A method for simultaneously determining the contents of multiple impurities in refined TiCl4

Abstract

The invention discloses a method for simultaneously determining the fine TiCl 4 The method comprises the following steps: (1) setting chromatographic conditions; (2) CCl 3 COCl, CHCl 2 COCl, CH 2 ClCOCl, CS 2 and CCl 4 The method of the present invention has high efficiency, high selectivity, high sensitivity and fast analysis speed, and can simultaneously determine CCl 3 COCl, CHCl 2 COCl, CH 2 ClCOCl, CS 2 and CCl 4 Five kinds of impurity contents, and the detection method is accurate and feasible.

Description

Technical Field

[0001] The invention relates to the field of detection technology, and in particular to a method for simultaneously determining the contents of multiple impurities in refined TiCl4. Background Art

[0002] The quality of refined titanium tetrachloride (TiCl4) in sponge titanium production is closely related to the quality of sponge titanium. The key impurities in sponge titanium are four times enriched in the key impurities in refined TiCl4. Strict quality inspection of the key impurities in refined TiCl4 is necessary to ensure the quality of the final sponge titanium.

[0003] After chemical vanadium removal and distillation, most of the impurities such as VOCl3, most of the gases and solid compounds are removed from refined TiCl4, but there are still some impurities such as CCl3COCl, CHCl2COCl, CH2ClCOCl, CS2, CCl4, CO2, TiOCl2, etc., which can be miscible with titanium tetrachloride in any proportion. These impurities are the most difficult to separate from titanium tetrachloride. To remove the key impurities in refined TiCl4, it is necessary to quickly and accurately analyze the composition and content of the key impurities. Therefore, the analysis and control of key impurities in refined TiCl4 are also the key to the quality control of titanium materials, and the detection of the key impurity components and contents of refined TiCl4 is the basis and basis for the control of key impurities. If the technical difficulties of the analysis of the key impurity components and contents in refined TiCl4 can be solved, it can be used to guide the improvement of production processes and improve the quality of sponge titanium products, which will promote the upgrading of titanium industry products, promote the export of titanium products and increase the domestic market share of titanium products, and have huge economic benefits. At present, there are few relevant literature reports on the simultaneous determination of the impurity content in TiCl4.

[0004] Therefore, a method for simultaneously determining the impurity contents of CCl3COCl, CHCl2COCl, CH2ClCOCl, CS2, CCl4, CO2, and TiOCl2 in TiCl4 is urgently needed. To this end, the present invention team has provided a gas chromatography analysis method with simple operation, fast analysis, and accurate results after long-term experimental research, and has achieved good results. Summary of the invention

[0005] The object of the present invention is to provide a method for simultaneously determining the contents of multiple impurities in refined TiCl4.

[0006] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0007] The method for simultaneously determining the contents of multiple impurities in refined TiCl4 of the present invention comprises the following steps: (1) setting chromatographic conditions; (2) preparing a mixed standard working solution of CCl3COCl, CHCl2COCl, CH2ClCOCl, CS2 and CCl4; and (3) determining the contents by gas chromatography.

[0008] The chromatographic conditions of step (1) of the present invention are set as follows: chromatographic column: PEG-1500 quartz capillary column, specification is 0.25mm×30m; column temperature: programmed temperature rise; injection port temperature: 140-160°C; carrier gas: N2; carrier gas linear velocity: 5-15cm / s; detector: FID; detector temperature: 150-170°C; injection volume: 1μL.

[0009] The PEG-1500 quartz capillary column in step (1) of the present invention may also be a SE-54 capillary column.

[0010] The programmed temperature rise in step (1) of the present invention is: initial temperature 50°C, maintained for 3 minutes, heated to 140°C at a rate of 10°C / min, and maintained for 10 minutes.

[0011] Preferably, the injection port temperature in step (1) of the present invention is 150°C.

[0012] The N2 in step (1) may also be H2.

[0013] Preferably, the carrier gas linear velocity in step (1) of the present invention is 10 cm / s.

[0014] Preferably, the detector temperature in step (1) of the present invention is 160°C.

[0015] The mixed standard working solution of CCl3COCl, CHCl2COCl, CH2ClCOCl, CS2 and CCl4 described in step (2) of the present invention is prepared as follows:

[0016] (1) Preparation of calibration stock solutions: 5 μl CCl3COCl, 10 μl CHCl2COCl, 45 μl CH2ClCOCl, 15 μl CS2 and 1 ml CCl4 were added to five 20 ml quartz volumetric flasks with rubber stoppers, and fine TiCl4 was added to make the volume to 20 ml. The mixture was mixed and accurately weighed to prepare five calibration stock solutions.

[0017] (2) Preparation of mixed standard working solutions: Pipette 50 μl, 100 μl, 200 μl, 150 μl and 250 μl of the five calibration stock solutions into 25 20 ml quartz volumetric flasks, add refined TiCl4 to make up to 20 ml, mix well, and prepare five standard working solutions of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl, respectively.

[0018] The content determination in step (3) of the present invention is as follows: taking a TiCl4 sample to be tested and a mixed standard working solution, injecting them into a gas chromatograph system, performing chromatographic analysis under chromatographic conditions, and calculating the contents of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl impurities in the sample according to the chromatographic analysis results.

[0019] Beneficial effects of the present invention:

[0020] 1. The method of the present invention can determine the contents of five impurities, namely, CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl, in refined TiCl4.

[0021] 2. The method of the present invention adopts the standard addition method, and there is no need to prepare reagents with other solvents. The added impurities of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl can be well dissolved in TiCl4, thus avoiding the influence of the added solvent on the matrix.

[0022] 3. The detection method of the present invention has high accuracy, simple operation, high efficiency, rapidity, accuracy and feasibility. Specific embodiments

[0023] The technical solution of the present invention is further described in detail below through specific embodiments.

[0024] Example 1 Method for simultaneously determining the contents of multiple impurities in refined TiCl4

[0025] (1) Chromatographic condition setting:

[0026] Chromatographic column: PEG-1500 quartz capillary column, specification is 0.25mm×30m; column temperature: programmed temperature rise; injection port temperature: 150℃; carrier gas: N2; carrier gas linear velocity: 10cm / s; detector: FID; detector temperature: 160℃; injection volume: 1μL.

[0027] (2) Preparation of mixed standard working solution of CCl3COCl, CHCl2COCl, CH2ClCOCl, CS2 and CCl4:

[0028] S1. Preparation of mother solutions for calibration: 5 μl CCl3COCl, 10 μl CHCl2COCl, 45 μl CH2ClCOCl, 15 μl CS2 and 1 ml CCl4 were added to 5 20 ml quartz volumetric flasks with rubber stoppers, and fine TiCl4 was added to make the volume to 20 ml, mixed and accurately weighed to prepare 5 mother solutions for calibration;

[0029] S2. Preparation of mixed standard working solution: Pipette 50μl, 100μl, 200μl, 150μl and 250μl of the five calibration stock solutions into 25 20ml quartz volumetric flasks, add refined TiCl4 to make up to 20ml, mix well, and prepare five standard working solutions of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl respectively.

[0030] (3) Determination of content by gas chromatography: Take the TiCl4 sample to be tested and the mixed standard working solution, inject them into the gas chromatography system, perform chromatographic analysis under chromatographic conditions, and calculate the content of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl impurities in the sample based on the chromatographic analysis results.

[0031] Example 2 Method for simultaneously determining the contents of multiple impurities in refined TiCl4

[0032] (1) Chromatographic condition setting:

[0033] Chromatographic column: PEG-1500 quartz capillary column, specification is 0.25mm×30m; column temperature: programmed temperature rise; injection port temperature: 140℃; carrier gas: N2; carrier gas linear velocity: 5cm / s; detector: FID; detector temperature: 150℃; injection volume: 1μL.

[0034] (2) Preparation of mixed standard working solution of CCl3COCl, CHCl2COCl, CH2ClCOCl, CS2 and CCl4:

[0035] S1. Preparation of mother solutions for calibration: 5 μl CCl3COCl, 10 μl CHCl2COCl, 45 μl CH2ClCOCl, 15 μl CS2 and 1 ml CCl4 were added to 5 20 ml quartz volumetric flasks with rubber stoppers, and fine TiCl4 was added to make the volume to 20 ml, mixed and accurately weighed to prepare 5 mother solutions for calibration;

[0036] S2. Preparation of mixed standard working solution: Pipette 50μl, 100μl, 200μl, 150μl and 250μl of the five calibration stock solutions into 25 20ml quartz volumetric flasks, add refined TiCl4 to make up to 20ml, mix well, and prepare five standard working solutions of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl respectively.

[0037] (3) Determination of content by gas chromatography: Take the TiCl4 sample to be tested and the mixed standard working solution, inject them into the gas chromatography system, perform chromatographic analysis under chromatographic conditions, and calculate the content of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl impurities in the sample based on the chromatographic analysis results.

[0038] Example 1 Method for simultaneously determining the contents of multiple impurities in refined TiCl4

[0039] (1) Chromatographic condition setting:

[0040] Chromatographic column: PEG-1500 quartz capillary column, specification is 0.25mm×30m; column temperature: programmed temperature rise; injection port temperature: 160℃; carrier gas: N2; carrier gas linear velocity: 15cm / s; detector: FID; detector temperature: 170℃; injection volume: 1μL.

[0041] (2) Preparation of mixed standard working solution of CCl3COCl, CHCl2COCl, CH2ClCOCl, CS2 and CCl4:

[0042] S1. Preparation of mother solutions for calibration: 5 μl CCl3COCl, 10 μl CHCl2COCl, 45 μl CH2ClCOCl, 15 μl CS2 and 1 ml CCl4 were added to 5 20 ml quartz volumetric flasks with rubber stoppers, and fine TiCl4 was added to make the volume to 20 ml, mixed and accurately weighed to prepare 5 mother solutions for calibration;

[0043] S2. Preparation of mixed standard working solution: Pipette 50μl, 100μl, 200μl, 150μl and 250μl of the five calibration stock solutions into 25 20ml quartz volumetric flasks, add refined TiCl4 to make up to 20ml, mix well, and prepare five standard working solutions of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl respectively.

[0044] (3) Determination of content by gas chromatography: Take the TiCl4 sample to be tested and the mixed standard working solution, inject them into the gas chromatography system, perform chromatographic analysis under chromatographic conditions, and calculate the content of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl impurities in the sample based on the chromatographic analysis results.

[0045] Although the present invention has been described in detail above by general explanation and specific implementation methods, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A method for simultaneously determining the contents of multiple impurities in refined TiCl4, characterized in that: The method comprises the following steps: (1) setting chromatographic conditions; (2) preparing a mixed standard solution of CCl3COCl, CHCl2COCl, CH2ClCOCl, CS2 and CCl4; (3) determining the content by gas chromatography; The chromatographic conditions are set as follows: chromatographic column: PEG-1500 quartz capillary column, specification 0.25 mm × 30 m; Column temperature: programmed temperature rise; injection port temperature: 140-160°C; carrier gas: N2; carrier gas linear velocity: 5-15 cm / s; detector: FID; detector temperature: 150-170°C; injection volume: 1 μL; The temperature program is as follows: initial temperature 50°C, maintained for 3 min, heated to 140°C at 10°C / min, and maintained for 10 min.

2. The method for simultaneously determining the contents of multiple impurities in refined TiCl4 according to claim 1, characterized in that: The injection port temperature in step (1) is 150°C.

3. The method for simultaneously determining the contents of multiple impurities in refined TiCl4 according to claim 1, characterized in that: The N2 in step (1) may also be H2.

4. The method for simultaneously determining the contents of multiple impurities in refined TiCl4 according to claim 1, characterized in that: The carrier gas linear velocity in step (1) is 10 cm / s.

5. The method for simultaneously determining the contents of multiple impurities in refined TiCl4 according to claim 1, characterized in that: The detector temperature in step (1) is 160°C.

6. The method for simultaneously determining the contents of multiple impurities in refined TiCl4 according to claim 1, characterized in that: The mixed standard working solution of CCl3COCl, CHCl2COCl, CH2ClCOCl, CS2 and CCl4 described in step (2) is prepared as follows: (1) Preparation of calibration stock solutions: 5 μl CCl3COCl, 10 μl CHCl2COCl, 45 μl CH2ClCOCl, 15 μl CS2 and 1 ml CCl4 were added to five 20 ml quartz volumetric flasks with rubber stoppers, and fine TiCl4 was added to make the volume to 20 ml. The mixture was mixed and accurately weighed to prepare five calibration stock solutions. (2) Preparation of mixed standard working solutions: Pipette 50 μl, 100 μl, 200 μl, 150 μl and 250 μl of the five calibration stock solutions into 25 20 ml quartz volumetric flasks, add refined TiCl4 to make up to 20 ml, mix well, and prepare five standard working solutions of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl, respectively.

7. The method for simultaneously determining the contents of multiple impurities in refined TiCl4 according to claim 1, characterized in that: The content determination in step (3) is as follows: taking a TiCl4 sample to be tested and a mixed standard working solution, injecting them into a gas chromatograph system, performing chromatographic analysis under chromatographic conditions, and calculating the contents of CCl4, CS2, CH2ClCOCl, CHCl2COCl and CCl3COCl impurities in the sample according to the chromatographic analysis results.