Method for measuring content of TiO2 in boiling chlorination bed waste residues

Abstract

The invention provides a method for measuring the content of TiO2 in boiling chlorination bed waste residues. The method comprises the following steps: S1, accurately weighing 0.4-0.6 g of a chlorination bed waste residue sample and 8.0-10.0 g of a fluorescent mixed flux; the fluorescent mixed flux is prepared from 33%-67% of lithium tetraborate and 33%-67% of lithium metaborate; s2, uniformly mixing the weighed chlorinated bed waste residue sample with a fluorescent mixed flux, putting the mixture into a platinum-based alloy crucible, adding 0.2-0.4 g of a 30% lithium bromide solution, and stirring while adding until the mixture is uniformly stirred; s3, in a high-frequency automatic sample melting machine, performing piece melting according to a preset automatic sample melting program, pouring into a mold, and cooling and solidifying into a slide; and S4, putting the prepared slide into an X-ray fluorescence spectrophotometer, selecting working parameters of the X-ray fluorescence spectrophotometer for measurement, and automatically calculating the content of TiO2 in the boiling chlorination bed waste residues. The method provided by the invention can effectively reduce the interference effect on the TiO2 element in the boiling chlorination bed waste residue, and improve the accuracy of the test result of the content of the TiO2 in the boiling chlorination bed waste residue.

Description

Technical Field

[0001] The invention relates to the technical field of metallurgical chemical analysis and detection, in particular to a method for determining the TiO2 content in boiling chlorination bed waste residue. Background Art

[0002] In the industrial boiling chlorination process, it is difficult to accurately monitor the conversion rate due to high temperature, difficulty in sampling chlorine-related intermediates, and large fluctuations in the content in the residue. Usually, only the TiO2 content in the rutile raw material can be detected to guide production. Accurately measuring the TiO2 content in the boiling chlorination residue can ensure the continuous operation of the chlorination furnace and improve the reaction conversion rate through the ingredient ratio, which is of great significance for guiding the industrial continuous production of titanium tetrachloride.

[0003] Currently, common TiO2 detection methods include XRF (X-ray fluorescence), AAS (atomic absorption spectrometry), and ICP-AES (inductively coupled plasma spectroscopy) chemical analysis. XRF, among others, offers highly reliable and accurate results, along with relatively simple sample preparation. XRF is widely used due to its relatively simple sample preparation. Sample preparation for XRF is typically performed using three methods: pelleting, adsorption, and fusion. The pelleting method typically involves grinding the sample to a size of less than 200 mesh. The test results are significantly affected by particle size and uniformity. The adsorption method involves dropping an organic solution containing one or more components onto filter paper or a special adsorbent and drying it. The test results are significantly affected by the sample's adsorption capacity and physical properties. The fusion method involves adding a specific proportion of flux to the sample, melting it at high temperature, and then cooling it to form a glass slide. This method mitigates the influence of particle size, uniformity, and adsorption capacity on the test results. Currently, no glass fusion X-ray fluorescence spectrometric method for boiling chlorinated residues has been developed.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The problem solved by the invention is how to quickly and accurately detect the TiO2 content in the boiling chlorination bed waste residue.

[0006] To solve the above problems, the present invention provides a method for determining the TiO2 content in a boiling chlorination bed waste residue, comprising:

[0007] S1. Accurately weigh 0.4-0.6 g of chlorination bed waste residue sample and 8.0-10.0 g of fluorescent mixed flux; the fluorescent mixed flux is composed of 33-67% lithium tetraborate and 33-67% lithium metaborate;

[0008] S2. After the weighed chlorination bed waste residue sample and the fluorescent mixed flux are mixed evenly, the mixture is placed in a platinum-based alloy crucible, and 0.2-0.4 g of 30% lithium bromide solution is added while stirring until the mixture is evenly mixed;

[0009] S3, in a high-frequency automatic melting machine, melt the sample according to the preset automatic melting program, pour it into a mold, cool and solidify it into a glass slide;

[0010] S4. Place the prepared glass slide into an X-ray fluorescence spectrometer, select the working parameters of the X-ray fluorescence spectrometer for measurement, and automatically calculate the TiO2 content in the boiling chlorination bed waste residue.

[0011] Preferably, step S1 specifically comprises: accurately weighing 0.4 g of chlorination bed waste residue sample and 8.0 g of fluorescent mixed flux; the fluorescent mixed flux is composed of 67% lithium tetraborate and 33% lithium metaborate by mass.

[0012] Preferably, the melting conditions of step S3 are: preheating time 170-190s, melting temperature 900-950°C, melting time 330-390s, self-cooling time 220-260s, and air cooling time 110-130s.

[0013] Preferably, the melting conditions of step S3 are: preheating time 175-185s, melting temperature 930-950°C, melting time 350-370s, self-cooling time 230-250s, and air cooling time 115-125s.

[0014] Preferably, the chlorination bed waste residue sample in step S1 is pretreated by the following method: drying the chlorination bed waste residue in an oven at 120-130° C. for 1.5-2.5 h, grinding it in a vibrating grindstone for 120-150 s after cooling, and placing it in a dryer for later use.

[0015] Preferably, the operating parameters of the X-ray fluorescence spectrometer in step S4 are: the Kα line of Ti is selected as the analysis line, the peak of 2θ is 86.153°, the crystal is LiF200, the detector is a Flow Counter, the detection voltage is 50V, the detection current is 60mA, and the measurement time is 30s.

[0016] Preferably, the TiO2 content in the boiling chlorination bed waste residue ranges from 20% to 60%.

[0017] Compared with the prior art, the method for determining the TiO2 content in boiling chlorination bed waste residue described in an embodiment of the present invention has the following beneficial effects: 1) By adjusting the sample preparation method of the ratio of the sample, flux and release agent, the interference effect of the TiO2 element in the boiling chlorination bed waste residue can be effectively reduced, the accuracy of the test results of the TiO2 content in the boiling chlorination bed waste residue can be improved, and the excessive waste caused by the imbalance of material ratios due to excessive addition of raw materials in the boiling chlorination ratio process can be reduced, the efficiency of boiling chlorination in producing titanium tetrachloride can be improved, and the benefits for the enterprise can be increased; 2) the sample preparation operation is simple, the test time is short and the test accuracy is relatively high. DETAILED DESCRIPTION

[0018] To make the above-mentioned objects, features and advantages of the present invention more clearly understood, the following describes in detail the specific embodiments of the present invention. The technical features of the embodiments of the present invention may be combined with each other without conflict.

[0019] In addition, the descriptions involving "first", "second", etc. in the present invention are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features.

[0020] In the description of the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood broadly. For example, they may refer to fixed, detachable, or integral connections; mechanical connections; direct connections or indirect connections through an intermediary; and internal communication between two components. Those skilled in the art will understand the specific meanings of these terms in the present invention based on the specific circumstances.

[0021] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that a specific feature, structure, material, or characteristic described in conjunction with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, illustrative uses of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0022] Example 1

[0023] A method for determining the TiO2 content in fluidized chlorination bed waste residue comprises:

[0024] S1. Accurately weigh 0.6 g of a chlorination bed waste residue sample and 10.0 g of a fluorescent mixed flux; the fluorescent mixed flux is prepared from lithium tetraborate and lithium metaborate in a mass percentage ratio of 67% lithium tetraborate and 33% lithium metaborate; the chlorination bed waste residue sample is pretreated by the following method: the chlorination bed waste residue is dried in an oven at 125°C for 2.5 h, then cooled, crushed and ground on a vibrating grindstone for 150 s, and placed in a desiccator for later use.

[0025] S2. After the weighed chlorination bed waste residue sample and the fluorescent mixed flux are mixed evenly, the mixture is placed in a platinum-based alloy crucible, and 0.2 g of 30% lithium bromide solution is added while stirring until the mixture is evenly mixed;

[0026] S3. In a high-frequency automatic sample melting machine, melt the sample according to the preset automatic sample melting program, pour it into a mold, cool and solidify it into a glass slide. The preset melting conditions are: preheating time 175 seconds, melting temperature 900°C, melting time 350 seconds, self-cooling time 230 seconds, and air cooling time 110 seconds;

[0027] S4. Place the prepared glass slide into an X-ray fluorescence spectrometer, select the operating parameters of the X-ray fluorescence spectrometer for measurement, and automatically calculate the TiO2 content in the boiling chlorination bed waste residue. The results are shown in Table 1. The operating parameters of the X-ray fluorescence spectrometer are: the Kα line of Ti is selected as the analysis line, the peak value of 2θ is 86.153°, the crystal is LiF200, the detector is FlowCounter, the detection voltage is 50V, the detection current is 60mA, and the measurement time is 30s.

[0028] Example 2

[0029] A method for determining the TiO2 content in fluidized chlorination bed waste residue comprises:

[0030] S1. Accurately weigh 0.4 g of a chlorination bed waste residue sample and 8.0 g of a fluorescent mixed flux; the fluorescent mixed flux is prepared from lithium tetraborate and lithium metaborate in a mass percentage ratio of 67% lithium tetraborate to 33% lithium metaborate; the chlorination bed waste residue sample is pretreated by the following method: the chlorination bed waste residue is dried in an oven at 125°C for 2.5 h, then cooled, crushed and ground on a vibrating grindstone for 140 s, and placed in a desiccator for later use.

[0031] S2. After the weighed chlorination bed waste residue sample and the fluorescent mixed flux are mixed evenly, the mixture is placed in a platinum-based alloy crucible, and 0.4 g of 30% lithium bromide solution is added while stirring until the mixture is evenly mixed;

[0032] S3. In a high-frequency automatic sample melting machine, melt the sample according to the preset automatic sample melting program, pour it into a mold, cool and solidify it into a glass slide. The preset melting conditions are: preheating time 180 seconds, melting temperature 930°C, melting time 370 seconds, self-cooling time 240 seconds, and air cooling time 120 seconds;

[0033] S4. Place the prepared glass slide into an X-ray fluorescence spectrometer, select the operating parameters of the X-ray fluorescence spectrometer for measurement, and automatically calculate the TiO2 content in the boiling chlorination bed waste residue. The results are shown in Table 1. The operating parameters of the X-ray fluorescence spectrometer are: the Kα line of Ti is selected as the analysis line, the peak value of 2θ is 86.153°, the crystal is LiF200, the detector is FlowCounter, the detection voltage is 50V, the detection current is 60mA, and the measurement time is 30s.

[0034] Example 3

[0035] A method for determining the TiO2 content in fluidized chlorination bed waste residue comprises:

[0036] S1. Accurately weigh 0.4 g of a chlorination bed waste residue sample and 8.0 g of a fluorescent mixed flux; the fluorescent mixed flux is prepared from lithium tetraborate and lithium metaborate in a mass percentage ratio of 67% lithium tetraborate to 33% lithium metaborate; the chlorination bed waste residue sample is pretreated by the following method: the chlorination bed waste residue is dried in an oven at 120° C. for 2 h, then pulverized and ground on a vibrating grindstone for 120 s after cooling, and placed in a desiccator for later use.

[0037] S2. After the weighed chlorination bed waste residue sample and the fluorescent mixed flux are mixed evenly, the mixture is placed in a platinum-based alloy crucible, and 0.4 g of 30% lithium bromide solution is added while stirring until the mixture is evenly mixed;

[0038] S3. In a high-frequency automatic sample melting machine, melt the sample according to the preset automatic sample melting program, pour it into a mold, cool and solidify it into a glass slide. The preset melting conditions are: preheating time 185 seconds, melting temperature 940°C, melting time 365 seconds, self-cooling time 240 seconds, and air cooling time 125 seconds;

[0039] S4. Place the prepared glass slide into an X-ray fluorescence spectrometer, select the operating parameters of the X-ray fluorescence spectrometer for measurement, and automatically calculate the TiO2 content in the boiling chlorination bed waste residue. The results are shown in Table 1. The operating parameters of the X-ray fluorescence spectrometer are: the Kα line of Ti is selected as the analysis line, the peak value of 2θ is 86.153°, the crystal is LiF200, the detector is FlowCounter, the detection voltage is 50V, the detection current is 60mA, and the measurement time is 30s.

[0040] Example 4

[0041] A method for determining the TiO2 content in fluidized chlorination bed waste residue comprises:

[0042] S1. Accurately weigh 0.5 g of a chlorination bed waste residue sample and 9.0 g of a fluorescent mixed flux; the fluorescent mixed flux is prepared from lithium tetraborate and lithium metaborate in a mass percentage ratio of 67% lithium tetraborate to 33% lithium metaborate; the chlorination bed waste residue sample is pretreated by the following method: the chlorination bed waste residue is dried in an oven at 130° C. for 1.5 h, then cooled, crushed and ground on a vibrating grindstone for 140 s, and placed in a desiccator for later use.

[0043] S2. After the weighed chlorination bed waste residue sample and the fluorescent mixed flux are mixed evenly, the mixture is placed in a platinum-based alloy crucible, and 0.6 g of 30% lithium bromide solution is added while stirring until the mixture is evenly mixed;

[0044] S3. In a high-frequency automatic sample melting machine, melt the sample according to the preset automatic sample melting program, pour it into a mold, cool and solidify it into a glass slide. The preset melting conditions are: preheating time 190 seconds, melting temperature 950°C, melting time 390 seconds, self-cooling time 260 seconds, and air cooling time 130 seconds;

[0045] S4. Place the prepared glass slide into an X-ray fluorescence spectrometer, select the operating parameters of the X-ray fluorescence spectrometer for measurement, and automatically calculate the TiO2 content in the boiling chlorination bed waste residue. The results are shown in Table 1. The operating parameters of the X-ray fluorescence spectrometer are: the Kα line of Ti is selected as the analysis line, the peak value of 2θ is 86.153°, the crystal is LiF200, the detector is FlowCounter, the detection voltage is 50V, the detection current is 60mA, and the measurement time is 30s.

[0046] Example 5

[0047] A method for determining the TiO2 content in fluidized chlorination bed waste residue comprises:

[0048] S1. Accurately weigh 0.4 g of a chlorination bed waste residue sample and 8.0 g of a fluorescent mixed flux; the fluorescent mixed flux is prepared from lithium tetraborate and lithium metaborate, with a mass percentage ratio of 50% lithium tetraborate and 50% lithium metaborate; the chlorination bed waste residue sample is pretreated by the following method: the chlorination bed waste residue is washed with 5% HCl at a ratio of 1 g:10 ml for 30 min, dried in a 120°C oven for 1.5 h, cooled, and then crushed and ground in a vibrating grindstone for 140 s, followed by ashing in a 500°C muffle furnace for 1 h, cooled to room temperature, and placed in a desiccator for use.

[0049] S2. After the weighed chlorination bed waste residue sample and the fluorescent mixed flux are mixed evenly, the mixture is placed in a platinum-based alloy crucible, and 0.3 g of 30% LiNO3 solution is added while stirring until the mixture is evenly mixed;

[0050] S3. In a high-frequency automatic sample melting machine, the sample is melted according to a preset automatic sample melting program, poured into a mold, cooled and solidified into a glass slide. The preset melting conditions are: preheating time 190 seconds, melting temperature 1010°C, melting time 450 seconds, self-cooling time 260 seconds, and air cooling time 130 seconds;

[0051] S4. Place the prepared glass slide into an X-ray fluorescence spectrometer, select the operating parameters of the X-ray fluorescence spectrometer for measurement, and automatically calculate the TiO2 content in the boiling chlorination bed waste residue. The results are shown in Table 1. The operating parameters of the X-ray fluorescence spectrometer are: the Kα line of Ti is selected as the analysis line, the peak value of 2θ is 86.153°, the crystal is LiF200, the detector is FlowCounter, the detection voltage is 50V, the detection current is 60mA, and the measurement time is 30s.

[0052] Comparative Example 1

[0053] The same determination method as in Example 2 was used, with the only difference being that in step S2, no 30% lithium bromide solution was added, and the glass slide was directly prepared by melting.

[0054] Comparative Example 2

[0055] The same determination method as in Example 2 was used, with the only difference being that the KEC61092 standard sample (theoretical TiO2 content of 52.327%) was used instead of the chlorination bed waste residue sample.

[0056] Table 1 Measurement results of different examples

[0057] Corresponding embodiment 30%LiBr addition / g Fused film effect <![CDATA[TiO2 / %]]> Example 1 0.2 Melt hanging on the wall 50.008 Example 2 0.3 No molten material hanging on the wall 48.541 Example 3 0.4 No molten material hanging on the wall 48.114 Example 4 0.6 No molten material hanging on the wall 47.322 Example 5 0.3 No molten material hanging on the wall 49.846 Comparative Example 1 0 The phenomenon of molten material hanging on the wall occurs 50.332 Comparative Example 2 0.3 No molten material hanging on the wall 52.311

[0058] As shown in Table 1, when the boiling chlorination bed waste residue: releasing agent = 4:3, the melting preparation glass slide = can effectively improve the test accuracy of the boiling chlorination bed waste residue TiO2 content. In addition, the same sample was measured 5 times using the methods of Example 2 and Example 5, respectively. The relative errors were -3.0% and -0.4%, respectively, and the RSDs were 1.8% and 0.5%, respectively. This shows that the reproducibility of the determination method is significantly improved. The reason may be that the waste residue sample is treated by pickling and ashing to remove Cl⁻ and C, avoiding melt volatilization and XRF scattering. Using LiNO3 as a releasing agent can eliminate Br absorption interference, and the absence of Br-Kα peak is verified by XRF spectrum. The detection method of the present application can accurately detect the TiO2 content of the waste residue in the boiling chlorination furnace, reduce the waste residue discharge by about 15%, and save about 12,000 tons of rutile raw materials per year based on an annual output of 100,000 tons of titanium tetrachloride, thereby significantly reducing production costs.

[0059] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope defined by the claims.

Claims

1. A method for determining the TiO2 content in boiling chlorination bed waste residue, characterized in that: include: S1. Accurately weigh 0.4-0.6 g of chlorination bed waste residue sample and 8.0-10.0 g of fluorescent mixed flux; the fluorescent mixed flux is composed of 33-67% lithium tetraborate and 33-67% lithium metaborate; S2. After the weighed chlorination bed waste residue sample and the fluorescent mixed flux are mixed evenly, the mixture is placed in a platinum-based alloy crucible, and 0.2-0.4 g of 30% lithium bromide solution is added while stirring until the mixture is evenly mixed; S3, in a high-frequency automatic melting machine, melt the sample according to the preset automatic melting program, pour it into a mold, cool and solidify it into a glass slide; S4. Place the prepared glass slide into an X-ray fluorescence spectrometer, select the working parameters of the X-ray fluorescence spectrometer for measurement, and automatically calculate the TiO2 content in the boiling chlorination bed waste residue.

2. The method for determining the TiO2 content in the fluidized bed chlorination waste residue according to claim 1, wherein: Step S1 specifically comprises: accurately weighing 0.4 g of a chlorination bed waste residue sample and 8.0 g of a fluorescent mixed flux; the fluorescent mixed flux is composed of 67% by mass of lithium tetraborate and 33% by mass of lithium metaborate.

3. The method for determining the TiO2 content in the fluidized chlorination bed waste residue according to claim 1, wherein: The melting conditions in step S3 are: preheating time 170-190s, melting temperature 900-950°C, melting time 330-390s, self-cooling time 220-260s, and air cooling time 110-130s.

4. The method for determining the TiO2 content in the fluidized chlorination bed waste residue according to claim 3, wherein: The melting conditions in step S3 are: preheating time 175-185s, melting temperature 930-950°C, melting time 350-370s, self-cooling time 230-250s, and air cooling time 115-125s.

5. The method for determining the TiO2 content in the fluidized chlorination bed waste residue according to claim 1, wherein: The chlorination bed waste residue sample in step S1 is pretreated by the following method: the chlorination bed waste residue is dried in an oven at 120-130° C. for 1.5-2.5 h, and after cooling, it is crushed and ground in a vibrating grindstone for 120-150 s, and placed in a desiccator for use.

6. The method for determining the TiO2 content in the fluidized chlorination bed waste residue according to claim 1, wherein: The operating parameters of the X-ray fluorescence spectrometer in step S4 are: Ti Kα line is selected as the analysis line, the peak of 2θ is 86.153°, the crystal is LiF200, the detector is Flow Counter, the detection voltage is 50V, the detection current is 60mA, and the measurement time is 30s.

7. The method for determining the TiO2 content in the fluidized chlorination bed waste residue according to claim 1 or 2, characterized in that: The TiO2 content in the boiling chlorination bed waste residue ranges from 20% to 60%.