Digestion method of solid matter containing titanium tetrachloride

Abstract

The invention discloses a digestion method of a solid matter containing titanium tetrachloride. The digestion method comprises the following steps: contacting and mixing a digestion agent with the solid matter containing titanium tetrachloride to carry out mass and heat transfer, and carrying out digestion reaction at the same time, the digestion agent is a mixture of an inert carrier and a reactant, and the inert carrier is selected from one or more of air, nitrogen, carbon dioxide, alkane gas, alkane liquid and carboxylic acid; the reactant is selected from a gaseous or liquid hydroxyl-containing compound. The digestion method provided by the invention can be used for safely and effectively digesting the titanium tetrachloride-containing solid matter formed in the rectifying kettle after the titanium-containing waste liquid is rectified / distilled, cleaning equipment and recovering the normal use function of the equipment, so that the problem of removing the titanium tetrachloride-containing solid matter gathered in the equipment is solved, and the energy consumption is reduced. And the safety problem caused by directly mixing reactants such as water and the like with the solid matter containing titanium tetrachloride is solved, and industrial implementation is easy.

Description

Technical Field

[0001] The present invention relates to the technical field of three wastes treatment, and particularly relates to a method for digesting a solid substance containing titanium tetrachloride. Background Art

[0002] In the polymerization reactions of polyolefin polymers such as polypropylene and polyethylene, highly active catalysts are required. Among the catalysts obtained for industrial production applications, Ziegler-Natta catalysts are the main type of catalysts. This catalyst is usually obtained by using titanium containing halogen or titanium oxyhalide as a catalyst. During the production and preparation process of Ziegler-Natta catalysts, a large amount of titanium tetrachloride waste liquid is generated. In addition to unreacted titanium tetrachloride, it may also contain organic components such as hydrocarbon organic solvents, titanium alkoxide or halogenated titanium alkoxide.

[0003] The waste liquid containing titanium tetrachloride can separate titanium tetrachloride from the mother liquor by distillation / distillation methods according to the differences in the volatilities of each component. There are also reports of using thin film evaporators for treatment. However, due to the characteristics of the material composition, during the actual distillation / distillation treatment of the material, as the amount of titanium tetrachloride decreases and the concentration of non-volatile components increases, solids composed of inorganic substances such as titanium oxychloride, carbides, titanium alkoxide, and complexes / coordination compounds of titanium tetrachloride will form on the heat exchange walls of the equipment, especially in the distillation still residue. A certain amount of titanium tetrachloride may also be mixed in this solid substance. Therefore, it is generally called a solid substance containing titanium tetrachloride. This solid substance can not only reduce the heat exchange efficiency as fouling, but also may block the pipeline, making it difficult to discharge the titanium tetrachloride-containing liquid in the equipment. While reducing production efficiency and production load, it may even lead to the interruption and accidents of the production process.

[0004] Moreover, the residue of the rectification still is included in the "National List of Hazardous Wastes" (2016 Edition), and titanium tetrachloride is included in the "Catalogue of Hazardous Chemicals" (2015 Edition). If the equipment is opened for mechanical cleaning, due to the fuming effect of titanium tetrachloride when it meets air, it will lead to a harsh (thick and strongly irritating acidic smoke, corrosive environment) and uncontrollable situation of dangerous materials at the scene. There are literature reports on the treatment method of adding high-boiling residue liquid to water for hydrolysis, and then adding alkaline substances (such as sodium hydroxide, calcium hydroxide, calcium oxide, etc.) to the strongly acidic hydrolysis waste liquid for neutralization; however, the solid substances containing titanium tetrachloride are deposited or attached inside the equipment, with the characteristics of high material enrichment degree, complex material conditions (especially the unclear composition of titanium tetrachloride component), and difficulty in transfer; moreover, titanium tetrachloride will violently fume when it meets moist air, and compounds such as titanium oxychloride and titanium alkoxide will also undergo violent hydrolysis reactions when they meet water, and release a large amount of reaction heat. Therefore, directly adding water into the equipment where titanium chloride solid substances are accumulated easily leads to violent gas release and exothermic reactions (the heat released by this reaction can cause the material to boil, vaporize rapidly or even completely evaporate and overheat the steam), thus triggering danger.

[0005] Water and titanium tetrachloride can undergo complex reactions, and the products include light yellow solids. In particular, in the case of non-uniform mixing (such as direct addition), when water contacts titanium tetrachloride, the solid substances formed or the original solid substances in the system have the phenomenon that a shell is formed to wrap the water and isolate it from the solid substances containing titanium tetrachloride, and the gas film / cushion formed by the gas release reaction occurring at the shell interface exacerbates this phenomenon. When the shell wrapped with a large amount of water breaks, the rapid mixing of a large amount of reactants will lead to violent reactions, and the strong exothermic and gas release will further strengthen this reaction process, resulting in the uncontrollability of the reaction process, and even the danger of material flushing / equipment rupture / explosion. The hydrogen chloride / hydrochloric acid in the gas release has strong corrosivity and irritation, which will further deteriorate the situation.

[0006] In this case, how to effectively and safely decompose the solid substances containing titanium tetrachloride, clean the equipment and restore its normal use function has become a key problem related to the normal progress of relevant production, and it is also a problem that has always existed in the industry and has not been effectively solved. Summary of the Invention

[0007] In view of this, the present invention provides a method for decomposing solid substances containing titanium tetrachloride, which can safely and effectively decompose the solid substances of titanium tetrachloride formed in the rectification still after the rectification / distillation treatment of titanium-containing waste liquid, clean the equipment and restore its normal use function. It not only solves the problem of removing the solid substances containing titanium tetrachloride accumulated inside the equipment, but also resolves the safety problems caused by directly mixing reactants such as water with the solid substances containing titanium tetrachloride, and is easy to be implemented industrially.

[0008] To achieve the above object, the present invention provides a method for digesting solids containing titanium tetrachloride, comprising: a digesting agent is contacted and mixed with the solids containing titanium tetrachloride to perform mass transfer and heat transfer while performing a digestion reaction;

[0009] The digester is a mixture of an inert carrier and a reactant, wherein the inert carrier is selected from one or more of air, nitrogen, carbon dioxide, alkane gas, alkane liquid and carboxylic acid; the reactant is selected from gaseous or liquid hydroxyl-containing compounds. The digester can be a mixture of a liquid inert carrier and a liquid reactant, a mixture of a gaseous inert carrier and a gaseous reactant, or a mixture of a gaseous inert carrier and a liquid reactant. The digester can be added according to the actual digestion reaction conditions.

[0010] The digestion reaction described in the present invention includes reaction and dispersion. The specific reaction refers to the substances in the solid containing titanium tetrachloride that can react with the reactants in the digester, which are dispersed or dissolved in the inert solvent through the reaction; the materials that do not participate in the reaction are changed from aggregated blocks to a suspension or dissolved state by the action of the digester. Moreover, the entire digestion reaction process is generally required to be carried out under the protection of an inert atmosphere, mainly to avoid the solid containing titanium tetrachloride from contacting with the air and generating a large amount of smoke. However, in the actual operation process, if the equipment where the solid containing titanium tetrachloride is located is closed (including a dedicated pipeline to collect the materials after the digestion reaction) or the environment permits, inert gas protection may not be required.

[0011] During the above-mentioned digestion reaction, a digester is added to the equipment containing titanium tetrachloride-containing solids so that the digester is in uniform contact with the titanium tetrachloride-containing solids. Specifically, the digester can be ensured to be in uniform contact with the titanium tetrachloride-containing solids by stirring or other methods. Since the titanium tetrachloride and other components in the titanium tetrachloride-containing solids react quickly with water or alcohol and release a lot of heat (the heat release can cause boiling, large-scale vaporization and even overpressure explosion of the reactant system under violent reaction conditions), and may be accompanied by gas release; to avoid the reaction being too violent and dangerous. Therefore, during the digestion reaction, it is necessary to control the temperature of the reaction system. The specific range in which the temperature of the reaction system needs to be controlled needs to be determined according to the actual situation, but the temperature and pressure of the digestion reaction need to be carried out safely within the tolerance range of the corresponding equipment. The digestion method provided by the present invention can be carried out under negative pressure, normal pressure or positive pressure. For example, under normal pressure, it can be carried out in a range of less than 110°C, preferably less than 60°C.

[0012] Whether the specific digestion reaction is completed can be judged or combined in the following ways, but not limited to the following: 1) Reaction temperature. When the reaction temperature of the system is stable and no longer rises, it can be determined that the digestion reaction is completed; 2) Visual inspection. Through the sight glass, check whether the solid matter containing titanium tetrachloride in the equipment has been completely digested; 3) If the pipeline of the equipment is blocked by the solid matter containing titanium tetrachloride, and the pipeline is unblocked and fluid is discharged, it indicates that most of the solid matter containing titanium tetrachloride has been digested; 4) Sampling and testing. If the reactants are detected after sampling and testing the reaction system, it indicates that the solid matter containing titanium tetrachloride has been digested.

[0013] Optionally, in the method for digesting the solid matter containing titanium tetrachloride provided by the present invention, the reactant is selected from one or more of liquid water, steam water, monohydric alcohols or polyhydric alcohols having 1 to 12 carbon atoms.

[0014] Optionally, in the method for digesting the solid matter containing titanium tetrachloride provided by the present invention, the volume concentration of the reactant in the digestion agent is ≤50%, such as 45%, 42%, 40%, 35%, 33%, 28%, 25%, 20%, 15%, 12%, 8%, 5%, 4%, etc.; preferably ≤30%, more preferably ≤10%.

[0015] Optionally, in the method for digesting the solid matter containing titanium tetrachloride provided by the present invention, the digestion agent is obtained by adding the reactant to the inert carrier in a one-time, batch or continuous manner for mixing.

[0016] Optionally, in the method for digesting the solid matter containing titanium tetrachloride provided by the present invention, the mode of contact mixing is achieved by stirring or fluid scouring, and at the same time, heat transfer and temperature control are achieved through temperature rise, evaporation and heat exchange. The purpose of stirring is to fully mix the materials. The scouring of the fluid, for example, in the pipeline, is achieved by the flow of the fluid such as the liquid digestion agent or the dispersion of the gaseous digestion agent to realize the contact between the digestion agent and the solid matter containing titanium tetrachloride.

[0017] The present invention controls the temperature of the digestion reaction (i.e., the rate of the digestion reaction) by further controlling the concentration of the reactant in the digestion agent that reacts with the solid matter containing titanium tetrachloride and the addition rate of the digestion agent; at the same time, keeping the space of the digestion reaction and the external gas phase channel unblocked (i.e., normal pressure state) to ensure that the space of the solid matter containing titanium tetrachloride is in a state where the pressure is controllable; after the digestion reaction is completed, the solid matter of titanium tetrachloride is transformed into a powdery / granular substance or a soluble substance that is easy to disperse (capable of dissolving in the digestion agent or the carrier solvent), realizing the digestion of the solid matter containing titanium tetrachloride.

[0018] According to the heat release of the reaction, means such as reducing the temperature of the material and / or heat exchange are adopted to control the average temperature of the reaction system and its discharged gas. Of course, the temperature of the material can also be controlled by evaporation of the liquid such as the carrier. The gaseous material released by the reaction system to the outside can be condensed and collected by a condenser, or can be transported to a gas treatment link for treatment.

[0019] Optionally, in the method for digesting the solid substance containing titanium tetrachloride provided by the present invention, when the digestant is a gas, the temperature of the digestion reaction zone is higher than the dew point temperature of the gas of the digestant, to prevent phase changes in the gaseous digestant. For example, water or ethanol in the gaseous digestant changes to a liquid state, and with the accumulation of phase changes, liquid water or ethanol aggregates are formed, and then danger occurs.

[0020] Optionally, in the method for digesting the solid substance containing titanium tetrachloride provided by the present invention, the apparent form of the solid substance containing titanium tetrachloride is one or a mixture of solid, paste-like, and viscous liquid states.

[0021] Optionally, in the method for digesting the solid substance containing titanium tetrachloride provided by the present invention, the solid substance containing titanium tetrachloride includes one or more of titanium tetrachloride, chlorooxides formed after hydrolysis of titanium tetrachloride, alkoxytitanium, and titanium tetrachloride complexes / coordination compounds. This solid substance containing titanium tetrachloride can undergo hydrolysis reactions with water (for example, titanium tetrachloride reacts with a small amount of water to form a pale yellow powdery solid, which is further hydrolyzed to titanium oxide, and hydrogen chloride and heat are released; chlorooxides of titanium, alkoxytitanium, titanium tetrachloride complexes / coordination compounds, etc. can react with water to form titanium oxide and substances such as hydrogen chloride and alcohol, and heat is released), and can also undergo alcoholysis reactions with alcohols (for example, titanium tetrachloride can react with alcohols to form alcohol-soluble titanate esters, and hydrogen chloride and heat are released). Usually, hydrolysis reactions or alcoholysis reactions are accompanied by strong heat release and gas release phenomena, and the local effects generated, combined with the dissolution and suspension effects of the digestant itself, can directly cause the disintegration and dissipation of the solid substance containing titanium tetrachloride.

[0022] Optionally, in the method for digesting the solid substance containing titanium tetrachloride provided by the present invention, after the digestion reaction is completed, the digested solid substance containing titanium tetrachloride is discharged together with the remaining digestant, or a solvent is added to carry out the digested solid substance containing titanium tetrachloride.

[0023] Compared with the prior art, the present invention has at least the following beneficial effects:

[0024] Beneficial effects: The digestion method of the solid substance containing titanium tetrachloride provided by the present invention dilutes the reactants in the digestion agent by using an inert component (which does not react violently with the solid substance containing titanium tetrachloride) as a carrier. This digestion agent not only provides buffer conditions for the release of the system pressure and heat, but also provides a regulation space for the replenishment of the digestion reactants, effectively resolving the uncontrollable risks caused by possible violent reactions. It not only solves the problem of removing the solid substance containing titanium tetrachloride accumulated inside the equipment, but also resolves the safety problems caused by directly mixing reactants such as water with the solid substance containing titanium tetrachloride.

[0025] The digestion method of the solid substance containing titanium tetrachloride provided by the present invention not only solves the controllability problem of the violent exothermic and gas-evolving reaction between the reactants and the solid substance containing titanium tetrachloride, but also solves the problems of dispersion and suspension / dissolution transfer of the solid substance, and further avoids the danger of mechanical cleaning operations. This method has the advantages of being safe, feasible, and controllable, and is easy to be applied industrially. Specific embodiments

[0026] The present invention will be specifically described below through examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be construed as limiting the protection scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention according to the above content of the present invention.

[0027] In the following examples, the mass of the solid substance containing titanium tetrachloride in the equipment involved is estimated according to the experiments carried out on the corresponding equipment and in accordance with the experimental ratio.

[0028] Example 1

[0029] In a 3m 3 volume titanium tetrachloride waste liquid rectification tower kettle with dimensions of 1400×2000(H), there is about 30 kg of black-brown solid rectification residue containing titanium tetrachloride accumulated. This solid substance residue containing titanium tetrachloride adheres to the kettle wall and the bottom of the kettle, has a violent fuming phenomenon when exposed to air, and releases irritating gases. The solid material in the kettle bottom basically has no fluidity and blocks the pipeline outlet at the bottom of the kettle, making it impossible to be directly discharged.

[0030] The condenser at the top of the distillation tower is opened and emptied, and a dry nitrogen replacement equipment system is used. The jacket cooling water is opened to cool down, and then under stirring conditions (about 65rpm), a digester (hexane is an inert carrier, ethanol is a reactant, and the volume concentration of ethanol is about 5%, and ethanol is added to hexane once and mixed evenly) about 500L is added to the tower kettle at one time, and the solid residue containing titanium tetrachloride in the kettle is infiltrated and dispersed under stirring. The exothermic steam of the tower kettle reaction and the digester condensate condensed through the kettle wall contact with the solid containing titanium tetrachloride on the surface of the kettle wall, and further digestion can occur. The rising steam in the kettle (exceeding the boiling point of hexane will form steam through the volatilization of hexane and will take away part of the heat at the same time) is condensed and recovered at the top of the tower, and the condensate is refluxed into the tower, and the non-condensable gas is discharged and collected and then transported to the hydrogen chloride acid gas recovery and treatment link. The temperature of the control system is less than 45°C during the entire digestion reaction process.

[0031] After the digestion agent is added, ethanol or ethanol-hexane mixture is added to the tower or kettle according to the digestion of the solid residue containing titanium tetrachloride, until there is basically no liquid reflux at the top of the tower and the kettle temperature begins to drop, indicating that the digestion reaction is completed.

[0032] Stop cooling the tower bottom, switch the tower bottom to heating, start distillation operation, and take out materials with a composition close to hexane-ethanol azeotrope (normal pressure azeotropic point is about 56.7°C, and the azeotrope contains about 21% ethanol) and part of the hexane from the top of the tower, and recycle them for subsequent batches; after the material recovery is completed, stop heating, discharge the kettle liquid and rinse the tower bottom, and end the digestion operation of solids containing titanium tetrachloride. The discharged kettle liquid can be used for waste liquid treatment or solid-liquid separation and recovery treatment of waste digestion agent (solids are treated as solid waste, and liquids are used).

[0033] After the air in the bottom of the distillation tower is replaced by inert gas after cleaning, the subsequent distillation operation is directly fed.

[0034] Example 2

[0035] exist 1400×2000(H)3m 3 In the reactor of the titanium tetrachloride waste liquid distillation tower, there are about 50kg of dark brown solid distillation residue containing titanium tetrachloride, and about 10kg of titanium tetrachloride liquid residue. The solid residue containing titanium tetrachloride adheres to the wall and bottom of the reactor, and emits violent smoke and irritating gas when it comes into contact with air. The solid material in the reactor has basically no fluidity and blocks the outlet of the pipeline at the bottom of the reactor, so it cannot be discharged directly.

[0036] Open the overhead condenser and vent of the above-mentioned rectification column, and use dry nitrogen to displace the equipment system. Then, under stirring conditions (about 65 rpm), add the digestion agent in two batches to the column still. (Cyclohexane is used as the carrier, water and ethanol are the reactants, the volume concentration of water is about 1%, and the volume concentration of ethanol is about 1%. Water and ethanol are continuously added to cyclohexane in parallel and mixed evenly) about 1000 L (about 500 L per batch), and infiltrate and disperse the solid residue containing titanium tetrachloride on the surface of the still wall under stirring. The rising steam from the column still is condensed and recovered at the top of the column, the condensate flows back into the column, and the non-condensable gas is discharged and collected and then sent to the hydrogen chloride acidic gas recovery and treatment section. After the feeding is completed, observe through the sight glass. According to the digestion situation of the solid residue containing titanium tetrachloride, add water, ethanol or their mixture with cyclohexane to the column or the still until there is basically no liquid reflux at the top of the column and the temperature of the still begins to drop. During the entire digestion reaction process, control the temperature of the system to be less than 50 °C.

[0037] Turn on the heating of the column still and start the rectification operation. The overhead product is a material with an azeotropic composition close to cyclohexane-water (atmospheric azeotropic point is about 68.95 °C, and the azeotrope contains about 8.4% water), cyclohexane-ethanol (atmospheric azeotropic point is about 64.9 °C, and the azeotrope contains about 30% ethanol), or cyclohexane-water-ethanol (atmospheric azeotropic point is about 62.1 °C, and the azeotrope contains about 7% water and about 17% ethanol). When the water content in the overhead product is relatively high, the oil-phase cyclohexane and the water-phase water can be separately recovered by phase separation. The overhead product can be collected and used for the next batch. Observe through the sight glass. Under the condition that the material has good fluidity (to avoid blockage), extract an appropriate amount of the main fraction of cyclohexane to recover the digestion agent (as long as the liquid level in the still and the fluidity of the material can be ensured). After the material recovery is completed, stop heating, discharge the still liquid and rinse the column still to end the digestion operation of the solid containing titanium tetrachloride. The discharged still liquid can be treated as waste liquid or sent to the waste digestion agent recovery and treatment section.

[0038] After replacing the air in the column still of the above-mentioned cleaned rectification column with inert gas, directly feed for the subsequent rectification operation.

[0039] Example 3

[0040] In a 3 m³ 3 volume titanium tetrachloride waste liquid rectification column still, there is about 100 kg of solid rectification residue containing titanium tetrachloride accumulated, and about 30 kg of titanium tetrachloride liquid remains. The solid residue containing titanium tetrachloride adheres to the still wall and the bottom of the still, and there is a strong fuming phenomenon when exposed to air and an irritating gas is released. The solid material in the still basically has no fluidity and blocks the pipeline outlet at the bottom of the still, making it impossible to discharge directly.

[0041] Open the top condenser and vent of the rectification column, use dry nitrogen to displace the equipment system, turn on the jacket cooling water to lower the temperature, and then, under stirring conditions (about 65 rpm), first add 500 L of digestion agent 1 (decane carrier, ethanol volume concentration is 0.5%) to the bottom of the column, and infiltrate and disperse the solid residue containing titanium tetrachloride on the surface of the column wall under stirring; then first add 1000 L of digestion agent 2 (decane carrier, ethanol volume concentration is about 5%) to the bottom of the column. The rising steam from the bottom of the column is condensed and recovered at the top of the column, the condensate flows back into the column, and the non-condensable gas is discharged and collected and then sent to the hydrogen chloride acidic gas recovery and treatment section. After the feeding is completed, observe through the sight glass, and according to the digestion situation of the solid residue containing titanium tetrachloride, add ethanol, decane or their mixture to the column or the kettle until there is basically no gas released at the top of the column and the temperature of the kettle begins to drop. During the whole digestion reaction process, control the temperature of the system to be less than 40°C.

[0042] Turn on the heating of the bottom of the column and start the rectification operation. The low-boiling components such as water and ethanol are taken out from the top of the column and used for the next batch. After the material recovery is completed, stop heating, discharge the kettle liquid and rinse the bottom of the column to end the digestion operation of the solid containing titanium tetrachloride. The discharged liquid is collected and can be treated as waste liquid or sent to the waste digestion agent recovery and treatment section.

[0043] After replacing the air in the bottom of the rectification column after the above cleaning with inert gas, directly feed for the subsequent rectification operation.

[0044] Example 4

[0045] In a 1.5 m long pipe, the wall of the pipe is adhered with solid matter containing titanium tetrachloride. This solid matter containing titanium tetrachloride has a violent fuming phenomenon when encountering air and releases irritating gases. The solid material in the pipe basically has no fluidity and blocks the pipe, making it impossible to be directly discharged.

[0046] Open the valve at one end of the pipe and connect it to the discharge collection pipeline or device that meets the multi-phase material storage / processing capacity after the digestion of the solid containing titanium tetrachloride. Starting from the side communicating with the discharge outlet, open the bypass of the pipe where the solid containing titanium tetrachloride accumulates (the bypass is equipped with a check valve), and introduce a mixture of superheated steam or saturated steam and nitrogen (the volume flow ratio of nitrogen / saturated steam is about 10:1, control the temperature of the digestion reaction to be higher than the dew point temperature of the steam to prevent the steam from turning into liquid water). Under the action of high-temperature rapid diffusion mass transfer, the solid containing titanium tetrachloride reacts with the steam and disintegrates, and is digested and dispersed out of the pipe under the action of the gas flow scouring. Keep the inside of the pipe in a positive pressure state until there is no significant fuming in the pipe discharge and the gas flow is smooth. After confirming that the pipe is unblocked, close the bypass valve and stop introducing the gas to end the digestion operation of the solid containing titanium tetrachloride.

[0047] During the above operations, it is necessary to ensure tight connections, and the pipelines, instruments, equipment, etc. involved in the treatment are in a safe state, with sufficient resistance to physical and chemical conditions (temperature, pressure, corrosion) shocks under the treatment conditions, so as to avoid possible material leakage and dangerous situations.

[0048] Example 5

[0049] In a 2m long pipeline, solid substances containing titanium tetrachloride adhere to the pipe wall. The solid substances containing titanium tetrachloride emit intense fumes when exposed to air and release irritating gases. The solid materials in the pipeline basically do not have fluidity and block the pipeline, making it impossible to discharge directly.

[0050] Open the valve at one end of the pipeline and connect it to the discharge collection pipeline or device that can accommodate the multiphase materials after the digestion of the solid substances containing titanium tetrachloride. Starting from the side communicating with the discharge outlet, open the bypass of the pipeline where the solid substances containing titanium tetrachloride have accumulated (a check valve is installed in the bypass), and introduce a mixture of ethanol vapor and nitrogen (the volume flow ratio of nitrogen / ethanol saturated vapor is about 5:1; control the temperature of the digestion reaction to be higher than the dew point temperature of ethanol vapor to prevent ethanol vapor from turning into liquid ethanol). Under the action of gas-phase diffusion mass transfer, the solid substances containing titanium tetrachloride react with ethanol in the gas and disintegrate, and are digested and dispersed out of the pipeline under the action of the gas flow scouring. Keep the pipeline in a positive pressure state until the pipeline flows smoothly. After confirming that the pipeline is unblocked, close the bypass valve and stop introducing the gas to end the digestion operation of the solid substances containing titanium tetrachloride.

[0051] During the above operations, it is necessary to ensure tight connections, and the pipelines, instruments, equipment, etc. involved in the treatment are in a safe state, with sufficient resistance to physical and chemical conditions (temperature, pressure, corrosion) shocks under the treatment conditions, so as to avoid possible material leakage and dangerous situations.

[0052] Of course, the present invention may also have many other embodiments and their variations. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding changes and deformations should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for digesting a solid substance containing titanium tetrachloride, characterized in that, it includes: While the digestion agent is in contact with the solid substance containing titanium tetrachloride for mass and heat transfer, a digestion reaction is carried out; The digestion agent is a mixture of an inert carrier and a reactant, and the inert carrier is selected from one or more of air, nitrogen, carbon dioxide, alkane gas, alkane liquid, and carboxylic acid; the reactant is selected from gaseous or liquid hydroxy-containing compounds.

2. The method for digesting a solid substance containing titanium tetrachloride according to claim 1, characterized in that, The reactant is selected from one or more of liquid water, steam water, monohydric alcohols or polyhydric alcohols having 1 to 12 carbon atoms.

3. The method for digesting a solid substance containing titanium tetrachloride according to claim 1, characterized in that, The volume concentration of the reactant in the digestion agent ≤ 50%.

4. The method for digesting a solid substance containing titanium tetrachloride according to claim 3, characterized in that, The volume concentration of the reactant in the digestion agent ≤ 30%.

5. The method for digesting a solid substance containing titanium tetrachloride according to claim 1, characterized in that, The digestion agent is obtained by adding the reactant to the inert carrier in a one-time, batch or continuous manner for mixing.

6. The method for digesting a solid substance containing titanium tetrachloride according to claim 1, characterized in that, The contact mixing is achieved by stirring or fluid flushing.

7. The method for digesting a solid substance containing titanium tetrachloride according to claim 1, characterized in that, When the digestion agent is a gas, the temperature of the digestion reaction region is higher than the dew point temperature of the gas of the digestion agent.

8. The method for digesting a solid substance containing titanium tetrachloride according to claim 1, characterized in that, The apparent form of the solid substance containing titanium tetrachloride is one or a mixed state of solid, paste-like, and viscous liquid.

9. The method for digesting a solid substance containing titanium tetrachloride according to claim 1, characterized in that, The solid substance containing titanium tetrachloride includes one or more of titanium tetrachloride, oxychloride formed after hydrolysis of titanium tetrachloride, alkoxytitanium, and titanium tetrachloride complex / coordination compound.

10. The method for digesting a solid substance containing titanium tetrachloride according to claim 1, characterized in that, After the digestion reaction is completed, the digested material is discharged together with the remaining digestion agent, or a solvent is added to carry out the digested material.