube;
Described carrier gas air feed and pressure control section comprise a hydrogen source gas, pressure regulator valve, tensimeter; Hydrogen source gas is connected with the other end of carrier gas transfer tube;
Described temperature control part comprises thermopair, heating tube, glass wool heat-insulation layer and temperature controller; Reaction tube cover is embedded in heating tube, on the circumference of heating tube side, be provided with glass wool heat-insulation layer, one end of thermopair is inserted in heating tube, and the other end is connected with temperature controller by wire, heating tube is connected with temperature controller by wire, by the temperature of temperature controller regulation and control heating tube;
Described interface section comprises an adapter, transmission pin; Transmission pin is fixed in the other end of reaction tube by adapter.
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| CN106645515A (en) * | 2016-12-29 | 2017-05-10 | 嘉兴学院 | Detection method for content of short-chain chlorinated paraffin in leather |
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| CN108061775A (en) * | 2017-07-10 | 2018-05-22 | Cem有限公司 | For analyzing the instrument of sample preparation |
| CN109731570A (en) * | 2018-12-17 | 2019-05-10 | 嘉兴学院 | It is a kind of for detecting the loaded palladium catalyst preparation method of short chain chlorinated paraffin |
| CN112730684A (en) * | 2020-12-27 | 2021-04-30 | 宁波市华测检测技术有限公司 | Test method for detecting seawater sediment organism short-chain chlorinated paraffin |
| CN114924010A (en) * | 2022-06-17 | 2022-08-19 | 广州海关技术中心 | Method for determining short-chain and medium-chain chlorinated paraffin content in chlorinated paraffin raw material |
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Cited By (9)
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| CN105842443A (en) * | 2015-01-16 | 2016-08-10 | 中国科学院大连化学物理研究所 | Method for determining influence of short-chain chlorinated paraffins on cell energy metabolic pathway |
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| CN106645515A (en) * | 2016-12-29 | 2017-05-10 | 嘉兴学院 | Detection method for content of short-chain chlorinated paraffin in leather |
| CN108061775A (en) * | 2017-07-10 | 2018-05-22 | Cem有限公司 | For analyzing the instrument of sample preparation |
| CN109731570A (en) * | 2018-12-17 | 2019-05-10 | 嘉兴学院 | It is a kind of for detecting the loaded palladium catalyst preparation method of short chain chlorinated paraffin |
| CN112730684A (en) * | 2020-12-27 | 2021-04-30 | 宁波市华测检测技术有限公司 | Test method for detecting seawater sediment organism short-chain chlorinated paraffin |
| CN114924010A (en) * | 2022-06-17 | 2022-08-19 | 广州海关技术中心 | Method for determining short-chain and medium-chain chlorinated paraffin content in chlorinated paraffin raw material |
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