A method and system for harmless treatment of titanium tetrachloride slurry

Abstract

The present application belongs to a kind of harmless treatment method and system for titanium tetrachloride slurry, including making hot flue gas parameters according to slurry component state data and heat source medium quality data, into fluidized bed reactor as fluidizing agent and heat source.Make low-temperature water parameters, send current titanium tetrachloride slurry and hot flue gas into fluidized bed reactor according to preset proportion, control reaction condition to obtain flue gas particle mixture.Enter porous metal filter, obtain titanium tetrachloride flue gas and solid particles.Pour titanium tetrachloride flue gas into cooler, cool according to low-temperature water parameters, recover titanium tetrachloride to obtain flue gas quality data.According to particle detection result and flue gas quality data, judge whether current titanium tetrachloride slurry is treated up to standard, otherwise adjust hot flue gas parameters and low-temperature water parameters;The present application can realize continuous treatment of titanium tetrachloride slurry, greatly improve the processing efficiency, promote the resource high-value utilization of titanium tetrachloride slurry that cannot return to chlorination furnace process.

Description

Technical Field

[0001] This invention belongs to the field of harmless treatment technology, specifically a method and system for harmless treatment of titanium tetrachloride slurry. Background Technology

[0002] Titanium tetrachloride is a core raw material in the titanium industry. During its refining process, it generates slurry containing titanium tetrachloride, vanadium oxychloride, inorganic salts, semi-coke, and other components. Due to its complex composition and strong corrosiveness, this type of slurry cannot be directly returned to the chlorination process and must be treated to render it harmless before it can be disposed of.

[0003] Currently, the mainstream processing method in the industry is batch evaporation in slurry evaporators. However, with the expansion of production scale, the shortcomings of this traditional process have become increasingly apparent. On the one hand, the intermittent processing mode has high investment costs and low processing efficiency, making it difficult to adapt to the needs of large-scale continuous production. On the other hand, after adopting the mineral oil vanadium removal process, the dried tailings generated by the electrically heated autoclave evaporation are prone to spontaneous combustion during the discharge process, posing a significant safety hazard.

[0004] More critically, traditional processes lack systematic analysis of sludge characteristics, and the formulation of core process parameters such as hot flue gas and cooling media relies heavily on experience, resulting in significant arbitrariness. Due to the natural fluctuations in the chemical composition and physical state of the sludge, fixed parameters cannot achieve precise matching, leading to incomplete vaporization of titanium tetrachloride, low condensation recovery efficiency, and severe resource waste. Furthermore, parameter mismatch also causes unstable treatment effects, such as excessive chlorine residue in particulate matter and emissions of harmful substances in flue gas failing to meet environmental standards, increasing the difficulty of subsequent treatment and posing environmental compliance risks. In addition, traditional processes lack a complete closed-loop monitoring and control system, making it impossible to assess treatment effectiveness in real time and lacking targeted adjustment plans for non-compliance, further exacerbating the uncertainty of the treatment process.

[0005] Therefore, developing a method and system for the harmless treatment of titanium tetrachloride slurry has become an urgent need to address industry pain points and promote green and sustainable industrial development. Summary of the Invention

[0006] To overcome the shortcomings of existing technologies, this invention proposes a method and system for the harmless treatment of titanium tetrachloride sludge. This invention primarily addresses the problems of low efficiency and high energy consumption, imprecise process control, and unstable treatment results associated with traditional intermittent treatment processes.

[0007] The technical solution adopted by this invention to solve its technical problem is: a method for the harmless treatment of titanium tetrachloride slurry provided by this invention, comprising: Collect data on material properties, heat source medium quality, and cooling medium quality, and analyze the mud state based on the material properties to obtain mud composition state data.

[0008] Based on the mud composition and state data and the heat source medium quality data, the parameters of the hot flue gas are determined and introduced into the fluidized bed reactor as the fluidizing agent and heat source.

[0009] Based on the mud composition and cooling medium quality data, low-temperature water parameters are determined. The current titanium tetrachloride mud and hot flue gas are fed into the fluidized bed reactor in a preset ratio, and the reaction conditions are controlled to obtain a flue gas particulate mixture.

[0010] The flue gas particulate mixture is passed through a porous metal filter to separate the flue gas and particulate matter, resulting in titanium tetrachloride flue gas and solid particulate matter. The composition of the solid particulate matter is then analyzed to obtain the particulate matter detection results.

[0011] Titanium tetrachloride flue gas is passed into a cooler, and titanium tetrachloride is recovered by cooling based on low-temperature water parameters to obtain flue gas quality data.

[0012] Based on the particle detection results and flue gas quality data, determine whether the current titanium tetrachloride slurry treatment meets the standards. If so, discharge the separated flue gas and solid particles; otherwise, adjust the hot flue gas parameters and low-temperature water parameters.

[0013] The present invention provides a method for the harmless treatment of titanium tetrachloride sludge, the steps of which include analyzing the sludge composition and state data as follows: Following the principle of multi-point uniform sampling, mud samples were collected from multiple locations in the mud storage device, and then subjected to physical treatment and anti-reaction treatment to obtain treated mud samples.

[0014] Chemical composition data were obtained by analyzing the content of titanium tetrachloride, oxychloride, inorganic salts, and semi-coke in the mud treatment samples.

[0015] Physical state data were obtained by physical state testing of mud samples in terms of moisture content, viscosity, and particle size.

[0016] Chemical index detection data and physical state data are integrated to obtain mud composition state data.

[0017] This invention provides a method for the harmless treatment of titanium tetrachloride sludge, the steps of which include determining the hot flue gas parameters are as follows: Collect heat source type, calorific value, purity and combustion characteristics as heat source medium quality data, and determine core requirements based on heat, oxygen and pressure.

[0018] The minimum requirements for temperature baseline are determined by the vaporization of titanium tetrachloride and the oxidation of oxychloride trichloride, and the temperature offset is determined according to the mud composition and state data.

[0019] Based on the design pressure range of the fluidized bed reactor, and combined with the heat source medium quality data and core requirements, the temperature baseline, temperature offset, and pressure range are adjusted to obtain the hot flue gas parameters.

[0020] This invention provides a method for the harmless treatment of titanium tetrachloride sludge, the steps of which include determining low-temperature water parameters: Collect cooling medium type, purity, specific heat capacity, freezing point, and maximum allowable operating temperature range as cooling medium quality data, and formulate low-temperature requirements based on cooling load, temperature, and stability.

[0021] The water temperature baseline is set with the goal of fully condensing titanium tetrachloride. The water temperature correction baseline value is obtained by correcting the amount of titanium tetrachloride vaporization. The low temperature water flow range is calculated based on the refrigeration load.

[0022] The low-temperature water parameters are obtained by adjusting the water temperature correction benchmark value and the low-temperature water flow range based on the cooling medium quality data and the low-temperature requirements.

[0023] The present invention provides a method for the harmless treatment of titanium tetrachloride slurry, wherein the preset ratio is titanium tetrachloride slurry: hot flue gas = 1:10~50.

[0024] The reaction conditions were as follows: the reaction temperature in the fluidized bed reactor was 500±150℃, and the pressure was 0.2±0.1MPa.

[0025] This invention provides a method for the harmless treatment of titanium tetrachloride sludge, comprising the following steps for separating flue gas from particulate matter: The porous metal filter has a filtration accuracy of 2μm and is equipped with heat preservation and electric heat tracing devices.

[0026] The separation temperature is controlled at 150±10℃ and the pressure at 0.1±0.1MPa. The porous metal filter can be replaced with a cyclone separator.

[0027] The present invention provides a method for the harmless treatment of titanium tetrachloride slurry, comprising the steps of obtaining particle detection results by analyzing the composition of solid particles: Solid particulate matter was collected according to the principles of continuous sampling and batch retention. Multiple parallel samples were obtained by labeling the batch number, sampling time and corresponding mud treatment conditions.

[0028] Each parallel sample was preprocessed, and the results were obtained by detecting the major elements, impurity elements, and harmlessness indicators.

[0029] Calculate the relative standard deviation of the detection results of each indicator for a preset number of parallel samples, perform consistency verification, and determine whether it exceeds the preset allowable range. If it does, re-detect the corresponding indicator; otherwise, output the particle detection result.

[0030] The present invention provides a method for the harmless treatment of titanium tetrachloride sludge, the steps of which include obtaining flue gas quality data: The cooling system is started according to the low-temperature water parameters to stabilize the circulation of low-temperature water in the cooler. Titanium tetrachloride flue gas is introduced into the cooler at a preset flow rate, and the initial parameters of the flue gas are recorded.

[0031] A multi-point timed sampling method was adopted to collect exhaust gas samples at the sampling locations according to preset requirements, and to record the exhaust gas batch number, exhaust gas sampling time and corresponding low-temperature water parameters.

[0032] The flue gas detection results were obtained by detecting the residual concentration of titanium tetrachloride, the concentration of chlorine-containing impurities, the temperature and pressure of the exhaust gas, and the content of particulate matter in the exhaust gas.

[0033] The flue gas quality data is obtained by combining the amount of liquid titanium tetrachloride recovered from condensation and the particle detection results to correct the flue gas detection results.

[0034] This invention provides a method for the harmless treatment of titanium tetrachloride sludge, the steps of which include determining whether the current titanium tetrachloride sludge treatment meets the standards are as follows: A dual compliance standard for particulate matter and flue gas is established based on the harmless particulate matter standard and the environmental protection recovery standard for flue gas, serving as the judgment benchmark.

[0035] The particle detection results and flue gas quality data are compared with the judgment criteria, and the judgment results are recorded.

[0036] Different treatment paths are implemented based on the judgment results, which are divided into compliance treatment and non-compliance treatment. The compliance treatment is used to treat solid particulate matter and flue gas that has been cooled and recovered.

[0037] Based on the non-compliance handling, control measures and problem identification are carried out. Based on the problem identification, the cause and type of non-compliance are analyzed, and corresponding adjustment measures are formulated for hot flue gas parameters and low temperature water parameters.

[0038] This invention provides a system for the harmless treatment of titanium tetrachloride sludge, comprising: The composition state analysis module is used to collect data on material characteristic factors, heat source medium quality data, and cooling medium quality data, and to analyze the mud state based on material characteristic factors to obtain mud composition state data.

[0039] The heat source parameter setting module is used to set the parameters of hot flue gas based on the mud composition state data and the heat source medium quality data, and then introduce it into the fluidized bed reactor as a fluidizing agent and heat source.

[0040] The reaction condition control module is used to formulate low-temperature water parameters based on the mud composition state data and cooling medium quality data, and to feed the current titanium tetrachloride mud and hot flue gas into the fluidized bed reactor in a preset ratio, thereby controlling the reaction conditions to obtain a flue gas particulate mixture.

[0041] The gas-solid separation detection module is used to pass the flue gas particulate mixture into a porous metal filter to separate the flue gas and particulate matter into titanium tetrachloride flue gas and solid particulate matter. The composition of the solid particulate matter is then analyzed to obtain the particle detection results.

[0042] The flue gas cooling and recovery module is used to pass titanium tetrachloride flue gas into a cooler, and to recover titanium tetrachloride by cooling based on low-temperature water parameters to obtain flue gas quality data.

[0043] The compliance determination and adjustment module is used to determine whether the current titanium tetrachloride slurry treatment meets the standards based on particle detection results and flue gas quality data. If it does, the separated flue gas and solid particles are discharged; otherwise, the hot flue gas parameters and low-temperature water parameters are adjusted.

[0044] The beneficial effects of this invention are as follows: 1. This invention achieves a high recovery rate of titanium tetrachloride by optimizing condensation parameters and conditions, transforming hazardous waste into usable chemical raw materials, creating significant economic value, and aligning with the concept of a circular economy. It can automatically adapt to titanium tetrachloride slurries of different sources and compositions, and achieve process self-optimization through data analysis and feedback adjustments, significantly improving the intelligence level and operational stability of the production line, reducing operational difficulty and reliance on personnel experience. Through strict control of dual compliance standards and dual detection and control of particulate matter and flue gas at the end, it ensures that the final emissions of solid waste and exhaust gas meet environmental protection requirements, effectively preventing secondary pollution and demonstrating outstanding environmental benefits. It achieves safe and efficient recovery of high-value resources, improving process adaptability and intelligence. Attached Figure Description

[0045] The invention will now be further described with reference to the accompanying drawings.

[0046] Figure 1 This is a schematic flowchart of a method for harmless treatment of titanium tetrachloride sludge provided in an embodiment of the present invention; Figure 2 This is a schematic diagram of a system for the harmless treatment of titanium tetrachloride sludge provided in an embodiment of the present invention; Figure 3 This is a schematic diagram of a system for the harmless treatment of titanium tetrachloride slurry provided in an embodiment of the present invention. Detailed Implementation

[0047] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0048] like Figures 1 to 3 As shown in the embodiment of the present invention, a method for the harmless treatment of titanium tetrachloride slurry includes: Collect data on material properties, heat source medium quality, and cooling medium quality, and analyze the mud state based on the material properties to obtain mud composition state data.

[0049] The steps for analyzing and obtaining mud composition and state data include: Following the principle of multi-point uniform sampling, mud samples were collected from multiple locations in the mud storage device, and then subjected to physical treatment and anti-reaction treatment to obtain treated mud samples.

[0050] Physical processing: The collected mud sample was quickly and thoroughly mixed and divided into two portions. One portion was kept in its original state for testing moisture content, viscosity, and particle size. The other portion was subjected to vacuum freeze-drying to remove volatile components, resulting in a solid residue sample for testing non-volatile components such as inorganic salts, semi-coke, and vanadates.

[0051] Anti-reaction treatment: The sampling and pretreatment process is carried out in a closed environment to prevent titanium tetrachloride and vanadium trichloride in the mud from reacting with moisture in the air to generate corrosive substances, while also preventing semi-coke oxidation, ensuring that the test results truly reflect the original state of the mud.

[0052] Chemical composition data were obtained by analyzing the content of titanium tetrachloride, oxychloride, inorganic salts, and semi-coke in the mud treatment samples.

[0053] Titanium tetrachloride (TiCl4) content: Gas chromatography (GC) was used to inject the original mud sample into the chromatograph with nitrogen as the carrier gas. The mass fraction of TiCl4 was quantitatively analyzed by standard curve method to ensure the detection accuracy is ≤±0.5% and to obtain quantitative data of "TiCl4 content ≥90%".

[0054] Vanadium oxychloride (VOCl3) content: Inductively coupled plasma optical emission spectrometry (ICP-OES) was used to digest the pretreated solid residue sample, detect the vanadium content, and then convert it into the mass fraction of VOCl3 through stoichiometry to obtain a specific value of "VOCl3 content 2% to 4%".

[0055] Inorganic salt (AlCl3, FeCl3, etc.) content: Ion chromatography was used to detect the Cl content in the digestion solution of the solid residue. - Al 3 + Fe 3+The plasma concentration is used to calculate the total mass fraction of inorganic salts based on the ion ratio, with the goal of obtaining data showing an "inorganic salt content of 2% to 3%".

[0056] Semi-coke content: The mass fraction of carbon in the solid residue is directly detected using a high-frequency infrared carbon-sulfur analyzer, which is the semi-coke content. The target is to obtain a specific value of "semi-coke content of 2% to 3%".

[0057] Physical state data were obtained by physical state testing of mud samples in terms of moisture content, viscosity, and particle size.

[0058] Moisture content: The gravimetric method is used. A certain mass of the original mud sample (denoted as m1) is weighed and dried at a constant temperature of 105℃ to a constant weight (denoted as m2). The moisture content is calculated using the formula "moisture content = (m1-m2) / m1×100%". The test results are required to be accurate to ±0.1%.

[0059] Viscosity: Using a rotational viscometer, at 25℃, select an appropriate rotor speed (adjusted according to the mud viscosity, usually 50-200 r / min) to measure the dynamic viscosity of the mud, expressed in mPa·s. Record the viscosity changes at different shear rates to determine the mud fluidity.

[0060] Particle size: A laser particle size analyzer was used to dilute the original mud sample and inject it into the instrument to detect the particle size distribution (D10, D50, D90) of the solid particles, to determine whether there are large particle impurities (particle size > 100μm), and to provide data support for the selection of fluidized bed distribution plates and anti-clogging design.

[0061] Chemical index detection data and physical state data are integrated to obtain mud composition state data.

[0062] Nitrogen gas is used to purge the system, and then the liquefied petroleum gas burner is turned on to preheat the system. Based on the mud composition and state data and the heat source medium quality data, the hot flue gas parameters are determined and introduced into the fluidized bed reactor as the fluidizing agent and heat source.

[0063] The steps for determining hot flue gas parameters include: Collect heat source type, calorific value, purity and combustion characteristics as heat source medium quality data, and determine core requirements based on heat, oxygen and pressure.

[0064] The heat requirement includes the total heat consumption to meet the requirements of "mud moisture evaporation + TiCl4 vaporization + VOCl3 oxidation + semi-coke combustion auxiliary heating". Among them, TiCl4 vaporization and VOCl3 oxidation are fixed heat requirements, while moisture content and semi-coke content are variable influencing factors.

[0065] Oxygen requirements include: matching the stoichiometric ratio of the VOCl3 oxidation reaction and the semi-coke combustion reaction to avoid incomplete reactions due to insufficient oxygen or increased energy consumption due to excessive oxygen.

[0066] Pressure requirements include: meeting the fluidization state of the fluidized bed (overcoming mud resistance + maintaining reactor pressure stability), which is related to mud viscosity and reactor distribution plate opening ratio.

[0067] The minimum requirements for temperature baseline are determined by the vaporization of titanium tetrachloride and the oxidation of oxychloride trichloride, and the temperature offset is determined according to the mud composition and state data.

[0068] The steps for determining the temperature offset may include: Moisture content correction: For every 1% increase in moisture content, the hot flue gas temperature needs to be increased by 10-15℃. If the moisture content is ≤1%, no additional heating is required. If the moisture content is ≥5%, the maximum heating range is 15℃.

[0069] Semi-coke content correction: For every 0.5% increase in semi-coke content, the temperature of the hot flue gas can be reduced by 5-8℃. If the semi-coke content is ≤2%, the temperature will not be reduced. If the semi-coke content is ≥3%, the temperature reduction will be the upper limit of 8℃.

[0070] Preliminary calculation of the final temperature range: base temperature ± offset, and it must fall within the core process range (600±100℃). For example: if the mud moisture content is 1.2%, it means a temperature increase of 12℃, and the semi-coke content is 3.1%, it means a temperature decrease of 8℃. Then the initial calculated temperature = 500 + 12 - 8 = 504℃. After correction, it is included in the 600±100℃ range, and is tentatively set at 550-650℃.

[0071] Based on the design pressure range of the fluidized bed reactor, and combined with the heat source medium quality data and core requirements, the temperature baseline, temperature offset, and pressure range are adjusted to obtain the hot flue gas parameters.

[0072] The flue gas temperature is controlled at 600±100℃ and the pressure is 0.2±0.1MPa. Its characteristic equipment is a hot air furnace.

[0073] The steps for adjusting based on the heat source medium quality data may include: High-calorific-value clean heat sources: high combustion efficiency and few impurities, suitable for scenarios with high requirements for temperature stability, can be directly set according to the initial calculated temperature and pressure without additional adjustments.

[0074] Solid heat source: The calorific value fluctuates greatly and the combustion rate is slow. It is necessary to appropriately increase the temperature of the hot flue gas by 5-10℃, while ensuring that the oxygen content is at the upper limit to promote the complete combustion of petroleum coke.

[0075] Electric heating: fast heating rate and high temperature control accuracy, suitable for small-scale or impurity-sensitive scenarios. The temperature of hot flue gas can be accurately set according to the initial calculation value, and the pressure is maintained within the reference range without considering the oxygen content.

[0076] When the system temperature reaches approximately 500℃, titanium tetrachloride slurry is added to the fluidized bed. Since the slurry contains semi-coke, the coke powder in the slurry reacts with oxygen in the compressed air as follows:

[0077] If the fluidized bed temperature is too high, the liquefied gas supply needs to be gradually reduced until it is shut off. At the same time, volatile substances such as titanium tetrachloride in the slurry change from liquid to gas under the influence of temperature, thereby achieving separation from other solids and becoming gaseous and dry particles. Meanwhile, easily oxidizable substances such as vanadium trichloride in vanadium-containing slurry react with excess oxygen in the flue gas to generate stable oxide particles.

[0078] Based on the mud composition and cooling medium quality data, low-temperature water parameters are determined. The current titanium tetrachloride mud and hot flue gas are fed into the fluidized bed reactor in a preset ratio, and the reaction conditions are controlled to obtain a flue gas particulate mixture.

[0079] The steps for determining low-temperature water parameters include: Collect cooling medium type, purity, specific heat capacity, freezing point, and maximum allowable operating temperature range as cooling medium quality data, and formulate low-temperature requirements based on cooling load, temperature, and stability.

[0080] Cooling load requirement: The total heat removal requirement of titanium tetrachloride flue gas condensation must be met. The latent heat of condensation of TiCl4 is a fixed value. The cooling load is positively correlated with the vaporization rate of TiCl4.

[0081] Temperature requirements: The temperature of TiCl4 flue gas needs to be reduced to ≤-5℃, and the temperature of the low-temperature water needs to be ≤-20℃.

[0082] Stability requirements: The low-temperature water must be free from freezing and corrosive, and the flow rate must match the cooling load to avoid insufficient local heat transfer.

[0083] The water temperature baseline is set with the goal of fully condensing titanium tetrachloride. The water temperature correction baseline value is obtained by correcting the amount of titanium tetrachloride vaporization. The low temperature water flow range is calculated based on the refrigeration load.

[0084] The formula for calculating the range of low-temperature water flow based on the cooling load is expressed as follows:

[0085]

[0086] In the formula, It is a cooling load. It is the specific heat capacity of the cooling medium. It is a low-temperature water flow rate. It refers to the temperature difference between the inlet and outlet of the low-temperature water.

[0087] The low-temperature water parameters are obtained by adjusting the water temperature correction benchmark value and the low-temperature water flow range based on the cooling medium quality data and the low-temperature requirements.

[0088] The cooling medium is an aqueous solution of ethylene glycol: If the purity of ethylene glycol is ≥99%, set the initial concentration. If the purity is ≤95%, the concentration needs to be increased by 3-5% to compensate for the increase in freezing point caused by impurities.

[0089] If the moisture content in the medium exceeds the standard, the freezing point needs to be recalculated, and the ethylene glycol concentration should be increased accordingly to prevent freezing.

[0090] The cooling medium is deionized water: it can be used directly if the purity is ≥99% or the conductivity is ≤10μS / cm, and the temperature should be set according to the initial value. If the purity is insufficient, the temperature should be avoided from being lower than -25℃, and if necessary, it should be replaced with an ethylene glycol aqueous solution.

[0091] If the cooling medium is another low-temperature medium, such as propylene glycol aqueous solution: adjust the parameters according to its specific heat capacity and freezing point characteristics. For example, the specific heat capacity of propylene glycol aqueous solution is lower than that of ethylene glycol, so the flow rate needs to be increased by 10-15%. At the same temperature, the concentration of propylene glycol needs to be 8-10% higher than that of ethylene glycol to ensure that the freezing point meets the standard.

[0092] Considering the actual cooling capacity of the cooling medium, if the cooling power of the cooler is insufficient, the temperature of the low-temperature water needs to be reduced by 3-5℃, such as from -25℃ to -28℃, to increase the heat transfer temperature difference and make up for the cooling power shortfall.

[0093] The preset ratio is titanium tetrachloride slurry: hot flue gas = 1:10~50.

[0094] The reaction conditions were as follows: the reaction temperature in the fluidized bed reactor was 500±150℃, and the pressure was 0.2±0.1MPa.

[0095] The flue gas particulate mixture is passed through a porous metal filter to separate the flue gas and particulate matter, resulting in titanium tetrachloride flue gas and solid particulate matter. The composition of the solid particulate matter is then analyzed to obtain the particulate matter detection results.

[0096] The steps to separate flue gas from particulate matter include: The porous metal filter has a filtration accuracy of 2μm and is equipped with heat preservation and electric heat tracing devices.

[0097] The separation temperature is controlled at 150±10℃ and the pressure at 0.1±0.1MPa. The porous metal filter can be replaced with a cyclone separator.

[0098] The mixture of flue gas, gaseous titanium tetrachloride, and particulate matter after the reaction enters a filter equipped with a metal filter. Titanium tetrachloride, tail gas, and other gaseous substances enter a recovery and purification device for further recovery and purification. Particulate matter is periodically discharged from the bottom of the filter, thereby achieving the separation of solids and titanium tetrachloride in the refined slurry.

[0099] The steps for obtaining particle detection results by analyzing the composition of solid particulate matter include: Solid particulate matter was collected according to the principles of continuous sampling and batch retention. Multiple parallel samples were obtained by labeling the batch number, sampling time and corresponding mud treatment conditions.

[0100] Each parallel sample was preprocessed, and the results were obtained by detecting the major elements, impurity elements, and harmlessness indicators.

[0101] The pretreatment steps include: placing each parallel sample separately into an agate mortar and grinding it until the particle size is ≤200 mesh to ensure sample homogeneity and avoid detection deviations caused by large particles. The ground samples are then placed in a vacuum drying oven and dried at 105℃ and a vacuum degree ≤10Pa for 2 hours to remove adsorbed water and residual trace volatile components. After cooling to room temperature, each parallel sample is divided into three portions: one portion for major element detection (vanadium, titanium, carbon, chlorine), one portion for impurity element detection (iron, aluminum, etc.), and one portion as a reserve sample.

[0102] Vanadium (V) content detection: Inductively coupled plasma optical emission spectrometry (ICP-OES) was used. ① Sample digestion: Weigh 0.1g of the pretreated sample and place it in a polytetrafluoroethylene digestion vessel. Add 5mL of nitric acid, 2mL of hydrofluoric acid, and 1mL of perchloric acid. Place the vessel in a microwave digester and digest according to the program of "heating to 180℃ → holding for 30min". After cooling, transfer the digested sample to a 50mL volumetric flask and dilute to the mark with deionized water. ② Standard curve plotting: Prepare a series of vanadium standard solutions ranging from 0.1-100μg / mL, import them into the ICP-OES instrument, and plot the standard curve. ③ Sample detection: Import the digested solution into the instrument and measure the intensity of the characteristic spectral lines of vanadium. Calculate the mass fraction of vanadium using the standard curve. The detection accuracy is ≤±0.5%.

[0103] Titanium (Ti) content determination: ICP-OES method is used. ① The same digestion solution used for vanadium detection is employed, requiring no additional treatment. ② A series of titanium standard solutions ranging from 0.5 to 200 μg / mL are prepared, and a standard curve is plotted. ③ The intensity of characteristic spectral lines of titanium is measured, and the mass fraction of titanium is calculated.

[0104] Carbon (C) content detection: A high-frequency infrared carbon-sulfur analyzer was used. ① 0.05g of pretreated sample was weighed and placed in a special ceramic crucible. An appropriate amount of flux was added to prevent incomplete combustion of the sample. ② The crucible was placed in the analyzer, oxygen was introduced, and the sample was burned in a high-frequency induction furnace. The carbon element was converted into carbon dioxide. The carbon dioxide concentration was detected by an infrared detector, and the mass fraction of carbon was calculated. The detection accuracy was ≤ ±0.3%.

[0105] Chlorine (Cl) content detection: Ion chromatography (IC) was used. ① Sample extraction: Weigh 0.2g of pretreated sample, place it in a centrifuge tube, add 20mL of deionized water, and extract ultrasonically for 30min in an ultrasonic cleaner. Then centrifuge at 8000r / min for 15min and collect the supernatant. ② Sample purification: Filter the supernatant through a 0.45μm organic phase filter membrane to remove suspended impurities and avoid clogging the chromatographic column. ③ Standard curve preparation: Prepare a series of chlorine standard solutions ranging from 1-100μg / mL, import them into the ion chromatograph, and plot the standard curve. ④ Sample detection: Import the purified supernatant into the instrument, determine the chloride ion retention time and peak area, and calculate the chlorine mass fraction. The detection accuracy is ≤±0.4%.

[0106] Impurity element detection method: ICP-OES was used, employing the same digestion solution used for vanadium and titanium detection to simultaneously determine the content of elements such as iron (Fe), aluminum (Al), and calcium (Ca). A series of standard solutions for the corresponding elements were prepared (iron: 0.1-50 μg / mL, aluminum: 0.1-50 μg / mL), and standard curves were plotted. The mass fraction of each impurity element was calculated by converting the intensity of characteristic spectral lines to determine the degree of particulate matter contamination.

[0107] Methods for detecting harmless indicators may include: Detection of water-soluble chlorine content: using the gravimetric method, supplemented by ion chromatography results, to verify the migration of chlorine. ① Weigh 1g of the pretreated sample, add 50mL of deionized water, stir for 30min, filter, and collect the filtrate. ② Place the filtrate in a constant-weight evaporating dish, evaporate to dryness in a water bath, and then dry in a 105℃ drying oven to constant weight. Calculate the mass fraction of water-soluble chlorine.

[0108] Vanadium oxide stability verification: X-ray diffraction (XRD) was used. ① A small amount of pretreated sample was taken, pressed into a thin slice, and placed in the XRD instrument. The scanning range was 2θ = 10°-80°. ② The XRD pattern was compared with the standard spectral library to confirm whether vanadium exists in a stable oxide form, avoiding the presence of unoxidized vanadium oxychloride residue.

[0109] Calculate the relative standard deviation of the detection results of each indicator for a preset number of parallel samples, perform consistency verification, and determine whether it exceeds the preset allowable range. If it does, re-detect the corresponding indicator; otherwise, output the particle detection result.

[0110] The results of particulate matter testing may include batch information, testing items and methods, specific content of each component, and determination of harmlessness.

[0111] Titanium tetrachloride flue gas is passed into a cooler, and titanium tetrachloride is recovered by cooling based on low-temperature water parameters to obtain flue gas quality data.

[0112] The steps to obtain flue gas quality data include: The cooling system is started according to the low-temperature water parameters to stabilize the circulation of low-temperature water in the cooler. Titanium tetrachloride flue gas is introduced into the cooler at a preset flow rate, and the initial parameters of the flue gas are recorded.

[0113] A multi-point timed sampling method was adopted to collect exhaust gas samples at the sampling locations according to preset requirements, and to record the exhaust gas batch number, exhaust gas sampling time and corresponding low-temperature water parameters.

[0114] The flue gas detection results were obtained by detecting the residual concentration of titanium tetrachloride, the concentration of chlorine-containing impurities, the temperature and pressure of the exhaust gas, and the content of particulate matter in the exhaust gas.

[0115] Detection of titanium tetrachloride residual concentration: Detection method: gas chromatography, equipped with an electron capture detector (ECD).

[0116] Sample preparation: The tail gas sample in the sealed sampling container was quantitatively injected into the chromatograph using a syringe, with nitrogen as the carrier gas and the column temperature set to 80℃.

[0117] Standard curve preparation: Prepare 0.01~10 mg / m³ 3 The TiCl4 standard gas series was imported into the chromatograph to plot the standard curve.

[0118] Results Calculation: By comparing the sample peak area with the standard curve, the residual concentration of TiCl4 in the exhaust gas was calculated, with a detection accuracy of ≤ ±0.005 mg / m³. 3 .

[0119] Detection of chlorine impurity concentration: Detection method: Ion chromatography (IC).

[0120] Sample preparation: Pass the exhaust gas sample into an absorption bottle containing 50 mL of deionized water to fully absorb the HCl in the exhaust gas for ≥15 min. Then filter the absorption solution through a 0.45 μm filter membrane to remove suspended impurities.

[0121] Standard curve preparation: Prepare 0.1~50 μg / mL Cl - Import the standard solution series into the ion chromatograph and plot the standard curve.

[0122] Result calculation: Through the Cl in the absorption liquid - The concentration, combined with the exhaust gas sampling volume, is used to calculate the total concentration of chlorine impurities in the exhaust gas.

[0123] Exhaust gas temperature and pressure detection: Data is read directly from the online temperature sensor and pressure transmitter on the cooler outlet pipe. Each batch is recorded 3 times, and the average value is taken as the final result. The temperature accuracy is ±0.1℃ and the pressure accuracy is ±0.005MPa.

[0124] Detection of particulate matter content in exhaust gas: Detection method: Gravimetric method.

[0125] Sample processing: A constant-weight glass fiber filter membrane is installed on a dedicated sampling device, and a quantitative amount of exhaust gas is passed through the filter membrane to capture particulate matter.

[0126] Results Calculation: The sampled filter membrane was dried in a 105℃ drying oven to constant weight. The particulate matter content was calculated by the mass difference of the filter membrane before and after drying and the exhaust gas volume. The detection accuracy was ≤ ±0.01 mg / m³. 3 .

[0127] The flue gas quality data is obtained by combining the amount of liquid titanium tetrachloride recovered from condensation and the particle detection results to correct the flue gas detection results.

[0128] Flue gas quality data can include cooling recovery conditions, specific values ​​of each quality indicator, condensation recovery efficiency (TiCl4 recovery rate = recovery amount ÷ total vaporization amount × 100%), and exhaust gas compliance status.

[0129] Based on the particle detection results and flue gas quality data, determine whether the current titanium tetrachloride slurry treatment meets the standards. If so, discharge the separated flue gas and solid particles; otherwise, adjust the hot flue gas parameters and low-temperature water parameters.

[0130] The steps to determine whether the current titanium tetrachloride sludge treatment meets the standards include: A dual compliance standard for particulate matter and flue gas is established based on the harmless particulate matter standard and the environmental protection recovery standard for flue gas, serving as the judgment benchmark.

[0131] The particle detection results and flue gas quality data are compared with the judgment criteria, and the judgment results are recorded.

[0132] Different treatment paths are implemented based on the judgment results, which are divided into compliance treatment and non-compliance treatment. The compliance treatment is used to treat solid particulate matter and flue gas that has been cooled and recovered.

[0133] Based on the non-compliance handling, control measures and problem identification are carried out. Based on the problem identification, the cause and type of non-compliance are analyzed, and corresponding adjustment measures are formulated for hot flue gas parameters and low temperature water parameters.

[0134] Adjustment Measures Comparison Table:

[0135] Based on the same general inventive concept, this invention also protects a system for the harmless treatment of titanium tetrachloride slurry, comprising: The composition state analysis module is used to collect data on material characteristic factors, heat source medium quality data, and cooling medium quality data, and to analyze the mud state based on material characteristic factors to obtain mud composition state data.

[0136] The heat source parameter setting module is used to set the parameters of hot flue gas based on the mud composition state data and the heat source medium quality data, and then introduce it into the fluidized bed reactor as a fluidizing agent and heat source.

[0137] The reaction condition control module is used to formulate low-temperature water parameters based on the mud composition state data and cooling medium quality data, and to feed the current titanium tetrachloride mud and hot flue gas into the fluidized bed reactor in a preset ratio, thereby controlling the reaction conditions to obtain a flue gas particulate mixture.

[0138] The gas-solid separation detection module is used to pass the flue gas particulate mixture into a porous metal filter to separate the flue gas and particulate matter into titanium tetrachloride flue gas and solid particulate matter. The composition of the solid particulate matter is then analyzed to obtain the particle detection results.

[0139] The flue gas cooling and recovery module is used to pass titanium tetrachloride flue gas into a cooler, and to recover titanium tetrachloride by cooling based on low-temperature water parameters to obtain flue gas quality data.

[0140] The compliance determination and adjustment module is used to determine whether the current titanium tetrachloride slurry treatment meets the standards based on particle detection results and flue gas quality data. If it does, the separated flue gas and solid particles are discharged; otherwise, the hot flue gas parameters and low-temperature water parameters are adjusted.

[0141] In summary, this embodiment provides a method and system for the harmless treatment of titanium tetrachloride slurry, achieving continuous treatment without batch interruptions or repeated equipment disassembly and assembly, significantly improving processing efficiency, adapting to large-scale production scenarios, and solving the inefficiency problem of traditional intermittent processes. It precisely matches the parameters of hot flue gas and low-temperature water with the characteristics of the slurry and the quality of the medium, ensuring a significant increase in the vaporization rate and condensation recovery rate of titanium tetrachloride, reducing resource waste, and avoiding equipment failures caused by parameter imbalances. Furthermore, the porous metal filter can be replaced with a cyclone separator, and multiple types of heat sources and cooling media can be selected. Parameters can be dynamically adjusted according to the slurry state and medium quality to adapt to the treatment needs of titanium tetrachloride slurry with different compositions and scales. This promotes the high-value resource utilization of titanium tetrachloride slurry that cannot be returned to the chlorination furnace process.

[0142] Through the above description of the embodiments, those skilled in the art can clearly understand that each embodiment can be implemented by means of software plus necessary general-purpose hardware platforms, and of course, it can also be implemented by hardware. Based on this understanding, the above technical solutions, in essence or the part that contributes to the prior art, can be embodied in the form of a software product. This computer software product can be stored in a computer-readable storage medium, such as ROM / RAM, magnetic disk, optical disk, etc., and includes several instructions to cause a computer device (which may be a personal computer, server, or network device, etc.) to execute the methods described in the various embodiments or some parts of the embodiments.

[0143] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for the harmless treatment of titanium tetrachloride slurry, comprising: characterized in that: Collect data on material characteristics, heat source medium quality, and cooling medium quality, and analyze the mud state based on the material characteristics to obtain mud composition state data; Based on the mud composition and state data and the heat source medium quality data, the hot flue gas parameters are determined and introduced into the fluidized bed reactor as a fluidizing agent and heat source. Based on the mud composition state data and the cooling medium quality data, low-temperature water parameters are determined, and the current titanium tetrachloride mud and hot flue gas are fed into the fluidized bed reactor in a preset ratio. The reaction conditions are controlled to obtain a flue gas particulate mixture. The flue gas particulate mixture is passed through a porous metal filter to separate the flue gas and particulate matter, resulting in titanium tetrachloride flue gas and solid particulate matter. The solid particulate matter is then subjected to component analysis to obtain particulate matter analysis results. The titanium tetrachloride flue gas is passed into a cooler, and titanium tetrachloride is recovered by cooling according to the low temperature water parameters to obtain flue gas quality data. Based on the particle detection results and the flue gas quality data, determine whether the current titanium tetrachloride slurry treatment meets the standards. If yes, discharge the separated flue gas and solid particles; otherwise, adjust the hot flue gas parameters and low-temperature water parameters.

2. The method for harmless treatment of titanium tetrachloride slurry according to claim 1, characterized in that: The steps for analyzing and obtaining the mud composition and state data include: Following the principle of multi-point uniform sampling, mud samples were collected from multiple locations in the mud storage device, and then physical and anti-reaction treatments were performed to obtain mud-treated samples. Chemical index detection data were obtained by detecting the chemical composition ratio of titanium tetrachloride, oxychloride, inorganic salts and semi-coke in the mud treatment sample. Physical state data of the mud treatment sample were obtained by physical state testing in terms of moisture content, viscosity and particle size. The chemical index detection data and the physical state data are integrated to obtain the mud composition state data.

3. The method for harmless treatment of titanium tetrachloride slurry according to claim 1, characterized in that: The steps for determining the hot flue gas parameters include: Collect heat source type, calorific value, purity and combustion characteristics as the quality data of the heat source medium, and determine the core requirements based on heat, oxygen and pressure; The minimum requirements for titanium tetrachloride vaporization and oxychloride oxidation are determined, and the temperature offset is determined according to the mud composition state data. Based on the design pressure range of the fluidized bed reactor, and combined with the quality data of the heat source medium and the core requirements, the temperature baseline, the temperature offset, and the pressure range are adjusted to obtain the hot flue gas parameters.

4. The method for harmless treatment of titanium tetrachloride slurry according to claim 1, characterized in that: The steps for determining the low-temperature water parameters include: Collect the type, purity, specific heat capacity, freezing point, and maximum allowable operating temperature range of the cooling medium as the quality data of the cooling medium, and formulate low-temperature requirements based on refrigeration load, temperature, and stability; The water temperature baseline is set with the goal of fully condensing titanium tetrachloride. The water temperature correction baseline value is obtained by correcting the amount of titanium tetrachloride vaporization. The low temperature water flow range is calculated based on the refrigeration load. The low-temperature water parameters are obtained by adjusting the water temperature correction benchmark value and the low-temperature water flow range based on the cooling medium quality data and the low-temperature requirements.

5. The method for harmless treatment of titanium tetrachloride slurry according to claim 1, characterized in that: The preset ratio is titanium tetrachloride slurry: hot flue gas = 1:10-50; The reaction conditions are as follows: the reaction temperature of the fluidized bed reactor is 500±150℃, and the pressure is 0.2±0.1MPa.

6. The method for harmless treatment of titanium tetrachloride slurry according to claim 1, characterized in that: The steps to separate flue gas from particulate matter include: The porous metal filter has a filtration accuracy of 2μm and is equipped with heat preservation and electric heat tracing devices. The separation temperature is controlled at 150±10℃ and the pressure at 0.1±0.1MPa. The porous metal filter can be replaced with a cyclone separator.

7. The method for harmless treatment of titanium tetrachloride slurry according to claim 1, characterized in that: The steps for obtaining particle detection results by performing component analysis on the solid particulate matter include: The solid particulate matter was collected according to the principles of continuous sampling and batch retention, and multiple parallel samples were obtained by labeling the batch number, sampling time and corresponding mud treatment conditions. Each parallel sample was preprocessed and tested according to major elements, impurity elements, and harmlessness indicators to obtain the indicator test results; Calculate the relative standard deviation of the detection results of each indicator for a preset number of parallel samples, perform consistency verification, and determine whether it exceeds the preset allowable range. If it does, re-detect the corresponding indicator; otherwise, output the particle detection result.

8. The method for harmless treatment of titanium tetrachloride slurry according to claim 1, characterized in that: The steps for obtaining the flue gas quality data include: The cooling system is started according to the low-temperature water parameters, so that the low-temperature water circulates stably in the cooler. The titanium tetrachloride flue gas is introduced into the cooler at a preset flow rate, and the initial parameters of the flue gas are recorded. A multi-point timed sampling method was adopted to collect exhaust gas samples at the sampling locations according to preset requirements, and to record the exhaust gas batch number, exhaust gas sampling time and corresponding low-temperature water parameters. The flue gas detection results were obtained by detecting the residual concentration of titanium tetrachloride, the concentration of chlorine-containing impurities, the temperature and pressure of the exhaust gas, and the content of particulate matter in the exhaust gas. The flue gas quality data is obtained by correcting the flue gas detection results by combining the amount of liquid titanium tetrachloride recovered by condensation and the particle detection results.

9. The method for harmless treatment of titanium tetrachloride slurry according to claim 1, characterized in that: The steps to determine whether the current titanium tetrachloride sludge treatment meets the standards include: Establish dual compliance standards for particulate matter and flue gas based on particulate harmlessness standards and flue gas environmental protection recovery standards, and use them as the judgment benchmark; The particle detection results and the flue gas quality data are compared with the judgment criteria, and the judgment results are recorded. Different treatment paths are executed according to the judgment result, which are divided into compliance treatment and non-compliance treatment. The solid particulate matter and the cooled and recovered flue gas are treated according to the compliance treatment. Based on the non-compliance handling, control and problem identification are carried out, and the cause type of non-compliance is analyzed based on the problem identification. Corresponding adjustment measures are formulated for the hot flue gas parameters and the low temperature water parameters.

10. A system for the harmless treatment of titanium tetrachloride slurry, wherein the system is applied to a method for the harmless treatment of titanium tetrachloride slurry as described in any one of claims 1 to 9, characterized in that, The system includes: The composition state analysis module is used to collect data on material characteristic factors, heat source medium quality data, and cooling medium quality data, and to analyze the mud state based on the material characteristic factors to obtain mud composition state data. The heat source parameter setting module is used to set the hot flue gas parameters based on the mud composition state data and the heat source medium quality data, and introduce them into the fluidized bed reactor as a fluidizing agent and heat source. The reaction condition control module is used to formulate low-temperature water parameters based on the mud composition state data and the cooling medium quality data, and to feed the current titanium tetrachloride mud and hot flue gas into the fluidized bed reactor in a preset ratio, and control the reaction conditions to obtain a flue gas particulate mixture. The gas-solid separation detection module is used to pass the flue gas particulate mixture into a porous metal filter to separate the flue gas and particulate matter into titanium tetrachloride flue gas and solid particulate matter, and to perform component detection on the solid particulate matter to obtain the particle detection result. The flue gas cooling and recovery module is used to pass the titanium tetrachloride flue gas into a cooler and cool and recover titanium tetrachloride according to the low temperature water parameters to obtain flue gas quality data. The compliance determination and adjustment module is used to determine whether the current titanium tetrachloride slurry treatment meets the standards based on the particle detection results and the flue gas quality data. If it does, the separated flue gas and solid particles are discharged; otherwise, the hot flue gas parameters and low-temperature water parameters are adjusted.

Images