CN111929369A - Method for measuring sulfur content in high-pressure sulfurized isobutylene by gas chromatography - Google Patents
Method for measuring sulfur content in high-pressure sulfurized isobutylene by gas chromatography Download PDFInfo
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- CN111929369A CN111929369A CN201910771985.0A CN201910771985A CN111929369A CN 111929369 A CN111929369 A CN 111929369A CN 201910771985 A CN201910771985 A CN 201910771985A CN 111929369 A CN111929369 A CN 111929369A
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- 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
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Abstract
The invention discloses a method for measuring sulfur content in high-pressure sulfurized isobutylene by a gas chromatography, which solves the problem of measuring sulfur content in sulfurized isobutylene (T321) by the conventional high-pressure or one-step method, and comprises the following specific steps: measuring each component of the product by using gas chromatography, dividing intervals occupied by each component in the chromatography, calculating the content of each component in the product by using an area normalization method, calculating the sulfur content of each component in the product by using the sulfur content of each component and known pure substances of each component, summing the sulfur content of each component, and calculating the total sulfur content of the product. The method has the characteristics of universal equipment, simple and feasible method, high accuracy and the like, and is suitable for the sulfur content in the high-pressure sulfurized isobutylene prepared by various catalysts and auxiliaries.
Description
Technical Field
The invention relates to the technical field of accurate determination of sulfur content in high-pressure sulfurized isobutylene, in particular to a method for determining sulfur content in high-pressure sulfurized isobutylene by using a gas chromatography.
Background
Gas chromatography is a separation technique. In actual work, a sample to be analyzed is often a multi-component mixture in a complex matrix, and for a sample containing unknown components, the content of the sample must be separated firstly, and then the related components can be further analyzed;
in order to measure the sulfur content of the sulfurized isobutylene product, most of current manufacturers, laboratories, detection units and scientific research institutions adopt a lamp burning method, a tube furnace method, a coulomb method, a far infrared method, an X fluorescence method and the like. The lamp burning method consumes long time, has large measurement error and long consumed time, and is generally not adopted basically. The tube furnace method and the coulombic method basically adopt an oxidation method to introduce a sample into a cracking tube for reaction, a measured object is converted into titratable ions, the titratable ions are brought into a titration cell by carrier gas for titration, the electric quantity consumed in the process of electrolytic titration is measured, and the total sulfur content of the sample is calculated according to the Faraday's law; the method has good effect on measuring the trace sulfur content of PPM level in the product, but because the sulfur content of the high-pressure vulcanized isobutene is high and the sulfur index is 40-46%, the sample needs to be diluted by 500-fold and 1000-fold solvent during measurement, so that a large amount of solvent waste is caused by the detection of the sample, in addition, the measured data is not very stable, the method is particularly easily influenced by air humidity and electronic drift of equipment, the error of the measured value is larger, the configured test liquid medicine needs to be continuously replaced, the instrument is frequently cleaned, and the operation requirement of an operator is also very high. The far infrared and X fluorescence method for detecting the sulfur content has simple test, but the equipment cost is very expensive.
The problem of measuring the sulfur content of sulfurized isobutylene products with high precision has been plagued.
Disclosure of Invention
The invention aims to provide a method for accurately measuring the sulfur content of sulfurized isobutylene by using the existing equipment and technology, and solves the defects of the existing test method.
The invention provides the following technical scheme:
the high-pressure sulfurized isobutylene product is composed of di-tert-butyl polysulfide and isomers, and generally comprises the main components of di-tert-butyl monosulfide, S1 for short, di-tert-butyl disulfide, S2 for short, di-tert-butyl trisulfide, S3 for short, di-tert-butyl tetrasulfide, S4 for short, and di-tert-butyl pentasulfide, S5 for short;
in the technical scheme, in order to measure and calculate the sulfur content of the product and reduce errors, a component containing di-tert-butyl hexasulfide, namely sulfur 6, in the product is firstly provided, the content is divided, and the sulfur content calculation is introduced.
The invention also provides a method for measuring the sulfur content in high-pressure sulfurized isobutylene by using the gas chromatography, which comprises the following steps:
1) determination of product chromatography
Setting analysis conditions of each part of a chromatogram: the setting of temperature and time can be adjusted as required, and the setting principle is as follows: the components of the sulfurized isobutylene product can be obviously separated on a chromatogram map;
secondly, placing a prepared sample on the chromatograph according to the operation specification for chromatographic detection;
2) dividing intervals of each component on chromatogram map
Dividing main component intervals on the chromatogram, and reading corresponding test data of each main component in the chromatogram;
3) counting the percentage of each main component in the total components of the product
Calculating the percentage of each main component in the product according to a chromatographic area normalization method and corresponding chromatographic data;
4) calculating the ratio of sulfur element in each main component
Obtaining the total molecular weight of each main component according to the molecular formula of each main component, and then calculating the percentage of the molecular weight of the sulfur element in the total molecular weight of the whole components;
5) calculation of the Total Sulfur content of the product
And obtaining the sulfur content of each part according to the proportion of sulfur elements in each main component, and then accumulating to obtain the total sulfur content of the product.
Preferably, the chromatographic analysis conditions are set as follows:
a) column box: the initial temperature of the column box is 50 ℃ and the initial time is 5 min;
b) the first-stage heating rate is 5 ℃/min, and the termination temperature is 150 ℃;
c) the second-stage heating rate is 15 ℃/min, and the termination temperature is 240 ℃;
d) the third-stage heating rate is 20 ℃/min, and the termination temperature is 280 ℃; the final temperature holding time was 005 seconds.
The measuring range of the sulfur content measuring method provided by the invention is as follows: the sulfur content is 20-46%.
Advantageous effects
The invention provides a method for measuring sulfur content in high-pressure sulfurized isobutylene by using a gas chromatography, which has the following beneficial effects:
the measuring method provided by the invention utilizes the commonly used gas chromatograph to measure and calculate the sulfur content, the method has the advantages of universal equipment, high accuracy of measured values, simple calculation method, no need of medicament or solvent in the measuring process and low cost.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention is described in detail below.
1) Determination of product chromatography
Setting analysis conditions of each part of a chromatogram:
a) column box: the initial temperature of the column box is 50 ℃ and the initial time is 5 min;
b) the first-stage heating rate is 5 ℃/min, and the termination temperature is 150 ℃;
c) the second-stage heating rate is 15 ℃/min, and the termination temperature is 240 ℃;
d) the third-stage heating rate is 20 ℃/min, and the termination temperature is 280 ℃; the final temperature holding time was 005 seconds.
Secondly, placing a prepared sample on the chromatograph according to the operation specification for chromatographic detection;
2) dividing intervals of each component on chromatogram map
On the chromatogram, the main components S1, S2, S3, S4, S5 and S6 are divided into intervals, and the corresponding test data of each main component in the chromatogram are read;
for example, the following is the chromatographic test data for a certain sample (wherein the column for the peak name has been omitted)
3) Counting the percentage of each main component in the total components of the product
Calculating the percentage of each main component in the product according to a chromatographic area normalization method and corresponding chromatographic data;
for example, the chromatographic test data of the sample results in the following ratios of S1: 5.6518 percent; the S2 ratio is: 29.6065 percent; the S3 ratio is: 42.1302 percent; the S4 ratio is: 17.622 percent; the S5 ratio is: 4.1089 percent; the S6 ratio is: 0.8802 percent;
4) calculating the ratio of sulfur element in each main component
Obtaining the total molecular weight of each main component according to the molecular formula of each main component, and then calculating the percentage of the molecular weight of the sulfur element in the total molecular weight of the whole components;
for example, the calculation is continued according to the proportion of each part in S1-S6 in the above sample:
5) calculation of the Total Sulfur content of the product
And obtaining the sulfur content of each part according to the proportion of sulfur elements in each main component, and then accumulating to obtain the total sulfur content of the product.
For example, in the above sample, the sulfur content of S1 is: 5.6518% × 0.219178 ═ 1.238751%; s2 contains the following sulfur content: 29.6065% × 0.359551 ═ 10.64503% … …
Then, the sulfur content of S3 is 19.25952 percent through calculation; s4 contains the following sulfur content: 9.320727 percent; s5 contains the following sulfur content: 2.399358 percent; s6 contains the following sulfur content: 0.552282 percent;
the total sulfur content of the product is as follows: s1+ S2+ S3+ S4+ S5+ S6 ═ 43.4156716%
Namely: the sulfur content of the product was 43.415%.
The following 5 groups of high-pressure sulfurized isobutylene samples were randomly selected and subjected to sulfur content determination by the method, and the results were as follows:
sample 1:
the chromatogram and data were measured and were obtained using area normalization (in%):
S1：8.7175；S2：26.2628；S3：37.5405；S4：19.1051；S5：4.6371；S6：3.7366
calculating to obtain the sulfur content: 43.67 percent
Actually measuring: 43.73
Error: 0.06 percent
Sample 2:
measuring the chromatogram and data, and obtaining the result by area normalization statistics (unit percent)
S1：6.6727；S2：28.3754；S3：37.4896；S4：18.9755；S5：5.9766；S6：2.5098
Calculating to obtain the sulfur content: 43.90 percent
Actually measuring: 43.87 percent
Error: 0.03 percent
Sample 3:
measuring the chromatogram and data, and obtaining the result by area normalization statistics (unit percent)
S1：1.6326；S2：33.4857；S3：40.5733；S4：17.5963；S5：3.9498；S6：2.7619
Calculating to obtain the sulfur content: 43.73 percent
Actually measuring: 43.69 percent
Error: 0.04 percent
Sample 4:
measuring the chromatogram and data, and obtaining the result by area normalization statistics (unit percent)
S1：1.6326；S2：33.4857；S3：40.5733；S4：17.5963；S5：3.9498S6：2.7619
Calculating to obtain the sulfur content: 43.73 percent
Actually measuring: 43.64 percent
Error: 0.09 percent
Sample 5:
measuring the chromatogram and data, and obtaining the result by area normalization statistics (unit percent)
S1：3.6915；S2：27.0938；S3：41.8981；S4：19.3071；S5：7.8594；S6：0.1506
Calculating to obtain the sulfur content: 45.61 percent
Actually measuring: 45.49 percent
Error: 0.12 percent of
The method can also be used for measuring the sulfur content of other sulfurized single olefins, and is also within the protection scope of the method.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. A method for measuring the sulfur content in high-pressure sulfurized isobutylene by using a gas chromatography is characterized by comprising the following steps: the method comprises the following steps:
1) determination of product chromatography
Setting analysis conditions of each part of a chromatogram: the setting of temperature and time can be adjusted as required, and the setting principle is as follows: the components of the sulfurized isobutylene product can be obviously separated on a chromatogram map;
secondly, placing a prepared sample on the chromatograph according to the operation specification for chromatographic detection;
2) dividing intervals of each component on chromatogram map
Dividing main component intervals on the chromatogram, and reading corresponding test data of each main component in the chromatogram;
3) counting the percentage of each main component in the total components of the product
Calculating the percentage of each main component in the product according to a chromatographic area normalization method and corresponding chromatographic data;
4) calculating the ratio of sulfur element in each main component
Obtaining the total molecular weight of each main component according to the molecular formula of each main component, and then calculating the percentage of the molecular weight of the sulfur element in the total molecular weight of the whole components;
5) calculation of the Total Sulfur content of the product
And obtaining the sulfur content of each part according to the proportion of sulfur elements in each main component, and then accumulating to obtain the total sulfur content of the product.
2. The method for measuring the sulfur content in the high-pressure sulfurized isobutylene as claimed in claim 1, wherein: the analysis conditions of each part of the chromatogram are as follows:
a) column box: the initial temperature of the column box is 50 ℃ and the initial time is 5 min;
b) the first-stage heating rate is 5 ℃/min, and the termination temperature is 150 ℃;
c) the second-stage heating rate is 15 ℃/min, and the termination temperature is 240 ℃;
d) the third-stage heating rate is 20 ℃/min, and the termination temperature is 280 ℃; the final temperature holding time was 005 seconds.
3. The method for measuring the sulfur content in high-pressure sulfurized isobutylene as claimed in claim 1 or 2, wherein: the main components of the high-pressure sulfurized isobutylene product comprise di-tert-butyl monosulfide, S1 for short, di-tert-butyl disulfide, S2 for short, di-tert-butyl trisulfide, S3 for short, di-tert-butyl tetrasulfide, S4 for short, and di-tert-butyl pentasulfide, S5 for short.
4. The method for measuring the sulfur content in high-pressure sulfurized isobutylene as claimed in claim 1 or 2, wherein: the main components of the high-pressure sulfurized isobutylene product comprise di-tert-butyl monosulfide, S1 for short, di-tert-butyl disulfide, S2 for short, di-tert-butyl trisulfide, S3 for short, di-tert-butyl tetrasulfide, S4 for short, di-tert-butyl pentasulfide, S5 for short, and di-tert-butyl hexasulfide, S6 for short.
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Application publication date: 20201113 |