CN110146608A - The quantitative detecting method of each component in system containing water-soluble peroxide - Google Patents
The quantitative detecting method of each component in system containing water-soluble peroxide Download PDFInfo
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- CN110146608A CN110146608A CN201910372994.2A CN201910372994A CN110146608A CN 110146608 A CN110146608 A CN 110146608A CN 201910372994 A CN201910372994 A CN 201910372994A CN 110146608 A CN110146608 A CN 110146608A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
Abstract
The present invention provides the quantitative detecting methods of each component in the system containing water-soluble peroxide, the method includes the testing mixture of the system containing water-soluble peroxide is configured to aqueous solution, quantitative detection is carried out to each component in system using gas chromatography.The method is suitable for the mixture under high-temperature high-pressure state, and applies also for the detection for containing more high boiling each component in testing mixture；With easy to operate, peak shape is good, quickly, can be detected with quantitative analysis, and solving the problems, such as that water-soluble peroxide (such as TBHP) decomposes at high temperature causes quantitative analysis inaccurate.
Description
Technical field
The invention belongs to technical field of analysis and detection, and in particular to each group in a kind of system containing water-soluble peroxide
The quantitative detecting method divided.
Background technique
The quantitative detection of each component is always the key points and difficulties in analysis detection field in system containing peroxide.With
For oxidation of isobutane prepares the reaction system of the tert-butyl alcohol (TBA) and tert-butyl hydroperoxide (TBHP), in reaction mixture
It further include the tert-butyl alcohol and peroxide (such as TBHP, di-tert-butyl peroxide in addition to the oxygen for including iso-butane, addition
(DTBP)) etc., the quantitative detection of all components is a technological difficulties in said mixture.Reason is peroxide generally all
Unstable, such as TBHP plays pendulum at 75 DEG C or more, temperature, which is higher than 90 DEG C, then can acutely decompose, therefore first to containing
There are larger difficulty for peroxide (such as TBHP) progress quantitative detection in the system of peroxide.Secondly as peroxide
It is unstable, cause the quantitative detection of other components in the system containing peroxide also more difficult.
There are two types of traditional detection methods based on peroxide, and one is gas chromatographies, but as described above, peroxidating
Object is unstable, by taking TBHP as an example, is easy at least partly to be decomposed into the tert-butyl alcohol, TBHP and the tert-butyl alcohol in system is caused to be difficult to standard
Determine amount；Another kind is titration, but there are problems that peroxide and the separation of impurity difficulty, therefore be unable to accurate quantitative analysis, and same
Sample causes other components in peroxide and system to be unable to accurate quantitative analysis there are peroxide is unstable.And existing be directed to is contained
The quantitative detection of each component, also has related researcher to study in the system of peroxide.
Such as document report mistake, tert-butyl hydroperoxide and di-tert-butyl peroxide are separated using gas chromatography, utilized
Ethyl acetate is internal standard compound, but test process is cumbersome, needs to configure at least two standard curves, furthermore it is only applicable to room temperature
Synthesis under normal pressure system, for reaction under high pressure system, internal standard substance can not be added, therefore cannot achieve on-line real time monitoring, be limited
Furthermore its application range only contains TBA, TBHP, DTBP and internal standard compound in system of its research, the boiling point of DTBP is most in system
Height is also only 111 DEG C, in order to avoid TBHP is decomposed at high temperature, limits the setting of injector temperature, is not also suitable for it
Contain the analysis and measurement of high boiling impurity composition in system.
Such as document report mistake, by a certain amount of n-Hydroxyphthalimide catalyst, it is anti-that high pressure is added in acetonitrile solvent
It answers in kettle, is passed through iso-butane coolant liquid under normal temperature high voltage state, oxygen, required temperature is warming up to after closed, persistently stirs number
Hour, reaction kettle is taken out after reaction, room temperature is rapidly cooled to, takes out reaction solution after pressure release, with gas-chromatography cooperation hydrogen fire
Flame ionization detector (FID) carries out quantitative analysis to product, and specific quantitative analysis is using ethyl acetate as internal standard compound, using interior
Mark method carries out quantitative detection to TBHP therein, equally exists above-mentioned defect.
Such as document report mistake, di-tert-butyl peroxide in vinyl polymerization initiator tert butyl peroxy benzoate is had studied
It is solvent that the gas chromatography analysis method of object content, which is using hexane, prepares the standard of di-tert-butyl peroxide (DTBP)
Sample tests its external standard correction factor, additionally, due to containing tert-butyl hydroperoxide in the test system, and in order to avoid its point
Decomposition product after solution has an impact the quantitative analysis of DTBP, therefore the injector temperature for controlling gas chromatograph is 60 DEG C, but
Since injector temperature is low, the boiling point of sample is 124 DEG C, it is incomplete to may cause sample vaporization, so that heavy constituent exists in sample
It is remained at injection port, when instrument requires cool to preparation state after sample analysis, injection port cooling rate is slow, is not easy to reach
Cool-on-column inlet sample introduction is used, sample is directly injected into setting state so that the analysis time of batch sample be made to extend
Chromatographic column, but convenient cold on-column injection apparatus structure is complicated, cost is high, is suitble to the analysis of trace components；Nonvolatile element deposition
In column cap, pillar is polluted；It is inconvenient for operation；A large amount of solvents enter pillar, have an impact to liquid film, the expansion of Yi Yinqi peak shape；Retain
Value repetition is bad, is not easy to realize automation.
Summary of the invention
In order to improve the deficiencies in the prior art, the object of the present invention is to provide a kind of quantitative detecting method, the method is suitable
Water is only used for the quantitative detection of each component in the system containing water-soluble peroxide, in detection process as solvent, tool
Have low in cost, environmentally protective, easy to operate, peak shape is good, it is quick many advantages, such as, quantifying for each component in system may be implemented
Analysis detection solves the problems, such as that conventional method causes quantitative analysis inaccurate due to easily decomposing under peroxide high temperature.
The invention provides the following technical scheme:
The quantitative detecting method of each component in a kind of system containing water-soluble peroxide, the method includes containing
The testing mixture of the system of water-soluble peroxide is configured to aqueous solution, is carried out using gas chromatography to each component in system
Quantitative detection.
According to the present invention, the water-soluble peroxide is selected from R-OOH or R- (C=O)-OOH, the R selected from unsubstituted
Or optionally by one, two or more RaSubstituted following groups: C1-12Alkyl or C6-14Aryl, each RaIt is identical or not
Together, it is independently from each other C1-6Alkyl.
According to the present invention, the R is selected from unsubstituted or optionally by one, two or more RaSubstituted following groups:
C1-6Alkyl or C6-10Aryl, each RaIt is identical or different, it is independently from each other C1-6Alkyl.
According to the present invention, the R is selected from unsubstituted or optionally by one, two or more RaSubstituted following groups:
C1-6Alkyl, each RaIt is identical or different, it is independently from each other C1-3Alkyl.
According to the present invention, the water-soluble peroxide is selected from methyl hydroperoxide, ethyl hydrogen peroxide, isopropyl peroxide
Change hydrogen, butylhydroperoxide, isopentyl hydrogen peroxide, t-amyl peroxy hydrogen, Peracetic acid or Perpropionic Acid.
According to the present invention, also contain R-OH in the system, R is as defined above.
According to the present invention, the R-OH be selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol,
At least one of n-amyl alcohol, isoamyl alcohol and tert-pentyl alcohol.At least one preferably in methanol, isopropanol, the tert-butyl alcohol and isobutanol
Kind.
According to the present invention, also contain R-COOH in the system, R is as defined above.
According to the present invention, the R-COOH is selected from acetic acid, propionic acid, n-butyric acie, isobutyric acid, positive valeric acid, isovaleric acid and uncle penta
At least one of acid.Preferably acetic acid and/or isobutyric acid.
According to the present invention, oxidant is also contained in the system, the oxidant is, for example, oxygen, oxygenous gaseous mixture
Body (such as gaseous mixture of air, oxygen and nitrogen), peroxide (such as tert-butyl hydroperoxide, ethylbenzene hydroperoxide, peroxide
Acetic acid etc.) one of or it is a variety of.
According to the present invention, also contain R-CO-H in the system, R is as defined above.
According to the present invention, the R-CO-H is selected from acetaldehyde, propionic aldehyde, n-butanal, isobutylaldehyde, valeraldehyde, isopentyl aldehyde and uncle penta
At least one of aldehyde.Preferably acetaldehyde and/or positive propionic aldehyde.
According to the present invention, epoxyalkane, such as ethylene oxide and/or propylene oxide are also contained in the system.
According to the present invention, also contain ketone compounds, for example, acetone in the system.
A preferred embodiment according to the present invention contains in the testing mixture of the system containing water-soluble peroxide
Propylene oxide, the tert-butyl alcohol (TBA), tert-butyl hydroperoxide (TBHP), methanol, isopropanol, isobutanol, acetone, propionic aldehyde, acetic acid,
At least one of isobutyric acid, propylene glycol etc..
A preferred embodiment according to the present invention may be used also in the testing mixture of the system containing water-soluble peroxide
To contain at least one of ethylene glycol, methyl-1,3-propanediol etc..
According to the present invention, the testing mixture can be the mixture under high-temperature high-pressure state, and it is normal to be also possible to room temperature
The mixture of pressure.It can detecte the mixture under high-temperature high-pressure state due to the method, therefore the present processes are suitable for
Product and content in reaction process are detected, while being also applied for out the detection of the product liquid after kettle and content.
According to the present invention, there is no particular limitation for the content of water-soluble peroxide in the testing mixture, such as can
To be greater than 0 and be less than or equal to 100%；Other components in the testing mixture, such as R-COOH, R-OH, R-CO-H, ketone
There is no particular limitation for the content of class compound, epoxyalkane, oxidant etc., such as is may be greater than respectively equal to 0 and be less than
100%.
According to the present invention, the concentration of water-soluble peroxide is 0.1-12wt% in the aqueous solution being configured to, for example,
0.1wt%, 0.2wt%, 0.5wt%, 0.8wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%,
8wt%, 9wt%, 10wt%, 11wt% or 12wt%.Illustratively, in manufactured aqueous solution water-soluble peroxide concentration
For 0.5-8.0wt%.
According to the present invention, the concentration of ROH is 0-9wt%, for example, 0.05-1.35wt%, tool in the aqueous solution being configured to
Body can for 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%,
0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 2wt%, 3wt%,
4wt%, 5wt%, 6wt%, 7wt%, 8wt% or 9wt%.
According to the present invention, the concentration of R-COOH is 0-1.5wt%, for example, 0.05- in the aqueous solution being configured to
1.35wt%, be specifically as follows 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%,
0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%.
According to the present invention, the concentration of R-CO-H is 0-1.5wt%, for example, 0.05- in the aqueous solution being configured to
1.35wt%, be specifically as follows 0.01wt%, 0.02wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%,
0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%,
1.3wt%, 1.4wt%, 1.5wt%.
According to the present invention, the concentration of oxidant is 0-1.5wt%, for example, 0.05- in the aqueous solution being configured to
1.35wt%, be specifically as follows 0.01wt%, 0.02wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%,
0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%,
1.3wt%, 1.4wt%, 1.5wt%.
According to the present invention, the concentration of ketone compounds is 0-1.5wt%, for example, 0.05- in the aqueous solution being configured to
1.35wt%, be specifically as follows 0.01wt%, 0.02wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%,
0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%,
1.3wt%, 1.4wt%, 1.5wt%.
According to the present invention, the concentration for the aqueous solution alkylene oxide hydrocarbon being configured to is 0-1.5wt%, for example, 0.05-
1.35wt%, be specifically as follows 0.01wt%, 0.02wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%,
0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%,
1.3wt%, 1.4wt%, 1.5wt%.
According to the present invention, quantitative detection is carried out using external standard method, i.e., the method also includes the draftings of standard curve.
According to the present invention, the drafting of the standard curve includes the following steps:
S1. the aqueous solution of each component standard sample in the testing mixture of series of concentrations is prepared；
S2. using each component standard sample in the testing mixture of the series of concentrations in gas chromatography difference detecting step S1
The peak area of the aqueous solution of product；
S3. it is drawn according to the corresponding peak area of the aqueous solution of each component standard sample in the testing mixture of series of concentrations dense
Degree-peak area standard curve.
Illustratively, the drafting of the standard curve includes the following steps:
S01. the tert-butyl alcohol (TBA) standard sample of series of concentrations, tert-butyl hydroperoxide (TBHP) standard sample are prepared
Aqueous solution；
S02. using the tert-butyl alcohol (TBA) standard sample of the series of concentrations in gas chromatography difference detecting step S01, uncle
The peak area of the aqueous solution of butylhydroperoxide (TBHP) standard sample；
S03. according to the tert-butyl alcohol of series of concentrations (TBA) standard sample, tert-butyl hydroperoxide (TBHP) standard sample
The corresponding peak area of aqueous solution draws concentration-peak area standard curve.
According to the present invention, gas chromatograph cooperation flame ionization ditector (FID) uses.
According to the present invention, the gas chromatographic detection condition are as follows: 100-250 DEG C of injection port vapourizing temperature, for example, 120-
230 DEG C, such as 150 DEG C.Using the injection port vapourizing temperature in this temperature range, it can be ensured that all components are when shorter in system
Interior elution simultaneously detects；It avoids causing sample gasification rate slow since temperature setting is too low, extending sample peak, high boiling product
Matter is remained in injection port, and injection port is caused to pollute, while condensation, not appearance even pollution detection device in detector；Also it avoids
Temperature setting is too high, causes to decompose to peroxide, and then influences monitoring result.
According to the present invention, semi-polar stationary phase is used in the chromatographic column in the gas-chromatography.Illustratively, the chromatography
Column is capillary chromatographic column, and the semi-polar stationary phase is, for example, -86% dimethyl silicone polymer of 14% cyanogen propylbenzene, 6% cyanogen
- 94% methyl polysiloxane of propyl phenyl, -50% dimethyl polysiloxane of 50% diphenyl, 50% cyanogen propyl phenyl are (wherein
At least one of 25% cyanogen propyl, 25% phenyl) -50% dimethyl polysiloxane.
According to the present invention, the gas chromatographic detection condition are as follows: 180-300 DEG C of temperature of detector FID, for example, 230 DEG C；
According to the present invention, the gas chromatographic detection condition are as follows: carrier gas (N2) flow 0.1-2ml/min；H2Flow 20-
80mL/min, air mass flow 300-600mL/min, make-up gas flow 10-40mL/min；Illustratively, carrier gas (N2) flow
0.1-2ml/min, for example, 1ml/min；H2Flow 40mL/min, air mass flow 400mL/min, make-up gas flow 20mL/
min。
According to the present invention, the gas chromatographic detection condition are as follows: post case:, keeping 2-10min by 25-50 DEG C of initial column temperature, then
It is heated up with the rate of 15-40 DEG C/min, 110-250 DEG C of final temperature, keeps 2-10min.Illustratively, the gas-chromatography inspection
Survey condition are as follows: post case: 35 DEG C of initial column temperature, 5min is kept, then heat up with the rate of 30 DEG C/min, 200 DEG C of final temperature, kept
5min。
The utility model has the advantages that
The present invention provides the quantitative detecting method of each component in the system containing water-soluble peroxide, the method is suitable
For the mixture under high-temperature high-pressure state, and apply also for the inspection for containing more high boiling each component in testing mixture
It surveys；With easy to operate, peak shape is good, quickly, can be detected with quantitative analysis, solves water-soluble peroxide (such as TBHP) in height
Temperature is lower to decompose the problem for leading to quantitative analysis inaccuracy.
Detailed description of the invention
Fig. 1 is oxidation of isobutane system water absorbing reaction liquid gas chromatogram described in the embodiment of the present invention 1.
Specific embodiment
Further detailed description is done to preparation method of the invention below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Instrument and equipment
1) instrument: gas chromatograph matches hydrogen flameionization (FID) detector.
2) condition of gas chromatograph:
Capillary chromatographic column (- 86% dimethyl silicone polymer of 14% cyanogen propylbenzene, semi-polar stationary phase) (30m*
0.25mm*0.25μm)；150 DEG C of injection port vapourizing temperature, split ratio 100:1；230 DEG C of detector FID temperature；1 μ L of sample volume；
Carrier gas (N2) flow 1ml/min；H2Flow 40mL/min, air mass flow 400mL/min, make-up gas flow 20mL/min；Post case:
35 DEG C of initial column temperature, 5min is kept, then heat up with the rate of 30 DEG C/min, 200 DEG C of final temperature, keep 5min.
3) drafting of standard curve:
By taking iso-butane prepares tert-butyl hydroperoxide reaction system as an example, iso-butane reacts to obtain tert-butyl hydroperoxide,
And the by-product tert-butyl alcohol, by preparing the tert-butyl alcohol of series of concentrations, and its peak area is detected, draws tert-butyl alcohol standard sample
The equation of linear regression of standard curve；Similarly, by preparing the tert-butyl hydroperoxide of series of concentrations, and its peak area is detected,
Draw the equation of linear regression of the standard curve of tert-butyl hydroperoxide standard sample；Specific concentration and peak area are as shown in table 1:
1 Specification Curve of Increasing table of table
Process based on above-mentioned analysis is fitted by software, and test obtains the standard curve of the tert-butyl alcohol standard sample
Equation of linear regression is YTBA=42475.0XTBA- 33333.3, linearly dependent coefficient R=0.9991；
The equation of linear regression of the standard curve of the tert-butyl hydroperoxide standard sample is YTBHP=26335.8XTBHP-
6681.94, linearly dependent coefficient R=0.9998.
Embodiment 1
A kind of measurement iso-butane prepares the quantitative detection of each component in product liquid in tert-butyl hydroperoxide reaction system
Method, described method includes following steps:
The test substance for negating high temperature and pressure during answering, mixes with water, and preparation obtains tert-butyl hydroperoxide concentration and exists
Aqueous solution to be measured within the scope of 0.1-12wt% is then injected into the detection that constituent content is carried out in chromatographic column, injection port vaporization temperature
150 DEG C of degree.
Due to negating the high temperature and pressure test substance during answering, therefore can be using such as to the process for preparation of aqueous solution to be measured
Lower method:
1, band dual valve type thief hatch steel cylinder one is taken, in addition mating probe tube, weighing, are accurate to 0.01g, are denoted as W1。
2, sampling steel cylinder arrival end is accessed into reaction system thief hatch；Steel cylinder arrival end valve is opened, thief hatch valve is opened
Door opens steel cylinder outlet valve, sample is added into steel cylinder；There is big quantity of fluid to be discharged to outlet end, after steel cylinder fills sample,
Thief hatch valve is successively closed, sampling steel cylinder outlet valve is closed, closes sampling steel cylinder inlet valve.
3, the quality for being loaded product steel cylinder is weighed, 0.01g is accurate to, is denoted as W2, the quality of sample is calculated, W is denoted asSample=W2-
W1。
4, dried sample absorption bottle is weighed, is denoted as WBottle, deionized water about 150g is added into absorption bottle, claims
Amount obtains the quality of absorption bottle after water is added, WWater+bottle, absorption bottle, steel cylinder are connected, by the sampling bag vacuumized and absorption bottle
Outlet connection pays attention to the air-tightness of each connector connection, and the quality for the water being added in system is WWater=WWater+bottle-WBottle。
5, high pure nitrogen is poured into whole system, is full of to airbag, outlet valve is opened, and discharge section nitrogen is closed
Nitrogen charging switch.
6, steel cylinder outlet valve is opened, observation bubble bloats situation, to prevent liquid splash, to airbag full of opening outlet valve
Door bleeds off portion gas, closes valve and is again filled with.Sampling bag is removed, it is to be checked.
7, it emerges to no gas, removes steel cylinder, residual liquid in steel cylinder is blown into absorption bottle with air, weigh sample preparation
The quality of empty steel cylinder afterwards, is accurate to 0.01g, compared with before sample preparation.
8, the gross mass for weighing flask after absorbing sample respectively, is accurate to 0.01g, calculates the quality of absorption bottle weight gain
WIncrease, for calculating liquid sample gross mass.
9, aqueous solution is detected with gas chromatograph, and the testing conditions of gas chromatograph are seen above.
10, according to WLiquidThe concentration of each component in system to be measured is calculated.
According to above-mentioned test method, test result is as follows shown in table 2, and each component is calculated by above-mentioned standard curve
Concentration:
The content of TBA and TBHP in the aqueous solution that table 2 oxidation of isobutane, three batches of product configurations obtain
Note: the concentration in table 2 refers to the concentration of each component in aqueous solution that TBA and TBHP are prepared according to the above method,
The molar content of each component in sample to be tested is calculated according to the diluted multiple of each component and additional amount, concrete outcome is shown in Table
3。
The content of 3 three batches of product compositions of oxidation of isobutane of table
Embodiment 2
Identical as the operating process of embodiment 1, difference is only that, injector temperature difference and sample to be tested difference are chosen
Same sample to be tested is injected in chromatographic column under different injector temperatures and is analyzed, referring specifically to such as the following table 4.
Influence of 4 injector temperature of table to TBA, TBHP peak area and peak type
From the point of view of the peak area under the different injector temperatures of above-mentioned table 4, under different injector temperatures, the peak of TBA
Area is not much different, and the peak area of TBHP is also not much different, and the test result of the TBHP obtained within the scope of this 80-180 DEG C is identical
Or it is close, it was demonstrated that injector temperature without result in the decomposition of TBHP, can also illustrate be can be well due to being configured to aqueous solution
Avoid the influence of decomposition of the injector temperature to water-soluble peroxide；Through aqueous solution, treated that sample to be tested can fit
For being higher than 150 DEG C there are boiling point and retaining the system of stronger impurity, while at a temperature of also illustrating this, all groups in system
Divide and elutes and detect.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. the quantitative detecting method of each component in a kind of system containing water-soluble peroxide, wherein the method includes will
The testing mixture of system containing water-soluble peroxide is configured to aqueous solution, using gas chromatography to each component in system
Carry out quantitative detection.
2. the water-soluble peroxide is selected from R-OOH or R- (C=O)-OOH according to the method described in claim 1, wherein,
The R is selected from unsubstituted or optionally by one, two or more RaSubstituted following groups: C1-12Alkyl or C6-14Aryl, often
One RaIt is identical or different, it is independently from each other C1-6Alkyl.
Preferably, the R is selected from unsubstituted or optionally by one, two or more RaSubstituted following groups: C1-6Alkyl or
C6-10Aryl, each RaIt is identical or different, it is independently from each other C1-6Alkyl.
Preferably, the R is selected from unsubstituted or optionally by one, two or more RaSubstituted following groups: C1-6Alkyl, often
One RaIt is identical or different, it is independently from each other C1-3Alkyl.
3. method according to claim 1 or 2, wherein the water-soluble peroxide is selected from methyl hydroperoxide, ethyl
Hydrogen peroxide, hyperis, butylhydroperoxide, isopentyl hydrogen peroxide, t-amyl peroxy hydrogen, Peracetic acid or
Perpropionic Acid.
Preferably, in the aqueous solution being configured to the concentration of water-soluble peroxide be 0.1-12wt%, for example, 0.1wt%,
0.2wt%, 0.5wt%, 0.8wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%,
9wt%, 10wt%, 11wt% or 12wt%.Illustratively, the concentration of water-soluble peroxide is 0.5- in manufactured aqueous solution
8.0wt%.
4. method according to claim 1-3, wherein also contain R-OH in the system, R is as defined above.
Preferably, the R-OH is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, different
At least one of amylalcohol and tert-pentyl alcohol.Preferably at least one of methanol, isopropanol, the tert-butyl alcohol and isobutanol.
Preferably, the concentration of ROH is 0-9wt%, for example, 0.05-1.35wt% in the aqueous solution being configured to.
5. method according to claim 1-4, wherein also contain R-COOH in the system, R is as defined above.
Preferably, the R-COOH in acetic acid, propionic acid, n-butyric acie, isobutyric acid, positive valeric acid, isovaleric acid and trimethylacetic acid extremely
Few one kind.Preferably acetic acid and/or isobutyric acid.
Preferably, the concentration of R-COOH is 0-1.5wt%, for example, 0.05-1.35wt% in the aqueous solution being configured to.
6. method according to claim 1-5, wherein also contain oxidant, the oxidant in the system
For example, oxygen, oxygenous mixed gas (such as gaseous mixture of air, oxygen and nitrogen), peroxide such as t-butyl peroxy
Change hydrogen, ethylbenzene hydroperoxide, Peracetic acid etc..
Preferably, the concentration of oxidant is 0-1.5wt%, for example, 0.05-1.35wt% in the aqueous solution being configured to.
Preferably, also contain R-CO-H in the system, R is as defined above.
Preferably, the R-CO-H in acetaldehyde, propionic aldehyde, n-butanal, isobutylaldehyde, valeraldehyde, isopentyl aldehyde and trimethyl-acetaldehyde extremely
Few one kind.Preferably acetaldehyde and/or propionic aldehyde.
Preferably, the concentration of R-CO-H is 0-1.5wt%, for example, 0.05-1.35wt% in the aqueous solution being configured to.
Preferably, epoxyalkane, such as ethylene oxide and/or propylene oxide are also contained in the system.
Preferably, the concentration for the aqueous solution alkylene oxide hydrocarbon being configured to is 0-1.5wt%, for example, 0.05-1.35wt%.
Preferably, also contain ketone compounds, for example, acetone in the system.
Preferably, the concentration of ketone compounds is 0-1.5wt%, for example, 0.05-1.35wt% in the aqueous solution being configured to.
7. method according to claim 1-6, wherein the testing mixture can be under high-temperature high-pressure state
Mixture, the mixture being also possible under normal temperature and pressure.
8. method according to claim 1-7, wherein carry out quantitative detection, i.e. the method using external standard method
Further include: the drafting of standard curve.
Preferably, the drafting of the standard curve includes the following steps:
S1. the aqueous solution of each component standard sample in the testing mixture of series of concentrations is prepared；
S2. using each component standard sample in the testing mixture of the series of concentrations in gas chromatography difference detecting step S1
The peak area of aqueous solution；
S3. concentration-is drawn according to the corresponding peak area of the aqueous solution of each component standard sample in the testing mixture of series of concentrations
Peak area standard curve.
9. method according to claim 1-6, wherein the drafting of the standard curve includes the following steps:
S01. the tert-butyl alcohol (TBA) standard sample, tert-butyl hydroperoxide (TBHP) standard sample of preparation series of concentrations is water-soluble
Liquid；
S02. using the tert-butyl alcohol (TBA) standard sample, the tert-butyl of the series of concentrations in gas chromatography difference detecting step S01
The peak area of the aqueous solution of hydrogen peroxide (TBHP) standard sample；
S03. according to the tert-butyl alcohol of series of concentrations (TBA) standard sample, tert-butyl hydroperoxide (TBHP) standard sample it is water-soluble
The corresponding peak area of liquid draws concentration-peak area standard curve.
According to the present invention, gas chromatograph cooperation flame ionization ditector (FID) uses.
10. -9 described in any item methods according to claim 1, wherein the gas chromatographic detection condition are as follows: injection port vaporization
100-250 DEG C of temperature, for example, 120-230 DEG C, such as 150 DEG C.
Preferably, semi-polar stationary phase is used in the chromatographic column in the gas-chromatography.Illustratively, the chromatographic column is capillary
Pipe chromatographic column, the semi-polar stationary phase are, for example, -86% dimethyl silicone polymer of 14% cyanogen propylbenzene, 6% cyanogen propyl phenyl -
94% methyl polysiloxane, -50% dimethyl polysiloxane of 50% diphenyl, 50% cyanogen propyl phenyl (wherein 25% cyanogen propyl
At least one of 25% phenyl) -50% dimethyl polysiloxane.
Preferably, the gas chromatographic detection condition are as follows: 180-300 DEG C of temperature of detector FID, for example, 230 DEG C；
Preferably, the gas chromatographic detection condition are as follows: carrier gas (N2) flow 0.1-2ml/min；H2Flow 20-80mL/min, it is empty
Throughput 300-600mL/min, make-up gas flow 10-40mL/min；Illustratively, carrier gas (N2) flow 0.1-2ml/min, example
For example 1ml/min；H2Flow 40mL/min, air mass flow 400mL/min, make-up gas flow 20mL/min.
Preferably, the gas chromatographic detection condition are as follows: post case: 25-50 DEG C of initial column temperature, 2-10min is kept, then with 15-40
DEG C/heating of the rate of min, 110-250 DEG C of final temperature, keep 2-10min.Illustratively, the gas chromatographic detection condition
Are as follows: post case: 35 DEG C of initial column temperature, 5min is kept, then heat up with the rate of 30 DEG C/min, 200 DEG C of final temperature, keep 5min.
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| CN111220726A (en) * | 2020-01-16 | 2020-06-02 | 中国神华煤制油化工有限公司 | Method for measuring DTBP content |
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