CN112415100B - Method for detecting organic matters in titanium tetrachloride - Google Patents
Method for detecting organic matters in titanium tetrachloride Download PDFInfo
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Abstract
The invention discloses a method for detecting organic matters in titanium tetrachloride, which comprises the following steps of firstly, drawing a standard curve of alkane, benzene series, oxide and chloride; and then, carrying out hydrolysis reaction on the blank sample and the titanium tetrachloride sample to be detected, carrying out headspace-gas chromatography-mass spectrometry combined detection on the sample after the hydrolysis reaction to obtain a total ion current chromatogram of the titanium tetrachloride sample to be detected, and finally determining the type and the content of the organic matters in the titanium tetrachloride sample to be detected through a drawn standard curve and the total ion current chromatogram of the titanium tetrachloride sample to be detected. The method has the characteristics of simplicity, convenience, rapidness, environmental protection, accuracy and high sensitivity.
Description
Technical Field
The invention belongs to the field of chemical substance detection, particularly relates to a method for detecting organic matters in titanium tetrachloride, and particularly relates to a method for detecting a plurality of organic matters in titanium tetrachloride by a headspace-gas chromatography-mass spectrometry (HS-GC/MS) combined method.
Background
Titanium tetrachloride is an important intermediate for producing titanium sponge, metallic titanium and titanium dioxide, can also be used for manufacturing alloys, pigments and smoke screen agents for national defense, and is also a good solvent for dissolving polymers such as rubber and plastics. In the polyolefin industry, titanium tetrachloride is one of important active substances in a titanium-magnesium system Ziegler-Natta catalyst, and the type and content of impurities of the titanium tetrachloride can greatly influence the effect of the polyolefin catalyst.
Inductively coupled plasma atomic emission spectrometry (ICP) is used in the nonferrous metal industry standard YS/T655-2016 titanium tetrachloride of the people's republic of China to test SiCl in the nonferrous metal industry standard 4 、FeCl 3 、VOCl 3 、AlCl 3 、SnCl 4 However, no method for analyzing organic impurities is specified.
The analysis methods of organic substances in titanium tetrachloride include detection methods such as infrared spectroscopy and chromatography, for example:
in a literature of Tan hong and other infrared spectroscopic analysis of trace organic impurities in refined titanium tetrachloride, published in analytic test school report of 2012, a zinc selenide window and a polytetrafluoroethylene infrared liquid pool are used for detecting organic impurities such as trichloroacetyl chloride in titanium tetrachloride.
In 2014, metallurgical analysis discloses a comparison of different extracting agent extraction capacities for measuring trace carbon tetrachloride in a titanium tetrachloride hydrolysis system by liquid-liquid extraction gas chromatography, such as Liqing and the like, liquid-liquid extraction is performed by using organic solvents, such as heptane, normal hexane, normal octane, isooctane and the like, and quantitative analysis is performed on carbon tetrachloride in titanium tetrachloride by using gas chromatography.
A method for analyzing and detecting impurities containing chlorine compounds by using infrared spectroscopy, ion chromatography and gas chromatography is disclosed in a doctor's academic paper' analysis of main impurities in refined titanium tetrachloride and process control research 'of the main impurities in refined titanium tetrachloride' of Song Guanglin university of Beijing Physician 2015.
According to the method for detecting the organic impurities in the titanium tetrachloride reported in the literature, a special infrared absorption cell device is required to be arranged in the infrared spectrum method, the infrared spectrum sensitivity is low, the detection of the trace impurities is difficult, the liquid-liquid extraction and other pretreatment steps are required in the gas phase chromatography method, and the qualitative capability is poor.
In the polyolefin catalyst preparation industry, trace impurities in titanium tetrachloride can reduce the activity of the catalyst, so that the analytical method with simple establishment method, high sensitivity and strong qualitative capability is used for monitoring organic impurities in the refining and recycling of industrial titanium tetrachloride, and has important significance for avoiding environmental pollution and reasonably recycling waste liquid and waste residues in the production and use processes of titanium tetrachloride.
At present, no report on analysis of trace organic matters in titanium tetrachloride by a headspace-gas chromatography-mass spectrometry combined method exists, the method fills the blank, reduces the sample pretreatment steps, has no solvent pollution, and quickly performs qualitative and quantitative analysis on the organic matters in the titanium tetrachloride.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for detecting organic matters in titanium tetrachloride by using a headspace-gas chromatography-mass spectrometry combined method, which has the characteristics of simplicity, convenience, rapidness, accuracy and high sensitivity.
According to one aspect of the invention, the invention provides a method for detecting an organic substance in titanium tetrachloride, comprising:
step S1: preparing a series of working curve solutions containing alkane, benzene series, oxide and chloride;
step S2: performing headspace-gas chromatography-mass spectrometry combined detection by taking the series of working curve solutions as standard curve samples to obtain a standard curve sample total ion current chromatogram;
and step S3: drawing a standard curve of alkane, benzene series, oxide and chloride according to the standard curve solution prepared in the step S1 and the standard curve sample total ion current chromatogram in the step S2;
and step S4: carrying out hydrolysis reaction on titanium tetrachloride with the purity of more than 99.0 percent, preferably more than 99.9 percent, and detecting a sample after the hydrolysis reaction as a blank sample by using a headspace-gas chromatography-mass spectrometry combined method to obtain a blank sample total ion current chromatogram;
step S5: carrying out hydrolysis reaction on a titanium tetrachloride sample to be detected, and detecting the sample after the hydrolysis reaction by using a headspace-gas chromatography-mass spectrometry combined method to obtain a total ion current chromatogram of the titanium tetrachloride sample to be detected;
step S6: and determining the type and the content of the organic matters in the titanium tetrachloride sample to be detected according to the standard curve obtained in the step S3, the blank sample total ion current chromatogram obtained in the step S4 and the titanium tetrachloride sample total ion current chromatogram obtained in the step S5.
According to some embodiments of the invention, the method further comprises step S7: and (2) adding titanium tetrachloride with the purity of more than 99.0%, preferably more than 99.9% into the series of working curve solution in the step (S1) to perform hydrolysis reaction, and performing headspace-gas chromatography-mass spectrometry combined detection on a sample after the hydrolysis reaction as a standard sample to obtain a total ion current chromatogram of the standard sample.
According to some embodiments of the invention, in step S1, a series of working curve solutions are formulated using representative species of said alkanes, benzenes, oxides and chlorides, respectively.
According to a preferred embodiment of the present invention, in step S1, the representative of the alkane includes at least one selected from the group consisting of C4-C20 alkanes, the representative of the benzene series includes at least one selected from the group consisting of C6-C20 benzene series, the representative of the oxide includes at least one selected from the group consisting of C1-C12 alcohols, C3-C12 ketones, C4-C12 ethers, and C2-C12 esters, and the representative of the chloride includes a chloride selected from the group consisting of C1-C12 chlorides.
According to a preferred embodiment of the present invention, in step S1, a series of working curve solutions are prepared using hexane, toluene, methanol, 1, 2-dichloroethane as representative substances of the alkane, the benzene series, the oxide and the chloride, respectively.
According to a preferred embodiment of the invention, in step S1, a series of working curve solutions is formulated using ethanol as a representative of the oxide.
According to a preferred embodiment of the invention, in step S1, a series of working curve solutions is formulated using 1, 2-dichloroethane as representative of the chloride.
According to a preferred embodiment of the present invention, the method of preparing the standard solution is as follows: respectively weighing about 0.25g of hexane, toluene, methanol and 1, 2-dichloroethane in a 25mL volumetric flask, adding isopropanol to constant volume until the volume is scaled, preparing a series of working curve solution mother solutions with the concentrations of the hexane, the toluene, the methanol and the 1, 2-dichloroethane of 10mg/mL, and storing in a refrigerator at 4 ℃. The standard mother liquor has a shelf life of 1 month, and needs to be reconfigured when the standard mother liquor is overdue. The mother liquor of the standard solution is diluted to 0.01-1mg/mL standard solution with isopropanol.
According to the preferred embodiment of the present invention, the mother liquor of the standard solution is diluted stepwise to 0.01, 0.1, 0.2, 0.5, 1mg/mL of the standard solution using isopropanol.
According to some embodiments of the invention, the method of hydrolysis reaction is: and (3) taking a 20mL headspace bottle, adding 5-10mL ultrapure water or deionized water, and dropwise adding 0.1-1mL titanium tetrachloride for hydrolysis reaction. And after the hydrolysis reaction is finished, sealing the opening of the jaw with an aluminum cover to be tested.
According to a preferred embodiment of the present invention, the hydrolysis reaction is carried out by: and (3) taking a 20mL headspace bottle, adding 4.5-5.5mL ultrapure water or deionized water, and dropwise adding 0.4-0.6mL titanium tetrachloride for hydrolysis reaction. And after the hydrolysis reaction is finished, sealing the opening of the jaw with an aluminum cover to be tested.
According to a preferred embodiment of the present invention, the method of the hydrolysis reaction is: a20 mL headspace bottle was charged with 5mL ultrapure water or deionized water, and 0.5mL titanium tetrachloride was added dropwise for hydrolysis. And after the hydrolysis reaction is finished, sealing the opening of the jaw with an aluminum cover to be tested.
According to some embodiments of the invention, the temperature of the hydrolysis reaction is 15 to 35 ℃ and the time of the hydrolysis reaction is 5 to 30min.
According to a preferred embodiment of the invention, the temperature of the hydrolysis reaction is 20-25 ℃; the hydrolysis reaction time is 8-15min.
According to some embodiments of the invention, the standard curve sample is prepared as follows: and (3) taking a 20mL headspace bottle, and respectively adding 10-1000 mu L of the series of working curve solutions with different concentrations to perform hydrolysis reaction. And after the hydrolysis reaction is finished, sealing the jaw by using an aluminum cover, and adding a sample to be detected as a standard solution.
According to a preferred embodiment of the present invention, the standard curve sample is prepared as follows: and (3) taking a 20mL headspace bottle, and respectively adding 50-150 mu L of the series of working curve solutions with different concentrations to perform hydrolysis reaction. After the hydrolysis reaction is finished, the jaw is sealed by an aluminum cover, and the jaw is used as a standard solution to be added with a sample to be detected.
According to a preferred embodiment of the present invention, the standard curve sample is prepared as follows: and (3) taking a 20mL headspace bottle, and respectively adding 100 mu L of the series of working curve solutions with different concentrations to perform hydrolysis reaction. After the hydrolysis reaction is finished, the jaw is sealed by an aluminum cover, and the jaw is used as a standard solution to be added with a sample to be detected.
According to some embodiments of the invention, the blank sample is prepared as follows: titanium tetrachloride (analytically pure or otherwise of the same purity) of greater than 99.0%, preferably greater than 99.9%, is used as a blank sample reagent. And (3) taking a 20mL headspace bottle, adding 5-10mL ultrapure water or deionized water, and slowly dropwise adding 0.1-1mL titanium tetrachloride for hydrolysis reaction. And after the hydrolysis reaction is finished, sealing the opening of the jaw by using an aluminum cover, and taking the opening as a blank sample to be detected.
According to some embodiments of the invention, the blank sample is prepared as follows: titanium tetrachloride (analytically pure or otherwise of the same purity) of greater than 99.0%, preferably greater than 99.9%, is used as a blank sample reagent. A20 mL headspace bottle was charged with 5mL ultrapure water or deionized water, and 0.5mL titanium tetrachloride was slowly added dropwise for hydrolysis. And after the hydrolysis reaction is finished, sealing the opening of the jaw by using an aluminum cover, and taking the opening as a blank sample to be detected.
According to some embodiments of the invention, the preparation of the spiked sample is as follows: and (3) taking a 20mL headspace bottle, respectively adding 10-1000 μ L of the series of working curve solutions with different concentrations, adding 5-10mL of ultrapure water or deionized water, slowly dropwise adding 0.1-1mL of titanium tetrachloride (analytically pure or other same purity) with the purity of more than 99.0%, preferably more than 99.9%, and carrying out hydrolysis reaction. And after the hydrolysis reaction is finished, sealing the jaw by using an aluminum cover, and using the jaw as a labeled sample to be detected.
According to some embodiments of the invention, the preparation of the spiked sample is as follows: taking a 20mL headspace bottle, respectively adding 50-150 μ L of the series of working curve solutions with different concentrations, adding 5-10mL of ultrapure water or deionized water, slowly dropwise adding 0.1-1mL of titanium tetrachloride (analytically pure or other same purities) with the purity of more than 99.0%, preferably more than 99.9%, to perform hydrolysis reaction. And after the hydrolysis reaction is finished, sealing the jaw by using an aluminum cover, and using the jaw as a labeled sample to be detected.
According to a preferred embodiment of the invention, the preparation of the spiked sample is as follows: a20 mL headspace bottle was taken, 100. Mu.L of each of the above series of working curve solutions with different concentrations was added, 5mL of ultrapure water was added, and 0.5mL of titanium tetrachloride (analytically pure or otherwise of the same purity) with a purity of more than 99.0%, preferably more than 99.9% was slowly added dropwise to conduct hydrolysis reaction. And after the hydrolysis reaction is finished, sealing the jaw by using an aluminum cover, and taking the jaw as a labeled sample to be detected.
According to some embodiments of the invention, the conditions of the headspace are: heating the headspace at 80-95 deg.C, the temperature of the transmission line at 80-120 deg.C, the temperature of the headspace sampling needle at 80-130 deg.C, and heating time for 5-60min.
According to a preferred embodiment of the invention, the conditions of the headspace are: heating the headspace at 85-95 deg.C, the temperature of the transmission line at 90-110 deg.C, the temperature of the headspace sampling needle at 100-120 deg.C, and heating time for 20-40min.
According to a preferred embodiment of the invention, the conditions of the headspace are: the headspace is heated to 90 ℃, the temperature of the transmission line is 100 ℃, the temperature of the headspace sampling needle is 110 ℃, and the heating time is 30min.
According to some embodiments of the invention, the gas chromatography conditions are: the sample inlet temperature is 200-280 ℃, the type of the sample inlet is a shunt sample inlet or a shunt/no-shunt sample inlet, the shunt ratio of the sample inlet is 1-50, the carrier gas is high-purity helium, the flow rate of the carrier gas is 0.5-1.2mL/min, the temperature rise method is that the temperature is programmed to 280 ℃ at 35 ℃, and the temperature of the chromatographic mass spectrometry connecting rod is 200-280 ℃.
According to a preferred embodiment of the invention, the gas chromatography conditions are: the injection port temperature is 200-240 ℃, the injection port split ratio is 30.
According to a preferred embodiment of the present invention, the conditions of the gas chromatography are: the injection port temperature is 200 ℃, the injection port type is a split injection port, the split ratio of the injection port is 50:1, the flow rate of carrier gas is 1.0mL/min, the chromatographic column is an HP-5MS chromatographic column, the temperature rise method is to maintain 3min at 35 ℃, maintain 5min at 10 ℃/min to 250 ℃, and the temperature of a connecting rod of the chromatographic mass spectrometer is 200 ℃.
According to some embodiments of the invention, the chromatography column used in the gas chromatography comprises any one selected from the group consisting of an HP-5MS column, a medium polarity DB-35MS column, and a polar HP-INNOWAX column.
According to a preferred embodiment of the invention, the chromatography column used for the gas chromatography is an HP-5MS column.
According to some embodiments of the invention, the conditions of the mass spectrum are: the mass spectrum ion source is an electron bombardment ionization source, the temperature of the mass spectrum ion source is 200-280 ℃, and the mass spectrum acquisition type is full scanning m/z 20-500.
According to a preferred embodiment of the invention, the mass spectrometry ion source temperature is in the range of 220-240 ℃.
According to a preferred embodiment of the invention, the mass spectrometry ion source temperature is 230 ℃.
According to some embodiments of the present invention, the method for drawing the standard curve in step S3 is as follows: and detecting the standard curve samples with different concentrations according to the headspace-gas chromatography-mass spectrometry combined method to obtain the total ion current chromatogram of the standard curve samples. And (3) taking the mass of the added standard curve sample as an X axis, and taking the integrated peak area of the total ion current chromatogram as a Y axis to draw a standard curve of hydrocarbons, benzene series, oxides and chlorides.
According to some embodiments of the invention, the linear range of the standard curve is 0.01-1mg/mL, and the linear correlation coefficient is > 0.99.
According to some embodiments of the invention, a blank sample total ion current chromatogram is shown in figure 1.
Adding 20mg/kg addition levels of hexane, toluene, methanol and 1, 2-dichloroethane into a titanium tetrachloride blank sample, and detecting the standard samples with different concentrations according to the headspace-gas chromatography-mass spectrometry combined method to obtain a total ion current chromatogram of the standard samples, which is shown in fig. 2.
The purpose of the tests carried out on the spiked samples is to verify the feasibility of the process according to the invention, from which the recovery of alkanes, benzenes, oxides and chlorides, the relative standard deviation RSD and the limits of detection in the process according to the invention can be obtained.
According to some embodiments of the invention, the process has a recovery of alkanes, benzenes, oxides and chlorides of > 60%, a relative standard deviation RSD of < 20%, and a detection limit of 0.01mg/kg.
According to a preferred embodiment of the invention, the process has a recovery of hexane, toluene, methanol, 1, 2-dichloroethane of > 60%, a relative standard deviation RSD of < 20%, and a detection limit of 0.01mg/kg.
According to a preferred embodiment of the present invention, two addition levels of 20mg/kg and 100mg/kg of hexane, toluene, methanol, 1, 2-dichloroethane were added to a blank sample of titanium tetrachloride, each addition level prepared 6 parallel samples with sample recovery of 75-94% and RSD of 5.65-16.14%, and the specific results are shown in table 1.
TABLE 1 recovery with standard and precision test (n = 6)
According to some embodiments of the invention, the various spectral peaks in the total ion current chromatogram of the titanium tetrachloride sample to be detected are integrated, qualitative analysis is performed by NIST spectral library retrieval, classification is performed according to hydrocarbons, benzene series, oxides and chlorides, and the types and the contents of various organic matters in the titanium tetrachloride are obtained by using peak areas for quantitative analysis.
According to another aspect of the invention, there is provided use of the method according to the first aspect for the detection of titanium tetrachloride impurities or for quality control of the recovery of titanium tetrachloride in a mixed titanium tetrachloride waste residue effluent.
The invention discloses a method for detecting organic matters in titanium tetrachloride by a headspace-gas chromatography-mass spectrometry combined method. Firstly, ultrapure water or deionized water is added into a headspace bottle, and then titanium tetrachloride is slowly added to carry out hydrolysis reaction. After the hydrolysis reaction is finished, the headspace bottle is sealed and used for analysis by a headspace-gas chromatography-mass spectrometry combined method. Heating by using a static headspace method to volatilize organic matters from the water phase so as to achieve two-phase balance. Headspace gas was injected into the GC-MS for testing. The essential difference between the headspace method and the prior art is that the headspace method is green and environment-friendly, the use of an extraction solvent is reduced, the pretreatment process of a sample is simple, the headspace method is combined with the chromatographic mass spectrometry, the sensitivity is high, the qualitative capacity is strong, and the accuracy is high, so that the organic matter in the titanium tetrachloride can be quickly and accurately detected.
The method for detecting the organic matters in the titanium tetrachloride is simple and convenient to operate, can be used for detecting titanium tetrachloride impurities and controlling the quality of the titanium tetrachloride in the mixed titanium tetrachloride waste residue and waste liquid during the recovery of the titanium tetrachloride, provides technical support for the refining and recycling of the titanium tetrachloride production, improves the economic benefit of enterprises and reduces the environmental pollution.
Drawings
Fig. 1 is a blank sample total ion current chromatogram according to an embodiment of the present invention. The chromatographic peaks are: air for 1.376min.
FIG. 2 is a total ion flow chromatogram of a spiked sample at a 20mg/kg addition level, according to one embodiment of the invention. The chromatographic peaks are sequentially as follows: air for 1.386min; methanol 1.479min, isopropanol 1.744min, hexane 2.198min, 1, 2-dichloroethane 2.740min, toluene 4.859min, hexane impurity isohexane 2.705min, and methylcyclopentane 2.475min.
FIG. 3 is a chromatogram of the total ion current of a titanium tetrachloride sample A to be measured in industry in example 1. The chromatographic peaks are sequentially as follows: air 1.389min, toluene 4.859min, ethylbenzene 6.829min, xylene isomer 6.998min, xylene isomer 7.472min, 1, 3-dichloropropene 8.014min methyl ethyl benzene isomer 8.821min, methyl ethyl benzene isomer 8.846min, methyl ethyl benzene isomer 9.162min.
FIG. 4 is a chromatogram of the total ion current of a titanium tetrachloride sample B to be tested in industrial recovery in example 2. The chromatographic peaks are sequentially as follows: air 1.387min, ethanol 1.577min, isopropanol 1.69min, chloroethylene 2.737min, toluene 4.846min, ethylbenzene 6.831min, xylene 7.0min, 1, 3-dichloropropene 8.014min, methyl ethyl benzene isomer 8.821min, methyl ethyl benzene isomer 8.845min, and methyl ethyl benzene isomer 9.162min.
In the total ion current chromatogram, an air peak is introduced during sampling, and the peak area does not participate in calculation.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the following embodiments.
Example 1 and example 2 were each tested using the following method:
preparation of standard curve samples: respectively weighing about 0.25g of hexane, toluene, methanol and 1, 2-dichloroethane in a 25mL volumetric flask, adding isopropanol to fix the volume to the scale line, preparing a series of working curve solution mother liquor with the concentration of each substance of hexane, toluene, methanol and 1, 2-dichloroethane of 10mg/mL, and gradually diluting the standard solution mother liquor to 0.01, 0.1, 0.2, 0.5 and 1mg/mL by using isopropanol. And (3) taking a 20mL headspace bottle, respectively adding 100 mu L of standard solutions with different concentrations, sealing by using an aluminum cover with a jaw, and taking the obtained product as a standard curve sample to be detected.
Preparing a blank sample: titanium tetrachloride (analytically pure or of otherwise identical purity, purity > 99.9%) was used as a blank reagent. A20 mL headspace bottle was charged with 5mL ultrapure water, 0.5mL titanium tetrachloride (> 99.9%) was slowly added dropwise, and hydrolysis was carried out at room temperature for 10min. And after the hydrolysis reaction is finished, sealing the jaw by using an aluminum cover, and taking the jaw as a blank sample to be detected.
Respectively detecting the standard curve sample and the blank sample by adopting the following methods in a headspace-gas chromatography-mass spectrometry combined method:
the instrument comprises: an Agilent G1888A headspace sample injector and an Agilent 7890A-5975C gas chromatography-mass spectrometer.
Headspace conditions: the headspace is heated to 90 ℃, the temperature of the transmission line is 100 ℃, the temperature of the headspace sampling needle is 110 ℃, and the heating time is 30min.
Chromatographic conditions are as follows: sample inlet temperature: 200-250 ℃; split-flow sample introduction, split-flow ratio: 50; carrier gas: high purity helium, 1.0mL/min; HP-5MS column (30 m.times.0.25 mm.times.0.25 μm); the temperature rise method comprises the following steps: maintaining at 35 deg.C for 3min, heating at 10 deg.C/min to 250 deg.C, and maintaining for 5min; connecting rod temperature: at 200 ℃.
Mass spectrum conditions: electron impact ionization source (EI source), mass spectrometry ion source temperature: 230 ℃; and (3) mass spectrum acquisition type: the full scanning m/z is 20-500.
Drawing a standard curve: the mass (concentration of the solution in the standard curve multiplied by the volume of the solution added) is taken as the X axis, and the integrated peak area of the total ion current chromatogram is taken as the Y axis, so that the standard curve of hexane, toluene, methanol and 1, 2-dichloroethane is plotted as shown in Table 2.
TABLE 2 Standard Curve and Linear correlation coefficient
| Species of matter | Representative substances | Linear equation of state | R 2 |
| Alkane(s) | Hexane (C) | y＝2E+08x+202887 | 0.9936 |
| Benzene series compound | Toluene | y＝3E+08x+409082 | 0.9977 |
| Oxide of silicon | Methanol | y＝1E+08x+80814 | 0.9986 |
| |
1, 2-dichloroethane | y＝2E+08x+236510 | 0.9978 |
The blank sample total ion current chromatogram is shown in FIG. 1.
Example 1
Titanium tetrachloride sample A to be tested: titanium tetrachloride is used in the industry in certain polyolefin catalyst production lines.
Sample pretreatment: a20 mL headspace bottle was charged with 5mL ultrapure water, and 0.5mL (0.863 g) of a titanium tetrachloride sample to be measured was slowly added dropwise to conduct hydrolysis reaction. And after the hydrolysis reaction is finished, sealing the opening by using a jaw aluminum cover.
The instrument comprises the following steps: an Agilent G1888A headspace sample injector and an Agilent 7890A-5975C gas chromatography-mass spectrometer.
Headspace conditions: the headspace is heated to 90 ℃, the temperature of the transmission line is 100 ℃, the temperature of the headspace sampling needle is 110 ℃, and the heating time is 30min.
Chromatographic conditions are as follows: sample inlet temperature: 200-250 ℃; split-flow sample introduction, split-flow ratio: 50; carrier gas: high purity helium, 1.0mL/min; HP-5MS column (30 m.times.0.25 mm.times.0.25 μm); the temperature rise method comprises the following steps: maintaining at 35 deg.C for 3min, heating at 10 deg.C/min to 250 deg.C, and maintaining for 5min; connecting rod temperature: at 200 ℃.
Mass spectrum conditions: electron impact ionization source (EI source), mass spectrometry ion source temperature: 230 ℃; and (3) mass spectrum acquisition type: full scan m/z 20-500.
The chromatogram of the total ion current of the titanium tetrachloride sample A to be detected is shown in figure 3. The sample results of this example were characterized using a NIST library search, and the results are shown in table 3; quantification was done using an external standard curve and the results are shown in table 4.
Table 3 area of peak and assignment of peak in example 1
| Retention time | Peak area | Name of substance |
| 4.859 | 237998099 | Toluene |
| 6.829 | 443040 | Ethylbenzene production |
| 6.998 | 737297 | Xylene |
| 7.472 | 196387 | Xylene |
| 8.014 | 1719657 | 1, 3-dichloropropene |
| 8.821 | 2352228 | Methyl ethyl benzene |
| 8.846 | 1638044 | Methyl ethyl benzene |
| 9.162 | 798714 | Methyl ethyl benzene |
Table 4 example 1 calculation results
| Species of matter | Sum of Peak areas | Mass (mg) | Content (mg/kg) |
| Alkane(s) | —— | —— | —— |
| Benzene series compound | 244163809 | 0.81 | 971.91 |
| Oxide compound | —— | —— | —— |
| Chloride compound | 1719657 | 0.0074 | 8.87 |
Example 2
Titanium tetrachloride sample B to be tested: titanium tetrachloride is industrially recovered in a certain polyolefin catalyst production line.
Sample pretreatment: a20 mL headspace bottle was charged with 5mL ultrapure water, and 0.5mL (0.863 g) of titanium tetrachloride was slowly added dropwise to conduct hydrolysis. And after the hydrolysis reaction is finished, sealing the opening by using a jaw aluminum cover.
The instrument comprises the following steps: an Agilent G1888A headspace sample injector and an Agilent 7890A-5975C gas chromatography-mass spectrometer.
Headspace conditions: the headspace is heated to 90 ℃, the temperature of the transmission line is 100 ℃, the temperature of the headspace sampling needle is 110 ℃, and the heating time is 30min.
Chromatographic conditions are as follows: sample inlet temperature: 200-250 ℃; split-flow sample introduction, split-flow ratio: 50; carrier gas: high purity helium, 1.0mL/min; HP-5MS column (30 m.times.0.25 mm.times.0.25 μm); the temperature rising method comprises the following steps: maintaining at 35 deg.C for 3min, heating at 10 deg.C/min to 250 deg.C, and maintaining for 5min; connecting rod temperature: at 200 ℃.
Mass spectrum conditions: electron impact ionization source (EI source), mass spectrometry ion source temperature: 230 ℃; the type of mass spectrum acquisition: the full scanning m/z is 20-500.
The chromatogram of the total ion current of the titanium tetrachloride sample B to be detected is shown in figure 4. The sample results of this example were characterized using a NIST library search, with the results shown in table 5; the results are shown in Table 6, using external standard curve quantification.
TABLE 5 area of peak and peak assignment in example 2
| Retention time | Peak area | Name of substance |
| 1.577 | 46401 | Ethanol |
| 1.69 | 527205 | Isopropyl alcohol |
| 2.737 | 31163 | Vinyl chloride |
| 4.846 | 168314287 | Toluene |
| 6.831 | 329685 | Ethylbenzene production |
| 7 | 523448 | Xylene |
| 8.014 | 1183969 | 1, 3-dichloropropene |
| 8.821 | 1486049 | Methyl ethyl benzene |
| 8.845 | 968928 | Methyl ethyl benzene |
| 9.162 | 429571 | Methyl ethyl benzene |
Table 6 example 2 calculation results
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (18)
1. A method for detecting organics in titanium tetrachloride comprising:
step S1: preparing a series of working curve solutions containing alkane, benzene series, oxide and chloride;
step S2: performing headspace-gas chromatography-mass spectrometry combined detection by taking the series of working curve solutions obtained in the step S1 as standard curve samples to obtain a standard curve sample total ion current chromatogram;
and step S3: drawing a standard curve of alkane, benzene series, oxide and chloride according to the standard curve solution prepared in the step S1 and the standard curve sample total ion current chromatogram map in the step S2;
and step S4: carrying out hydrolysis reaction on titanium tetrachloride with the purity of more than 99.0%, and detecting a sample after the hydrolysis reaction as a blank sample by using a headspace-gas chromatography-mass spectrometry combined method to obtain a blank sample total ion chromatogram;
step S5: carrying out hydrolysis reaction on a titanium tetrachloride sample to be detected, and detecting the sample after the hydrolysis reaction by using a headspace-gas chromatography-mass spectrometry combined method to obtain a total ion current chromatogram of the titanium tetrachloride sample to be detected;
step S6: determining the type and content of organic matters in the titanium tetrachloride sample to be detected according to the standard curve obtained in the step S3, the blank sample total ion current chromatogram obtained in the step S4 and the titanium tetrachloride sample total ion current chromatogram obtained in the step S5;
wherein hexane, toluene, methanol, 1, 2-dichloroethane are used as representative substances of the alkane, benzene series, oxide and chloride, respectively;
wherein the conditions of the gas chromatography are as follows: the injection port temperature is 200-240 ℃, the injection port split ratio is 30.
2. The method of claim 1, wherein the titanium tetrachloride in step S4 has a purity of greater than 99.9%.
3. The method according to claim 1 or 2, characterized in that the method further comprises a step S7: and (3) adding titanium tetrachloride with the purity of more than 99.0% into the series of working curve solution obtained in the step (S1) to carry out hydrolysis reaction, and detecting a sample after the hydrolysis reaction as a standard sample by using a headspace-gas chromatography-mass spectrometry combined method to obtain a total ion current chromatogram of the standard sample.
4. The method according to claim 3, characterized in that the method further comprises a step S7: and (2) adding titanium tetrachloride with the purity of more than 99.9% into the series of working curve solutions in the step S1 to perform hydrolysis reaction.
5. The method according to claim 1 or 2, wherein in step S1, a series of working curve solutions are prepared using representative species of the alkane, benzene series, oxide and chloride, respectively.
6. The method according to claim 1 or 2, characterized in that the hydrolysis reaction is carried out by: adding 5-10mL of ultrapure water or deionized water into a 20mL headspace bottle, and dropwise adding 0.1-1mL of titanium tetrachloride sample for hydrolysis reaction;
and/or the temperature of the hydrolysis reaction is 15-35 ℃; the hydrolysis reaction time is 5-30min.
7. The method of claim 6, wherein the hydrolysis reaction is carried out by: 4.5-5.5mL of ultrapure water or deionized water is added into the headspace bottle, and 0.4-0.6mL of titanium tetrachloride sample is dripped for hydrolysis reaction;
and/or the temperature of the hydrolysis reaction is 20-25 ℃; the time of the hydrolysis reaction is 8-15min.
8. Method according to claim 1 or 2, characterized in that the conditions of the headspace are: heating the headspace at 80-95 deg.C, the temperature of the transmission line at 80-120 deg.C, the temperature of the headspace sampling needle at 80-130 deg.C, and heating time for 5-60min.
9. The method of claim 8, wherein the headspace is conditioned by: heating the headspace at 85-95 deg.C, the temperature of the transmission line at 90-110 deg.C, the temperature of the headspace sampling needle at 100-120 deg.C, and heating time for 20-40min.
10. The method of claim 9, wherein the headspace condition is: the headspace heating is 90 ℃, the temperature of the transmission line is 100 ℃, the temperature of the headspace sampling needle is 110 ℃, and the heating time is 30min.
11. The method according to claim 1 or 2, characterized in that the gas chromatography conditions are: the injection port temperature is 200 ℃, the injection port type is a split injection port, the split ratio of the injection port is 50:1, the carrier gas flow rate is 1.0mL/min, the temperature rise method is 35 ℃ for 3min,10 ℃/min for 250 ℃ for 5min, and the temperature of a chromatographic mass spectrometry connecting rod is 200 ℃.
12. The method of claim 1 or 2, wherein the conditions of mass spectrometry are: the mass spectrum ion source is an electron bombardment ionization source, the mass spectrum acquisition type is full scanning m/z 20-500, and the temperature of the mass spectrum ion source is 200-280 ℃.
13. The method of claim 12, wherein the mass spectrometry ion source temperature is 220-240 ℃.
14. The method of claim 13, wherein the mass spectrometry ion source temperature is 230 ℃.
15. The method according to claim 1 or 2, wherein in step S3, the mass is taken as the X-axis, and the integrated peak area of the total ion current chromatogram is taken as the Y-axis to plot a standard curve of hydrocarbons, benzenes, oxides, chlorides.
16. The method of claim 15, wherein in step S3, the linear range of the standard curve is 0.01-1mg/mL, and the linear correlation coefficient is > 0.99.
17. The method according to claim 1 or 2, characterized in that, the chromatographic peaks in the total ion current chromatogram of the titanium tetrachloride sample to be detected are integrated, qualitative analysis is carried out by NIST spectral library retrieval, and quantitative analysis is carried out by peak area, so as to obtain the types and contents of various organic matters in the titanium tetrachloride; and/or
In the method, the sample recovery rate of the alkane, the benzene series, the oxide and the chloride is more than 60 percent, the relative standard deviation is less than 20 percent, and the detection limit is 0.01mg/kg.
18. Use of a method according to any one of claims 1 to 17 in the detection of titanium tetrachloride impurities or in the quality control of the recovery of titanium tetrachloride in mixed titanium tetrachloride waste residue streams.
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