CN101241074A - Fish meat petroleum hydrocarbon content determination method - Google Patents
Fish meat petroleum hydrocarbon content determination method Download PDFInfo
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Abstract
The present invention relates to a method for detecting the content of petroleum hydrocarbon in fish by infrared spectroscopy. The present invention eliminates impurity disturb by fish saponification step, extraction step and adsorption step to detect petroleum hydrocarbon residual content in the marine lives rapidly and accurately by infrared spectrophotometry. The method of present invention has the characteristics of low detection limit, small relative standard deviation and high precision.
Description
[technical field]
The present invention relates to food technology field, more specifically, the present invention relates to the assay method that infra-red sepectrometry is used to oppress PetroChina Company Limited.'s hydrocarbon content.
[background technology]
The fish body contains abundant animal fat and protein, and petroleum hydrocarbon is enriched in the animal fat, and grease is distributed in again in the structure of fish muscle and combines closely with protein.People know, generally contain methyl and methylene group in the petroleum hydrocarbon material, and alkane, naphthenic hydrocarbon are the 70-80% of total hydrocarbon amount in the oil, the CH in these two kinds of hydro carbons
3, CH
2, CH is the basis of infrared spectrophotometric determination.By being determined at CH
2The stretching vibration 2930cm of group c h bond
-1, CH
3The stretching vibration 2960cm of group c h bond
-1Stretching vibration 3030cm with the aromatic rings c h bond
-1Absorbance, can measure and calculate petroleum hydrocarbon content in vivo.And ultraviolet method spectrophotometric method and fluorescence spectrophotometry can only be measured the oil that contains aromatic hydrocarbons, and aromatic hydrocarbons only accounts for the 20-30% of oil total amount, even lower, and in addition, people know that some aromatic compounds also contain CH
3, CH
2, the CH group, so they are at 2970cm
-1, 2930cm
-1, 2900cm
-1Absorption is arranged.Like this, the result of infrared spectrophotometric determination will more can embody the content of total petroleum hydrocarbon in the sample.Generally speaking, because natural organic matter contains a large amount of methyl, methylene, they can disturb this mensuration, cause the infrared analysis result to be much higher than actual value.
For example " agriculture environmental protection "; 1997; the 16th volume; the 6th phase; 257-258 has described with white Chinese croaker and jewel grouper for 278 pages and has tested, with the distribution of fluorescence spectrophotometry research aromatic hydrocarbon pollutant in each tissue of fish body; the result shows that it is fish tallow that aromatic hydrocarbon is polluted the most serious position.But, adopt the method for infrared spectrophotometric determination flesh of fish PetroChina Company Limited. hydrocarbon content also to have not seen reported, therefore, the inventor carries out a large amount of experimental studies for this reason and has made the present invention.
[summary of the invention]
[technical matters that will solve]
The purpose of this invention is to provide a kind of assay method of oppressing PetroChina Company Limited.'s hydrocarbon content, it is good to adopt this method to obtain data repeatability, measures the precision height, and method is simple to operation.
[technical scheme]
For improving the accuracy of infrared spectrophotometric determination, the flesh of fish need be cleared up, saponification and extraction pre-service, makes fat and the thorough hydrolysis of protein, therefrom isolates petroleum hydrocarbon, non-hydrocarbon materials is changed into water-soluble substances, from carbon tetrachloride extraction liquid, separate.
The present invention is achieved through the following technical solutions:
Assay method of oppressing PetroChina Company Limited.'s hydrocarbon content of the present invention, the step of its this method of feature is as follows:
One, flesh of fish treatment step
Get its meat after scaling, remove the peel fish, again with high speed biological tissue bruiser smash to pieces, mixing, the pasted fish meat that obtains is placed in the sealed glass jars, ℃ preserves standby down in temperature-20.
Described high speed biological tissue bruiser for example changzhou state China instrument plant is smashed equal pulp grinder product sold to pieces with trade name JJ-2 tissue.
Two, Yu Rou saponification
Step (one) is obtained pasted fish meat thaws, take by weighing 2.0-3.0 weight portion pasted fish meat and place iodine flask, add the 2-10mol/L sodium hydroxide solution of 10-40 parts by volume, the absolute ethyl alcohol of adding 10-25 parts by volume, under temperature 15-75 ℃, shook saponification 8-38 hour, and made flesh of fish digestive juice like this.
In the application's file, described weight portion all should be identical magnitude with parts by volume, for example weight portion is the gram order of magnitude, and then parts by volume is the ml quantity level, unless otherwise noted.
On meaning of the present invention, saponification should be appreciated that it is the basic hydrolysis of fatty glyceride, is about to fatty glyceride and is hydrolyzed into soap and glycerine.
According to a kind of preferred implementation, in described saponification step, add the 2-10mol/L sodium hydroxide solution of 10-20 parts by volume.
According to another kind of preferred implementation, in described saponification step, add the 6mol/L sodium hydroxide solution.
According to another kind of preferred implementation, in described saponification step, add the absolute ethyl alcohol of 10-20 parts by volume.
More preferably, described saponification step was carried out 12-24 hour under temperature 25-45 ℃.
Three, extraction and absorption
The flesh of fish digestive juice that step (two) obtains is poured in the separating funnel, use phenixin to extract described flesh of fish digestive juice three times then according to described flesh of fish digestive juice volume and phenixin volume ratio 2/5 to 2/3, the extract that obtains after each extraction makes water wash according to described extract volume and water volume ratio 2/5 to 1/1, then, the washing extract carries out drying with anhydrous sodium sulfate, dried extract adds in the 50mL volumetric flask, add phenixin again to graticule, mixing obtains carbon tetrachloride extraction liquid;
Use therein phenixin should be at 2600～3200cm
-1Between absorbance less than 0.03 (for example using the 1cm quartz colorimetric utensil, Wuxi true qualities Environmental Protection Technology Co., Ltd), each step of the inventive method is all used this phenixin.
According to a kind of preferred implementation, add saturated aqueous sodium chloride during extraction in described flesh of fish digestive juice volume 1-5 parts by volume.
More preferably, add saturated aqueous sodium chloride during extraction in described flesh of fish digestive juice volume 3-4 parts by volume.
Described carbon tetrachloride extraction liquid is removed impurity with the flow velocity of 0.8-1.2mL/min by the magnesium silicate post.Wherein magnesium silicate is the magnesium silicate that obtains through following processing: get the residual level of 60-100 purpose farming magnesium silicate and place crucible, in the high temperature muffle furnace, heat 2h at 500 ℃, in this stove, be chilled to about 150 ℃ then, move into again and be cooled to room temperature in the exsiccator, in ground glass stoppered bottle, preserve stand-by.Farming residual level silicic acid Florisil (60-100 order) purchases the three ring instrument Ltds in the BeiJing ZhongKe.
Four, infrared spectrum measurement typical curve plot step
At first prepare standard oil: n-hexadecane, isooctane and benzene are mixed according to volume ratio at 65: 25: 10 and obtain standard oil; Measure 0.25,0.50,0.75,1.00,1.25,1.50 respectively, the described standard oil of 1.75mL is added in the 10mL volumetric flask of a small amount of phenixin, adds phenixin again to graticule, mixing obtains standard oil solution;
Secondly, use infrared spectrometer, with the phenixin be background measure described standard oil solution at 3200～2600cm
-1Infrared absorption spectrum.
Described infrared spectrometer for example is Fourier transformation infrared spectrometer Nicolet Nexus, is made by Thermo Electron Corporation.
According to these infrared absorption spectrum drawing standard curves, obtain regression equation and be
y＝0.2642x+0.012，R
2＝0.9997。
Five, petroleum hydrocarbon assay step
Use infrared spectrometer to measure the infrared absorption spectrum that it removes the carbon tetrachloride extraction liquid of impurity under the following conditions:
Sweep limit: 3200～2600cm
-1
Scanning times: 28-36;
Resolution: 2-6cm
-1
Then by formula (1) calculates the petroleum hydrocarbon content in the described flesh of fish:
In the formula:
X
1-sample PetroChina Company Limited. hydrocarbon content, unit are milligram every gram (mg/g);
The petroleum hydrocarbon content (mg/L) that m-draws from typical curve;
V
1-extract constant volume (mL);
The M-sample quality, unit is gram (g).
Preferably, the extract that obtains after each extraction makes water wash according to described extract volume and water volume ratio 2/5 to 1/1, removes existing polar impurity in the extract.
Preferably, add saturated aqueous sodium chloride during extraction in described flesh of fish digestive juice volume 1-5 parts by volume.
More preferably, add saturated aqueous sodium chloride during extraction in described flesh of fish digestive juice volume 3-4 parts by volume.
In the magnesium silicate post, add aluminium oxide, remove the adsorbable unsaponifiables of aluminium oxide in magnesium silicate weight 0.5-2%.
The present invention is described in more detail below.
For the accuracy of measuring, the flesh of fish should carry out pre-service.Described pre-service comprises fatty saponification and proteolysis.Fatty glyceride is glycerine and fatty acid-esterified result.People are called saponification with the fatty acid glycerine ester alkaline hydrolysis.Use excessive alkali, grease can complete hydrolysis and is changed into soap and glycerine.In actual saponification hydrolysis of animal grease process, exist saponification time long, saponification is not exclusively even be difficult to problem such as saponification.Because natural oil and alkali lye are immiscible, saponification is again an interfacial reaction, and therefore, any factor that influences two phase molecules contact on profit two-phase degree of scatter and the interface all can influence saponification speed and saponification degree.The complexity of grease itself forms and the rheological in course of reaction, in the dispersion situation of aqueous phase, speed and grease molecule and the base molecule impact velocity etc. that soap-film breaks, all be the immediate cause that influences saponification.And these reasons are relevant with time, temperature and the alkali lye consumption etc. of saponification.Generally speaking, three kinds of methods, i.e. acid hydrolysis, basic hydrolysis and enzyme hydrolysis are adopted in the hydrolysis of protein.For short-cut method, the present invention adopts basic hydrolysis, and when fatty acid carried out saponification, the hydrolysis of protein was also carried out simultaneously in the flesh of fish.So sample pre-treatments involved in the present invention is to have comprised the fatty saponification and the hydrolysis of protein on saponification is handled in fact.
The saponification effect is the committed step that this method is handled, if the saponification effect is bad, more serious pale brown look can appear in extract, makes emulsion serious, the effect of influence extraction, thus influence measurement result.In the saponification process, adopt conditions such as adding the water yield, saponification time, temperature all can influence the saponification effect.For this reason, the inventor has carried out the saponification Study on Conditions.
One, flesh of fish saponification Study on Conditions
1, saponification temperature is to the influence of saponification effect
To oppress sample thaws, accurately take by weighing flesh of fish sample 2.0-3.0g (being accurate to 0.01g), place the 100mL iodine flask, the sodium hydroxide solution, the 20mL absolute ethyl alcohol that add 20mL 6mol/L, jump a queue, fully shake saponification 18h under uniform temperature, every jolting half an hour iodine flask once, make treatments of the sample liquid in the initial 2h.
Saponification temperature is selected 15,25,35,45,55,65,75 ℃ respectively.It the results are shown in Table 1 and Fig. 1.
Can see that by Fig. 1 its measured value is along with the rising of saponification temperature obviously reduces, change after arriving 35 ℃ and tend towards stability, continue the rising temperature, surpass 50 ℃ after measured value slowly reduce along with the rising of saponification temperature.Showed that low temperature was unfavorable for saponification, visible unsaponified molecule in the saponification liquor under 15 ℃, saponification is incomplete.Along with the rising of temperature, saponification speeds up, and the saponification liquor under 35 ℃ is relatively clarified, and saponification is more complete, and temperature is too high, some the low boiling volatility petroleum hydrocarbons volatilizations in the sample, and measured value descends, and therefore selects 35 ℃ of saponification temperatures, continues subsequent experimental.
2, saponification time is to the influence of saponification effect
Its embodiment is identical with the front, just at 35 ℃ of saponification 8,13,18,23,28,33 respectively down of saponification temperature, 38h.It the results are shown in Table 2 and Fig. 2.
Measured value reduces along with the increase of saponification time as can be seen from Figure 2, changes to the 18h and tends towards stability, and shows the prolongation along with saponification time, and hydrolysis degree constantly increases, and it is complete that saponification is tending towards.Continuing time expand there is no obvious influence to measured value, so select 18h continuation subsequent experimental.
3, the alkali lye consumption is to the influence of saponification effect
Its embodiment is identical with the front, only is to use 10,15,20,25,30, the NaOH solution of the 6mol/L of 35mL and 40mL is at 35 ℃ of following saponification time 18h of saponification temperature.It the results are shown in Table 3 and Fig. 3.
Fig. 3 shows that measured value reduces along with the increase of alkali lye consumption, change to the NaOH solution of the 6mol/L of 20mL and tend towards stability, show increase along with the alkali lye consumption, hydrolysis degree constantly increases, it is complete that saponification is tending towards, continue to increase the alkali lye consumption and no longer include significant change, therefore select the solution of the 6mol/L NaOH of 20mL to carry out subsequent experimental.
4, response surface analysis
Find that by experiment of single factor saponification temperature, saponification time and alkali lye consumption all have tangible influence to the petroleum hydrocarbon Determination on content, and have certain reciprocal effect between this three.Traditional single-factor analysis therapy can't be finished the optimization of reciprocal effect factor, but the response surface analysis method can satisfy this requirement.The response surface analysis method is a kind of analytical approach that mathematical method and statistical technique combine, be widely used for determining multivariable impact effect and optimization experiment process, condition in the experiment, the center rotary combination design is response surface analysis method a kind of experimental design method commonly used.
Test design and the results are shown in Table 1.The whole test design comprises 15 testing sites, and test 1-12 is the factorial point, and the independent variable span is in the three-dimensional vertices that each factor constituted, and test 13-15 is zero point, is the central point in zone, and the center experiment repeats 3 times, in order to the estimating experiment error.
Table 1 RSA test design and result
| Tested number | X 1Saponification temperature/℃ | X 2Saponification time/h | X 3Alkali lye consumption/mL | Petroleum hydrocarbon content (mg/g) |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 | -1 -1 -1 -1 0 0 0 0 1 1 1 1 0 0 0 | -1 0 0 1 -1 -1 1 1 -1 0 0 1 0 0 0 | 0 -1 1 0 -1 1 -1 1 0 -1 1 0 0 0 0 | 0.1502 0.1092 0.2637 0.2016 0.2112 0.1504 0.1630 0.1023 0.1511 0.2394 0.1245 0.2054 0.0989 0.0925 0.0934 |
Table 2 analysis of variance table
| Soruces of variation | Degree of freedom | Quadratic sum | All the side and | F | Conspicuousness |
| The once mutual total regression of a quadratic term | 3 3 3 9 | 0.02670 0.16266 0.00012 0.18948 | 0.00890 0.05422 0.00004 0.06316 | 201.75773 137.08107 0.94443 35.97927 | ** ** * |
F
0.05(3,2)=19.16 F
0.01(3,2)=99.17;
*Be that 0.05 level is remarkable,
*Be that 0.01 level is remarkable
Table 3 parameter estimation table
| Parameter | Degree of freedom | Standard error | The T value | Greater than | the probability of t| | Estimates of parameters |
| X1 X2 X3 X1*X1 X1*X2 X1*X3 X2*X2 X2*X3 X3* |
1 1 1 1 1 1 1 1 1 | 0.0041 0.0041 0.0041 0.0060 0.0058 0.0058 0.0060 0.0058 0.0060 | 11.528 -6.128 -5.596 9.154 -0.917 -0.322 5.250 0.004 5.071 | 0.0001 0.0017 0.0025 0.0003 0.4012 0.7608 0.0033 0.9967 0.0039 | 0.00469 -0.0249 -0.0228 0.0548 -0.0053 -0.0018 0.0314 0.00002 0.0304 |
From table 2 and table 3 as can be seen, the total regression model is significant, lose intend not remarkable.
The figure of response surface analysis method is the factor X of specific response surface Y correspondence
1, X
2, X
3A three dimensions that constitutes can reflect the influence of each factor to response intuitively, the relation of response and 3 influence factor saponification time, saponification temperature and alkali lye consumptions as can be seen from response surface analysis Fig. 4-6 of test gained.As can be seen from the figure in certain scope, total trend all is the increase along with saponification time, saponification temperature and alkali lye consumption, and the content elder generation of petroleum hydrocarbon reduces afterwards to increase tends towards stability.Adopt the SAS analytic system that regression equation is analyzed, optimized the saponification condition: saponification temperature is 30 ℃, and the time is 20h, and the alkali lye consumption is 16.5mL.The silver carp fish carries out saponification with this understanding, and in conjunction with solvent extraction and adsorption column absorption, the average content that records flesh of fish PetroChina Company Limited. hydrocarbon is 0.0821mg/g.
Two, extraction and absorption research
Described digestive juice is all poured in the separating funnel of 500mL, with 20mL saturated nacl aqueous solution and 80mL distilled water washing iodine flask, transfer to cleansing solution in the separating funnel successively, the digestive juice that divides three extraction samples with the 40mL phenixin, merge three times extract, and water washing three times, extract is by placing about 2g anhydrous sodium sulfate in the glass funnel inflow 50mL at filter paper vertex of a cone place volumetric flask.After treating that extract flows into volumetric flask, measure an amount of phenixin washing anhydrous sodium sulfate layer and funnel, cleansing solution is incorporated the 50mL volumetric flask into, adds phenixin to graticule, and mixing obtains carbon tetrachloride extraction liquid.Carbon tetrachloride extraction liquid is used determination of infrared spectroscopy after magnesium silicate post adsorption treatment.
1, the selection of standard oil
Infrared spectrophotometer has taken into full account the common influence of alkane and aromatic hydrocarbon, and the miscella of stipulating a kind of fixed mixing ratio is a standard oil, and is when the composition of various hydro carbons in the testing sample changes to some extent, little to the mensuration influence of infrared spectrophotometer.Standard oil used herein is according to the regulation of standard GB/T16488-1996, promptly by 65% n-hexadecane, 25% isooctane and 10% benzene mixed preparing.
2, the selection of extraction conditions
The standard oil that adds known quantity after the saponification of flesh of fish sample carries out the optimization of extraction conditionss such as phenixin consumption, extraction times.The result shows, divides three extractions can extract petroleum hydrocarbon in the sample fully with the phenixin of 40mL.Occur emulsion in extraction process sometimes, the sodium chloride saturated solution that adds a small amount of (1-3mL) helps breakdown of emulsion, makes the easier layering of solution to improve extraction efficiency.The results are shown in Table 4.
Table 4 sample adds standard oil and reclaims experiment
| Sample | Add scalar (mg) | Extracting twice measured value (mg) | Extract three measured values (mg) | The extracting twice recovery (%) | Extract three recovery (%) |
| 1 2 3 | 0.2976 0.2976 0.2976 | 0.2587 0.2392 0.2433 | 0.2699 0.2712 0.2794 | 86.93 80.38 81.75 | 90.69 91.13 93.88 |
3, the selection of column condition
(1) selection of dress column method
Point out among standard GB/T16488-1996 will soak 12h with pure water before the magnesium silicate dress post, wet method upper prop then, but in actual mechanical process, the wet method upper prop is difficult to avoid to introduce water, as can be seen from Figure 9 the effect of dry method upper prop effective than wet method upper prop.Because the wet method upper prop is introduced water easily, infrared analysis is seriously disturbed in the existence meeting of water, even the solution of crossing behind the post dewaters with anhydrous sodium sulfate, the result does not have the effective of dry method upper prop yet.Wet method upper prop on the other hand, the existence of water can influence fully contacting of extract and magnesium silicate, have reduced adsorption efficiency.So select the dry method upper prop for use in the test.Piston below the pillar necessarily can not be coated with lubricant, because lubricant can be taken in the effluent by phenixin, reduces accuracy as a result.
(2) the adsorbent consumption determines
(internal diameter is 10mm to regulation adsorbent magnesium silicate at glass chromatography column among standard GB/T16488-1996, long be 200mm) in packed height be 80mm, GB/T16488-1996 at working sample be water quality, and the sample of this test is the flesh of fish, consider that different samples also can be variant through contained impurity level in the extraction solvent behind the carbon tetrachloride extraction, so this test has been chosen the adsorbent of different amounts and crossed post, thereby determine the adsorbent consumption.The quality of finding the adsorbent about packed height 80mm in concrete dress post process is about 2g, so chosen 1g, 2g respectively, 3g magnesium silicate adsorbent adsorbs extract.Infrared analysis value after 1g, the 3g magnesium silicate adsorbents adsorb respectively with the 2g adsorbents adsorb after measured value compare.Measured value from table 5 is 1g MgSiO as can be seen
3Adsorbent can't be removed impurity fully, and the result of table 6 then shows 2gMgSiO
3Adsorbent can be removed impurity fully, so the use amount of this test subsequent experimental mesosilicic acid magnesium adsorbent all is 2g.
Table 5 MgSiO
3The comparative experiments result one of consumption
| 1g MgSiO 3Determining adsorption value (mg/g) | 2g MgSiO 3Determining adsorption value (mg/g) | Mean value (mg/g) | Error | Relative error | Standard deviation | Relative |
|
| 1 2 | 0.2762 0.2968 | 0.1041 0.1128 | 0.1901 0.2048 | 0.1721 0.1840 | 1.6532 1.6312 | 0.1217 0.1301 | 8.6％ 6.4％ |
Annotate: error and relative error are that the measured value after adsorbing with the 2g magnesium silicate is that true value is tried to achieve.
Table 6 MgSiO
3The comparative experiments result two of consumption
| 3g MgSiO 3Determining adsorption value (mg/g) | 2g MgSiO 3Determining adsorption value (mg/g) | Mean value (mg/g) | Error | Relative error | Standard deviation | Relative |
|
| 1 2 | 0.0973 0.1062 | 0.1041 0.1128 | 0.1007 0.1095 | -0.0068 -0.0066 | 6.5％ 5.9％ | 0.0119 0.0047 | 4.8％ 4.3％ |
Annotate: error and relative error are that the measured value after adsorbing with the 2g magnesium silicate is that true value is tried to achieve
(3) column flow rate determines
The flow velocity of carbon tetrachloride extraction liquid in the magnesium silicate post is unsuitable too fast also should not be slow excessively.Flow velocity is too fast, and the duration of contact of extract and magnesium silicate adsorbent is very short, and absorption not exclusively causes separating effect relatively poor; Because phenixin is a volatile solvent, if flow velocity is slow excessively, then can influence measurement result.So flow speed control gets final product about 1.0mL/min.
4, the optimization of extraction step
Infrared analysis value height very after the extract process magnesium silicate adsorbents adsorb of in experimentation, finding to obtain with the carbon tetrachloride extraction saponification liquor, to the adsorbed solution high-performance liquid chromatogram determination, found that that cholesterol is still arranged in the adsorbed solution is residual; Carbonyl absorption peak has appearred in (see figure 10) in the infrared spectrum.So extraction step is improved, extract has been carried out washing and added a spot of aluminium oxide in the magnesium silicate post, the existing polar impurity water soluble in the extract because petroleum hydrocarbon is water insoluble, aluminium oxide can adsorb to fall the interference of unsaponifiables such as pigment energy material.Through again adsorbed solution having been carried out high-performance liquid chromatogram determination and infrared coating method mensuration behind the water-washing step, the result shows that the step after the improvement helps the removal of impurity, has removed the infrared analysis interfering material.To not optimizing and extract after optimization step carries out infrared scan (Figure 11), change has taken place in the position of the vibration absorption peak of the c h bond of two figure as can be seen from the figure, and this is because the not influence of residual impurity to absorbing in the extract of washing.
5, the stability of extraction solution
In the process of the test stability of the carbon tetrachloride extraction solution after magnesium silicate absorption has been made mensuration, the result shows and the carbon tetrachloride extraction solution sealing that obtains at last is kept in the refrigerator (1-4 ℃) to measure its result who obtains after one month more constant, illustrate that the stability of carbon tetrachloride extraction solution is better.Figure 12 is that the carbon tetrachloride extraction solution after the magnesium silicate absorption is placed the infrared spectrogram of measuring after the different time sections.
6, method detection limit
The method detection limit is to determine that a kind of particular analysis method detects the Cmin or the minimum value of test substance in given degree of confidence from sample, and its meaning is accurately to judge that whether having concentration in the sample is higher than blank test substance.
This experiment adopts the method detection limit MDL=3.143Sb of defined among the U.S. EPA SW-846 as basis, prepares the standard oil solution of 1.50mg/L respectively and measures for 7 groups, calculates to such an extent that method detects and is limited to 0.14mg/L (the results are shown in Table 7).
Table 7 method detection limit is measured (mg/L)
7, precision
Consistent each other degree between each time measured value when precision is meant repeatedly the same amount of replication.Good precision is the condition precedent that guarantees to obtain good accuracy, and precision of measurement is bad, just good accuracy can not be arranged.Stochastic error in the mensuration process has determined the precision of measurement result, precision is represented with the form of deviation, standard deviation or relative standard deviation, the accuracy of deviation reflection precision is relatively poor, and standard deviation and relative standard deviation are the good methods of expression precision.For repeatability and the precision of verifying the infrared spectrophotometric determination result, the silver carp sample is carried out replicate determination 6 times, measurement result sees Table 8.Going out relative standard deviation according to the data computation that records is 5.9%, shows that this method precision is better, has reappearance preferably.
The precision experiment that table 8 silver carp petroleum hydrocarbon is measured
8, accuracy
Accuracy is the degree that the value mean value measured under certain experiment condition is consistent with true value.When systematic error exists, can make between the true value of the value that records and mensurated amount and produce skew.Bias size represents that with error or relative error error or relative error are more little, and the bias between expression measured value and the true value is more little, and accuracy is high more.In real work, adding standard substance commonly used or standard method compare test, and when no standard substance or standard method, the pure material that adds determined component commonly used carries out recovery test and estimates and definite accuracy.This test promptly adopts the mark-on recovery test to estimate the accuracy of measured value.Choosing high, medium and low three concentration levels joins and carries out recovery test in the sample, the determination of recovery rates result of low concentration is between 70-85%, the determination of recovery rates result of middle and high concentration shows that this experiment accuracy is higher between 90-105%, the results are shown in Table 9.
The mark-on recovery test that table 9 silver carp petroleum hydrocarbon is measured
| Sequence number | M Low＝0.0992mg | M In＝0.2976mg | M High＝0.4960mg | ||||||
| M Not/mg | M Add/mg | R/％ | M Not/mg | M Add/mg | R/％ | M Not/mg | M Add/mg | R/％ | |
| 1 2 3 4 5 6 | 0.2631 0.2544 0.2656 0.2731 0.2705 0.2810 | 0.3382 0.3347 0.3374 0.3497 0.3450 0.3628 | 75.7 80.9 72.4 77.2 75.1 82.5 | 0.2631 0.2544 0.2656 0.2583 0.2705 0.2689 | 0.5473 0.5228 0.5218 0.5360 0.5553 0.5344 | 95.4 90.2 86.1 93.3 95.7 89.2 | 0.2631 0.2544 0.2656 0.2583 0.2705 0.2689 | 0.7720 0.7494 0.7428 0.7727 0.7566 0.7284 | 102.6 99.8 96.2 103.7 98.0 92.6 |
| Annotate: M NotFor not adding the target measured value; M AddFor adding the target measured value; R is the recovery=(M Add-M Not)/M | |||||||||
This shows by assay method detection limit, precision, accuracy, proved the feasibility of infrared spectrophotometric determination aquatic products PetroChina Company Limited. hydrocarbon residual content.
By extraction step, adsorption step are optimized, removed the interference of impurity, improve extraction and adsorption efficiency.Divide with the 40mL phenixin three times saponification liquor to be extracted, extract magnesium silicate adsorption column with the dry method upper prop after washing further adsorbs impurity, the adsorbent solution infrared scan.The residual content mean value of PetroChina Company Limited.'s hydrocarbon that the silver carp fish silver carp petroleum hydrocarbon that obtains is measured is approximately 0.10mg/g.
[beneficial effect]
The present invention passes through flesh of fish saponification, extraction step, adsorption step, the interference of removing impurity, and the realization infrared spectrophotometer is measured aquatic products PetroChina Company Limited. hydrocarbon residual content rapidly and accurately, and the detection limit of the inventive method is low, and relative standard deviation is little, the accuracy height.
[description of drawings]
Fig. 1 is the influence of saponification temperature to the petroleum hydrocarbon assay
Fig. 2 is the influence of saponification time to the petroleum hydrocarbon assay
Fig. 3 is the influence of alkali lye consumption to the petroleum hydrocarbon assay
Fig. 4 is saponification time and the saponification temperature response surface figure to the petroleum hydrocarbon content influence
Fig. 5 is alkali lye consumption and the saponification temperature response surface figure to the petroleum hydrocarbon content influence
Fig. 6 is alkali lye consumption and the saponification time response surface figure to the petroleum hydrocarbon content influence
Fig. 7 is the typical curve of standard oil
Fig. 8 is the infrared spectrogram (3200～2600cm of variable concentrations standard oil
-1)
Fig. 9 is that same sample dry method is crossed the infrared spectrum after post and wet method are crossed post
Figure 10 is that petroleum hydrocarbon is measured the infrared spectrum that solution obtains by coating method
Figure 11 is the infrared spectrogram of not optimizing and passing through the extract after optimizing
Figure 12 is that the carbon tetrachloride extraction solution after the magnesium silicate absorption is placed the infrared spectrogram of measuring behind the different time.
[embodiment]
Measure according to following step:
One, flesh of fish treatment step
Get its meat after the silver carp fish of buying from market, green hill scales, removes the peel, the JJ-2 tissue of producing with changzhou state China instrument plant smashs that equal pulp grinder is smashed to pieces, mixing to pieces again, and the pasted fish meat that obtains is placed in the sealed glass jars, and ℃ preservation is standby down in temperature-20.
Two, Yu Rou saponification
Step (one) is obtained pasted fish meat thaws, take by weighing 2.5 gram pasted fish meats and place iodine flask, the 5mol/L that adds 15ml analyzes pure cerium hydroxide sodium solution (deionized water, meet one-level water quality standard among the GB/T 6682, chemicals company limited of traditional Chinese medicines group), add the 20mL absolute ethyl alcohol, under 30 ℃, shake saponification 20h, make flesh of fish digestive juice.
Three, extraction and absorption
The flesh of fish digestive juice 100mL that step (two) is obtained pours in the separating funnel, use 100mL to analyze the described flesh of fish digestive juice of pure phenixin (chemicals company limited of traditional Chinese medicines group product) extraction then, extract three times, then, combining extraction liquid carries out drying with analyzing pure anhydrous sodium sulfate (chemicals company limited of traditional Chinese medicines group product), measuring the dry extract of 10mL is added in the 50mL volumetric flask with the cleansing solution that 10mL washs phenixin, add phenixin to graticule, mixing obtains carbon tetrachloride extraction liquid;
Then, allow described carbon tetrachloride extraction liquid, remove impurity with the magnesium silicate post of 0.8mL/min by handling according to previous methods.
Four, infrared spectrum measurement typical curve plot step
At first prepare standard oil: n-hexadecane, isooctane and benzene are mixed according to volume ratio at 65: 25: 10 and obtain standard oil; Measure 0.25,0.50,0.75,1.00,1.25,1.50 respectively, the described standard oil of 1.75mL is added in the 10mL volumetric flask of a small amount of phenixin, adds phenixin again to graticule, mixing obtains standard oil solution;
Secondly, use infrared spectrometer, with the phenixin be background measure described standard oil solution at 3300～2600cm
-1Infrared absorption spectrum;
According to these infrared absorption spectrum drawing standard curves, obtain regression equation and be
y＝0.2642x+0.012，R
2＝0.9997；
Five, petroleum hydrocarbon assay step
Use Fourier infrared spectrograph Nicolet Nexus (Thermo Electron Corporation) to measure the infrared absorption spectrum of above-mentioned carbon tetrachloride extraction liquid under the following conditions, condition determination is as follows:
Sweep limit: 3200～2600cm
-1
Scanning times: 32;
Resolution: 4cm
-1
Then by formula (1) calculates the petroleum hydrocarbon content in the described flesh of fish:
In the formula:
X
1-sample PetroChina Company Limited. hydrocarbon content, unit are milligram every gram (mg/g);
The petroleum hydrocarbon content (mg/L) that m-draws from typical curve;
V
1-extract constant volume (mL);
The M-sample quality, unit is gram (g).
The petroleum hydrocarbon content that promptly obtains in the silver carp is 0.1060mg/g.
Embodiment 2 grass carp PetroChina Company Limited. hydrocarbon contents are measured
Measure according to following step:
One, flesh of fish treatment step
Get its meat after the grass carp of buying from market, green hill scales, removes the peel, the JJ-2 tissue of producing with changzhou state China instrument plant smashs that equal pulp grinder is smashed to pieces, mixing to pieces again, and the pasted fish meat that obtains is placed in the sealed glass jars, and ℃ preservation is standby down in temperature-20.
Two, Yu Rou saponification
Step (one) is obtained pasted fish meat thaws, take by weighing the 2.8g pasted fish meat and place iodine flask, the 6mol/L that adds 15mL analyzes pure cerium hydroxide sodium solution (deionized water, meet one-level water quality standard among the GB/T 6682, chemicals company limited of traditional Chinese medicines group), add the 15mL absolute ethyl alcohol, under 30 ℃, shake saponification 20h, make flesh of fish digestive juice.
Three, extraction and absorption
The flesh of fish digestive juice 100mL that step (two) is obtained pours in the separating funnel, use 100mL to analyze the described flesh of fish digestive juice of pure phenixin (chemicals company limited of traditional Chinese medicines group product) extraction then, extract three times, then, combining extraction liquid carries out drying with analyzing pure anhydrous sodium sulfate (chemicals company limited of traditional Chinese medicines group product), measuring the dry extract of 10mL is added in the 50mL volumetric flask with the cleansing solution that 10mL washs phenixin, add phenixin to graticule, mixing obtains carbon tetrachloride extraction liquid;
Then, allow described carbon tetrachloride extraction liquid, remove impurity with the magnesium silicate post of 1.0mL/min by handling according to previous methods.
Four, infrared spectrum measurement typical curve plot step
At first prepare standard oil: n-hexadecane, isooctane and benzene are mixed according to volume ratio at 65: 25: 10 and obtain standard oil; Measure 0.25,0.50,0.75,1.00,1.25,1.50 respectively, the described standard oil of 1.75mL is added in the 10mL volumetric flask of a small amount of phenixin, adds phenixin again to graticule, mixing obtains standard oil solution;
Secondly, use infrared spectrometer, with the phenixin be background measure described standard oil solution at 3300～2600cm
-1Infrared absorption spectrum;
According to these infrared absorption spectrum drawing standard curves, obtain regression equation and be
y＝0.2642x+0.012，R
2＝0.9997；
Five, petroleum hydrocarbon assay step
Use Fourier infrared spectrograph Nicolet Nexus (Thermo Electron Corporation) to measure the infrared absorption spectrum of above-mentioned carbon tetrachloride extraction liquid under the following conditions, condition determination is as follows:
Sweep limit: 3200～2600cm
-1
Scanning times: 30;
Resolution: 4cm
-1
Calculate by above-mentioned formula (1) then, the petroleum hydrocarbon content that promptly obtains in the grass carp is 0.0904mg/g.
Embodiment 3 squid PetroChina Company Limited. hydrocarbon contents are measured
Measure according to following step:
One, flesh of fish treatment step
The squid of buying from market, green hill is got its meat, and the JJ-2 tissue of producing with changzhou state China instrument plant smashs that equal pulp grinder is smashed to pieces, mixing to pieces again, and the pasted fish meat that obtains is placed in the sealed glass jars, and ℃ preservation is standby down in temperature-20.
Two, Yu Rou saponification
Step (one) is obtained pasted fish meat thaws, take by weighing 2.3 gram pasted fish meats and place iodine flask, the 6mol/L that adds 20mL analyzes pure cerium hydroxide sodium solution (deionized water, meet one-level water quality standard among the GB/T 6682, chemicals company limited of traditional Chinese medicines group), add the 15mL absolute ethyl alcohol, under 35 ℃, shake saponification 18h, make flesh of fish digestive juice.
Three, extraction and absorption
The flesh of fish digestive juice 100mL that step (two) is obtained pours in the separating funnel, use 100mL to analyze the described flesh of fish digestive juice of pure phenixin (chemicals company limited of traditional Chinese medicines group product) extraction then, extract three times, then, combining extraction liquid carries out drying with analyzing pure anhydrous sodium sulfate (chemicals company limited of traditional Chinese medicines group product), measuring the dry extract of 10mL is added in the 50mL volumetric flask with the cleansing solution that 10mL washs phenixin, add phenixin to graticule, mixing obtains carbon tetrachloride extraction liquid;
Then, allow described carbon tetrachloride extraction liquid, remove impurity with the magnesium silicate post of 0.9mL/min by handling according to previous methods.
Four, infrared spectrum measurement typical curve plot step
At first prepare standard oil: n-hexadecane, isooctane and benzene are mixed according to volume ratio at 65: 25: 10 and obtain standard oil; Measure 0.25,0.50,0.75,1.00,1.25,1.50 respectively, the described standard oil of 1.75mL is added in the 10mL volumetric flask of a small amount of phenixin, adds phenixin again to graticule, mixing obtains standard oil solution;
Secondly, use infrared spectrometer, with the phenixin be background measure described standard oil solution at 3300～2600cm
-1Infrared absorption spectrum;
According to these infrared absorption spectrum drawing standard curves, obtain regression equation and be
y＝0.2642x+0.012，R
2＝0.9997。
Five, petroleum hydrocarbon assay step
Use Fourier infrared spectrograph Nicolet Nexus (Thermo Electron Corporation) to measure the infrared absorption spectrum of above-mentioned carbon tetrachloride extraction liquid under the following conditions, condition determination is as follows:
Sweep limit: 3200～2600cm
-1
Scanning times: 32;
Resolution: 4cm
-1
Calculate by above-mentioned formula (1) then, the petroleum hydrocarbon content that promptly obtains in the squid is 0.1121mg/g.
Embodiment 4 neosalanx taihuensis PetroChina Company Limited. hydrocarbon contents are measured
Measure according to following step:
One, the treatment step of silverfish meat
The neosalanx taihuensis peeling of buying from market, green hill, decaptitate and get its meat, the JJ-2 tissue of producing with changzhou state China instrument plant smashs that equal pulp grinder is smashed to pieces, mixing to pieces again, and the pasted fish meat that obtains is placed in the sealed glass jars, and ℃ preservation is standby down in temperature-20.
Two, the saponification of white shrimp
Step (one) is obtained pasted fish meat thaws, take by weighing 3.0 gram pasted fish meats and place iodine flask, the 6mol/L that adds 16.5mL analyzes pure cerium hydroxide sodium solution (deionized water, meet one-level water quality standard among the GB/T 6682, chemicals company limited of traditional Chinese medicines group), add the 20mL absolute ethyl alcohol, under 30 ℃, shake saponification 20h, make flesh of fish digestive juice.
Three, extraction and absorption
The flesh of fish digestive juice 100mL that step (two) is obtained pours in the separating funnel, use 100mL to analyze the described flesh of fish digestive juice of pure phenixin (chemicals company limited of traditional Chinese medicines group product) extraction then, extract three times, then, combining extraction liquid carries out drying with analyzing pure anhydrous sodium sulfate (chemicals company limited of traditional Chinese medicines group product), measuring the dry extract of 10mL is added in the 50mL volumetric flask with the cleansing solution that 10mL washs phenixin, add phenixin to graticule, mixing obtains carbon tetrachloride extraction liquid;
Then, allow described carbon tetrachloride extraction liquid, remove impurity with the magnesium silicate post of 1.0mL/min by handling according to previous methods.
Four, infrared spectrum measurement typical curve plot step
At first prepare standard oil: n-hexadecane, isooctane and benzene are mixed according to volume ratio at 65: 25: 10 and obtain standard oil; Measure 0.25,0.50,0.75,1.00,1.25,1.50 respectively, the described standard oil of 1.75mL is added in the 10mL volumetric flask of a small amount of phenixin, adds phenixin again to graticule, mixing obtains standard oil solution;
Secondly, use infrared spectrometer, with the phenixin be background measure described standard oil solution at 3200～2600cm
-1Infrared absorption spectrum;
According to these infrared absorption spectrum drawing standard curves, obtain regression equation and be
Y＝0.2642x+0.012，R
2＝0.9997。
Five, petroleum hydrocarbon assay step
Use Fourier infrared spectrograph Nicolet Nexus (Thermo Electron Corporation) to measure the infrared absorption spectrum of above-mentioned carbon tetrachloride extraction liquid under the following conditions, condition determination is as follows:
Sweep limit: 3200～2600cm
-1
Scanning times: 32;
Resolution: 4cm
-1
Calculate by above-mentioned formula (1) then, the petroleum hydrocarbon content that promptly obtains in the neosalanx taihuensis is 0.0875mg/g.
Claims (8)
1, the assay method of flesh of fish PetroChina Company Limited. hydrocarbon content, the step of its this method of feature is as follows:
One, flesh of fish treatment step
Get its meat after scaling, remove the peel fish, again with high speed biological tissue bruiser smash to pieces, mixing, the pasted fish meat that obtains is placed in sealed glass jars or the safety box, ℃ preserve down in temperature-20 standby,
Two, Yu Rou saponification
The pasted fish meat that step () is obtained thaws, take by weighing 2.0-3.0 weight portion pasted fish meat and place iodine flask, add the 2-10mol/L sodium hydroxide solution of 10-40 parts by volume, the absolute ethyl alcohol of adding 10-25 parts by volume, under temperature 15-75 ℃, shook saponification 8-38 hour, and made flesh of fish digestive juice like this;
Three, extraction and absorption
The flesh of fish digestive juice that step (two) obtains is poured in the separating funnel, use phenixin to extract described flesh of fish digestive juice three times according to described flesh of fish digestive juice volume and phenixin volume ratio 2/5 to 2/3, the extract that obtains after each extraction makes water wash according to described extract volume and water volume ratio 2/5 to 1/1, then, extract carries out drying with anhydrous sodium sulfate, dried extract is added in the 50mL volumetric flask, add phenixin to graticule, mixing obtains carbon tetrachloride extraction liquid;
Described carbon tetrachloride extraction liquid is removed impurity with 0.8-1.2mL/min by the magnesium silicate adsorption column.
Four, infrared spectrum measurement typical curve plot step
At first prepare standard oil: n-hexadecane, isooctane and benzene are mixed according to volume ratio at 65: 25: 10 and obtain standard oil; Measure 0.25,0.50,0.75,1.00,1.25,1.50 respectively, the described standard oil of 1.75mL is added in the 10mL volumetric flask of a small amount of phenixin, adds phenixin again to graticule, mixing obtains standard oil solution;
Secondly, use infrared spectrometer, with the phenixin be background measure described standard oil solution at 3300～2600cm
-1Infrared absorption spectrum;
According to these infrared absorption spectrum drawing standard curves, obtain regression equation and be
y＝0.2642x+0.012，R
2＝0.9997；
Five, petroleum hydrocarbon assay step
Use infrared spectrometer to measure the infrared absorption spectrum that it removes the carbon tetrachloride extraction liquid of impurity under the following conditions:
Sweep limit: 3200～2600cm
-1
Scanning times: 28-36;
Resolution: 2-6cm
-1
Then by formula (1) calculates the petroleum hydrocarbon content in the described flesh of fish:
In the formula:
X
1-sample PetroChina Company Limited. hydrocarbon content, unit are milligram every gram (mg/g);
The petroleum hydrocarbon content (mg/L) that m-draws from typical curve;
V
1-extract constant volume (mL);
The M-sample quality, unit is gram (g).
2, method according to claim 1 is characterized in that described saponification step carries out under temperature 25-45 ℃.
3, method according to claim 1 is characterized in that described saponification step carried out 12-24 hour.
4, method according to claim 1 is characterized in that described saponification step adds the 2-10mol/L sodium hydroxide solution of 10-20 parts by volume.
5, method according to claim 1 is characterized in that the extract that obtains after each extraction makes water wash according to described extract volume and water volume ratio 2/5 to 1/1, removes existing polar impurity in the extract.
6, method according to claim 1 adds the saturated aqueous sodium chloride in described flesh of fish digestive juice volume 1-5 parts by volume when it is characterized in that extracting.
7, method according to claim 1 adds the saturated aqueous sodium chloride in described flesh of fish digestive juice volume 3-4 parts by volume when it is characterized in that extracting.
8, method according to claim 1 is characterized in that and add aluminium oxide in magnesium silicate weight 0.5-2% in the magnesium silicate post, remove the adsorbable unsaponifiables of aluminium oxide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262067A (en) * | 2010-05-31 | 2011-11-30 | 北京化工大学 | Attenuate total reflection infrared spectrometry for fast detection of iodine value of edible oil |
| CN102854167A (en) * | 2012-08-14 | 2013-01-02 | 浙江中一检测研究院股份有限公司 | Method for determination of concentration of mineral oil mist in workshop air |
| CN103472208A (en) * | 2013-09-12 | 2013-12-25 | 国家电网公司 | Method for testing oil content in absorption tower slurry |
| CN107490559A (en) * | 2016-06-13 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of method for determining oily area's solid waste petrochina class content |
| CN113252413A (en) * | 2021-04-16 | 2021-08-13 | 成都新基因格生物科技有限公司 | Diatom inspection method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100509161C (en) * | 2005-04-29 | 2009-07-08 | 中国石油化工股份有限公司 | Petroleum hydrocabon cracking catalyst and production thereof |
| US7858373B2 (en) * | 2006-02-03 | 2010-12-28 | Rohm And Haas Company | Chemical markers |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262067A (en) * | 2010-05-31 | 2011-11-30 | 北京化工大学 | Attenuate total reflection infrared spectrometry for fast detection of iodine value of edible oil |
| CN102854167A (en) * | 2012-08-14 | 2013-01-02 | 浙江中一检测研究院股份有限公司 | Method for determination of concentration of mineral oil mist in workshop air |
| CN103472208A (en) * | 2013-09-12 | 2013-12-25 | 国家电网公司 | Method for testing oil content in absorption tower slurry |
| CN103472208B (en) * | 2013-09-12 | 2016-01-20 | 国家电网公司 | A kind of method of testing oil content content in the slurries of absorption tower |
| CN107490559A (en) * | 2016-06-13 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of method for determining oily area's solid waste petrochina class content |
| CN113252413A (en) * | 2021-04-16 | 2021-08-13 | 成都新基因格生物科技有限公司 | Diatom inspection method |
| CN113252413B (en) * | 2021-04-16 | 2023-04-11 | 成都新基因格生物科技有限公司 | Diatom inspection method |
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