CN113880135A - Preparation of rutile TiO by waste gas of titanium white process by chlorination process2And method for dry ice - Google Patents
Preparation of rutile TiO by waste gas of titanium white process by chlorination process2And method for dry ice Download PDFInfo
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Abstract
Method for preparing rutile TiO by using waste gas of titanium white process by chlorination process2And dry ice, comprising: the method comprises the steps of reacting chlorination process waste gas and oxidation process waste gas in the chlorination process titanium dioxide production process with hot oxygen under the condition of a crystal form conversion agent, separating reaction products to obtain rutile type titanium dioxide particles, spraying the separated gas to obtain a dilute hydrochloric acid solution, and preparing the gas subjected to spraying treatment into dry ice. The method effectively recycles the waste gas generated in the industrial production of titanium white by the chlorination process to obtain hydrochloric acid solution and rutile TiO2And the dry ice can effectively control the emission of greenhouse gases generated in the titanium white production process by the chlorination process, and meet the requirements of China on carbon emission peak reaching and carbon neutralization standards.
Description
Technical Field
The invention relates to the field of comprehensive utilization of waste gas in a titanium white process by a chlorination method, in particular to a method for preparing rutile TiO by utilizing waste gas in the titanium white process by the chlorination method2And dry ice.
Background
Compared with the sulfuric acid process, the titanium dioxide product prepared by the chlorination process has the remarkable advantages of high weather resistance, uniform particle size distribution (the average particle size is 0.2-0.3 mu m), few impurity elements (the existence of Si element can not be detected in the product), uniform and smooth crystal particles, high lattice purity and the like, and particularly the particle size distribution, the content of the impurity elements and the configuration of the crystal particles are difficult to compare favorably with those of the sulfuric acid process.
At present, in the production process of titanium dioxide by a domestic chlorination method, the chlorination process mainly comprises boiling chlorination and molten salt chlorination, and the titanium raw material and chlorine gas are subjected to high-temperature chlorination reaction to obtain an intermediate product TiCl4The principle of the main production chemical reaction is as follows:
TiO2+C+2Cl2＝TiCl4+CO2
TiO2+2C+2Cl2＝TiCl4+2CO
TiCl4+O2＝TiO2+2Cl2
the oxidation process has the following main chemical reaction principle:
aluminum powder reacts with chlorine
2Al(s)+3Cl2(g)＝2AlCl3(g)
Combustion reaction of toluene and oxygen
C7H8(l)+9O2(g)＝7CO2(g)+4H2O(g)
Titanium tetrachloride vapor phase oxidation reaction
TiCl4(g)+O2(g)＝TiO2(R,s)+2Cl2(g)
Oxidation reaction of aluminium trichloride
4AlCl3(g)+3O2(g)＝2Al2O3(s)+6Cl2(g)
The global titanium dioxide productivity exceeds 900 million tons in 2020, and the yield exceeds 700 million tons. WhereinThe capacity of China is about 400 ten thousand tons, the output is about 351 ten thousand tons, and 70 percent of capacity is produced by a chlorination method in foreign countries. The chlorination process titanium white process is the mainstream process for producing titanium dioxide in the world, but CO is inevitably generated in the chlorination process titanium white process2The main production process comprises two processes of chlorination and oxidation, wherein the waste gas of the chlorination process mainly contains TiCl4、Cl2、CO2And CO, the exhaust gas from the oxidation step mainly contains CO2And Cl2. Under the background of increasingly strengthened environmental protection regulations and increasingly improved product quality requirements of users, under the background of realizing carbon peak reaching 2030 years ago and carbon neutralization 2060 years ago in Chinese strive, TiCl existing in titanium white process waste gas of chlorination process is reasonably utilized and treated4、Cl2、CO2And valuable substances such as CO and the like become a necessary way for the development of the industry and the realization of green production.
At present, the treatment of titanium dioxide tail gas by chlorination process is generally lime neutralization process, and carbide slag or lime powder and the like which mainly contain Ca (OH) are utilized2The alkaline substance and the waste acid are neutralized and then buried, and the acidic substance is also adopted to neutralize harmful TiCl in the waste gas4And Cl2After absorption, the remaining CO is removed2And the direct CO evacuation method, the treatment method causes resource waste to a certain extent and causes environmental pollution.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing rutile TiO by using waste gas of titanium white process by chlorination process2The method of mixing with dry ice can effectively control the greenhouse gas emission generated in the titanium white production process by the chlorination method, and solves the problem of CO in the waste gas emitted by the titanium white production process by the prior chlorination method2And recycling of CO.
In order to achieve the purpose, the invention provides the technical scheme that:
method for preparing rutile TiO by using waste gas of titanium white process by chlorination process2And dry ice, comprising: the waste gas of the chlorination process and the waste gas of the oxidation process in the production process of titanium white by a chlorination process are transformed into crystal formsReacting with hot oxygen under the condition of an agent, separating a reaction product to obtain rutile type titanium dioxide particles, spraying the separated gas to obtain a dilute hydrochloric acid solution, and preparing the gas subjected to spraying treatment into dry ice.
Further, the method comprises the following steps of reacting waste gas of a chlorination process and waste gas of an oxidation process in the production process of titanium white by a chlorination process with hot oxygen under the condition of a crystal form conversion agent:
step 1, introducing waste gas of a chlorination procedure and waste gas of an oxidation procedure into an oxidation reactor;
step 2, introducing hot oxygen into the oxidation reactor, and simultaneously adding a crystal form conversion agent into the oxidation reactor;
and 3, carrying out oxidation reaction on the chlorination process waste gas and the oxidation process waste gas and hot oxygen at the temperature of 1550-1750 ℃, wherein rutile type titanium dioxide particles, gaseous carbon dioxide and gaseous chlorine exist in reaction products.
Further, the reaction product is separated to obtain rutile titanium dioxide, which comprises: and (3) conveying the reaction product into a gas-solid separation bag filter to separate rutile type titanium dioxide particles, gaseous carbon dioxide and gaseous chlorine.
Further, spraying the separated gas to obtain a dilute hydrochloric acid solution, comprising the following steps:
step a, introducing the separated gaseous carbon dioxide and gaseous chlorine into a leaching tower;
b, spraying water in the leaching tower, absorbing gaseous chlorine to form a dilute hydrochloric acid solution, and discharging gaseous carbon dioxide out of the leaching tower;
step c separates a dilute hydrochloric acid solution.
Further, the gas after the spraying treatment is made into dry ice, and the process comprises the step of introducing gaseous carbon dioxide discharged after the spraying treatment in the elution tower into a dry ice generator to make into the dry ice.
Further, the chlorination process off-gas includes carbon dioxide, carbon monoxide, titanium tetrachloride and chlorine.
Further, the oxidation process off-gas comprises chlorine and carbon dioxide.
Further, the hot oxygen is oxygen preheated to 850-950 ℃.
Further, the oxidation reactor is an electromagnetic induction oxidation reactor.
Further, in step b, water and dilute hydrochloric acid are sprayed in the leaching tower to absorb gaseous chlorine.
The invention has the beneficial effects that:
the invention prepares rutile TiO by using waste gas of titanium white process of chlorination method2Introducing waste gas generated in the chlorination and oxidation processes in the production process of titanium dioxide by a chlorination method into an electromagnetic induction oxidation reactor, adding a proper amount of preheated oxygen and a crystal form conversion agent, and adding TiCl contained in the waste gas4Oxidation to rutile TiO2Conversion of CO to CO2Formation of TiO2、Cl2And CO2The gas-solid mixture is subjected to gas-solid separation treatment to obtain rutile TiO2Valuable resources can be directly utilized and can be directly sold. Cl2And CO2After leaching separation, the separated dilute hydrochloric acid solution can be sold or sent to a titanium dioxide system of a chlorination method for post-treatment and use, and CO2The gas is sent to a dry ice generator to be finally prepared into dry ice for sale. The invention effectively recycles the waste gas generated in the industrial production of titanium white by a chlorination process to obtain hydrochloric acid solution and rutile TiO2And the dry ice meets the national requirements on carbon emission peak reaching and carbon neutralization standards, the chlorination process titanium dioxide process is strengthened by a chemical process, green production is really realized, and the finally formed byproduct also has a certain economic utilization value.
The domestic titanium white chloride production capacity in 2021 can exceed 80 ten thousand tons, which accounts for about 19 percent. Because the domestic chlorination process has more types and is difficult to acquire data, the CO is generated by calculating each ton of titanium dioxide produced by using the oxidation process section253.5-58.5 kg of gas, the effective operating rate of the production line is calculated according to 81 percent, the effective capacity of titanium white chloride in 2021 years is 64.8 ten thousand tons, and CO can be generated at most20.0585 × 648000 ═ 37908t of gas, 5 yuan/kg of industrial carbon dioxide, and 189540000 yuan of value space theoretically (without counting labor cost and treatment process)Cost). The carbon dioxide dry ice with higher purity is prepared to be 7.8 yuan/kg, and theoretically has 295682400 yuan worth space.
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FIG. 1 shows the preparation of rutile TiO by using waste gas from titanium white chlorination process according to the present invention2And dry ice process flow schematic.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to embodiments and accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for preparing rutile TiO by using waste gas of titanium white process of chlorination process2And dry ice, comprising: the method comprises the steps of reacting chlorination process waste gas and oxidation process waste gas in the chlorination process titanium dioxide production process with hot oxygen under the condition of a crystal form conversion agent, separating reaction products to obtain rutile type titanium dioxide particles, spraying the separated gas to obtain a dilute hydrochloric acid solution, and preparing the gas subjected to spraying treatment into dry ice. Wherein the hot oxygen is oxygen preheated to 850-950 ℃.
The method comprises the following steps of reacting chlorination process waste gas and oxidation process waste gas in the production process of titanium dioxide by a chlorination method with hot oxygen under the condition of a crystal form conversion agent:
step 1, introducing chlorination procedure waste gas and oxidation procedure waste gas into an oxidation reactor, wherein the chlorination procedure waste gas comprises carbon dioxide, carbon monoxide, titanium tetrachloride and chlorine, and the oxidation procedure waste gas comprises chlorine and carbon dioxide;
step 2, introducing hot oxygen into an oxidation reactor, and simultaneously adding a crystal form conversion agent into the oxidation reactor, wherein the addition amount of the oxygen is related to the reaction of the oxygen and titanium tetrachloride, the reaction of the oxygen and the crystal form conversion agent, and the reaction of the oxygen and carbon monoxide;
and 3, carrying out oxidation reaction on the chlorination process waste gas and the oxidation process waste gas and hot oxygen at the temperature of 1550-1750 ℃, wherein rutile type titanium dioxide particles, gaseous carbon dioxide and gaseous chlorine exist in reaction products.
Among them, the oxidation reactor is preferably an electromagnetic induction oxidation reactor. The crystal transformation agent is preferably aluminum trichloride (AlCl)3) The following reactions mainly take place in the oxidation reactor:
TiCl4(g)+O2(g)＝TiO2(R,s)+2Cl2(g)
2CO(g)+O2(g)＝2CO2(g)
wherein, the crystal form transforming agent and oxygen have the following reactions:
4AlCl3(g)+3O2(g)＝2Al2O3(s)+6Cl2(g)
the chlorination process waste gas and the oxidation process waste gas which are introduced into the oxidation reactor form chlorination process waste gas, and the chlorination process waste gas comprises the following components in percentage by weight: titanium tetrachloride (TiCl)4): 2.317-2.885% of silicon tetrachloride (SiCl)4): 0.036-0.045% and carbon dioxide (CO)2): 64.375-65.613%, carbon monoxide (CO): 3.092-3.203%, chlorine (Cl)2): 0.005-0.009%, oxygen (O)2): 2.810-3.237%, nitrogen (N)2): 25.373-26.466%, argon (Ar): 0.216-0.338%. The total flow of the chlorination process waste gas introduced into the oxidation reactor is controlled by setting the flow of titanium tetrachloride in the chlorination process waste gas introduced into the oxidation reactor.
Separating the reaction product to obtain rutile type titanium dioxide, which comprises: and (3) conveying the reaction product into a gas-solid separation bag filter to separate rutile type titanium dioxide particles, gaseous carbon dioxide and gaseous chlorine.
Spraying the separated gas to obtain a dilute hydrochloric acid solution, comprising the following steps:
step a, introducing the separated gaseous carbon dioxide and gaseous chlorine into a leaching tower;
b, spraying water in the leaching tower, absorbing gaseous chlorine to form a dilute hydrochloric acid solution, and discharging gaseous carbon dioxide out of the leaching tower;
step c separates a dilute hydrochloric acid solution.
In step b, water and dilute hydrochloric acid may be sprayed in the leaching tower, and gaseous chlorine gas is absorbed by the water and the dilute hydrochloric acid.
And preparing the gas subjected to the spraying treatment into dry ice, wherein the step of introducing the gas carbon dioxide discharged after the spraying treatment in the elution tower into a dry ice generator to prepare the dry ice.
The invention prepares rutile TiO by using waste gas of titanium white process of chlorination method2And dry ice, with reference to figure 1, are described below.
Example 1
Preparation of rutile TiO by waste gas of titanium white process by chlorination process2And dry ice, comprising the steps of:
step 1, respectively introducing chlorination process waste gas and oxidation process waste gas in a chlorination-process titanium dioxide production process into an electromagnetic induction oxidation reactor, wherein the chlorination process waste gas comprises carbon dioxide, carbon monoxide, titanium tetrachloride and chlorine, the oxidation process waste gas comprises chlorine and carbon dioxide, and the chlorination process waste gas introduced into the electromagnetic induction oxidation reactor comprises the following components in percentage by weight: titanium tetrachloride (TiCl)4): 2.575%, silicon tetrachloride (SiCl)4): 0.039%, carbon dioxide (CO)2): 65.065%, carbon monoxide (CO): 3.129%, chlorine gas (Cl)2): 0.007% of oxygen (O)2): 2.936%, nitrogen (N)2): 25.911%, argon (Ar): 0.338 percent. Wherein the flow rate of titanium tetrachloride in the chlorination process waste gas is set to be 100kg/h, and the total flow rate of the chlorination process waste gas introduced into the electromagnetic induction oxidation reactor is 3883.50 kg/h;
step 2, introducing oxygen preheated to 890 ℃ into an electromagnetic induction oxidation reactor, and simultaneously adding a crystal form conversion agent into the electromagnetic induction oxidation reactor, wherein the crystal form conversion agent is aluminum trichloride, and the addition amount of the crystal form conversion agent is 3.26 kg; the adding amount of oxygen is related to the reaction of oxygen and titanium tetrachloride, the reaction of oxygen and a crystal form conversion agent and the reaction of oxygen and carbon monoxide, wherein 16.84kg/h of oxygen is required for the reaction of oxygen and titanium tetrachloride, 0.59kg/h of oxygen is required for the reaction of oxygen and the crystal form conversion agent, 69.7kg/h of oxygen is required for the reaction of oxygen and carbon monoxide, and 87.13kg/h of oxygen is added;
step 3, carrying out oxidation reaction on the chlorination process waste gas and the oxidation process waste gas and oxygen at 1600 ℃, reacting titanium tetrachloride in the waste gas with the oxygen to generate rutile type titanium dioxide, reacting carbon monoxide in the waste gas with the oxygen to generate carbon dioxide, and enabling rutile type titanium dioxide particles, gaseous carbon dioxide and gaseous chlorine to exist in reaction products;
step 4, the reaction product is sent into a gas-solid separation bag filter to separate rutile type titanium dioxide particles which can be directly sold, gaseous carbon dioxide and gaseous chlorine, and the separated rutile type titanium dioxide particles are collected and stored;
and 5, introducing the separated gaseous carbon dioxide and gaseous chlorine into the leaching tower, spraying water in the leaching tower, absorbing the gaseous chlorine to form a dilute hydrochloric acid solution, discharging the gaseous carbon dioxide which is not easy to dissolve in water and dilute hydrochloric acid out of the leaching tower, and separating the dilute hydrochloric acid solution. The separated dilute hydrochloric acid solution can be sold for external use, and can also be sent to a chlorination-process titanium dioxide system for post-treatment and use;
and 6, introducing gaseous carbon dioxide discharged after spraying in the elution tower into a dry ice generator to prepare dry ice.
Introducing chlorination process waste gas generated in chlorination and oxidation procedures in the production process of titanium dioxide by a chlorination method into an electromagnetic induction oxidation reactor, and adding a proper amount of 890 ℃ oxygen and a crystal form conversion agent to enable TiCl contained in the waste gas to be in contact with the carbon dioxide4Oxidation to rutile TiO2Conversion of CO to CO2Formation of TiO2、Cl2And CO2The gas-solid mixture is subjected to gas-solid separation treatment to obtain rutile TiO2Is valuable resource which can be directly utilized, wherein the conversion rate of the rutile type titanium dioxide is 99.24 percent. Cl2And CO2The formed dilute hydrochloric acid can be recycled through leaching separation, and CO is2The gas is sent to a dry ice generator to be finally prepared into dry ice for sale. Fully recovering CO and CO in the waste gas discharged by the titanium white chloride process production2And Cl2。
Example 2
Preparation of rutile TiO by waste gas of titanium white process by chlorination process2And dry ice, comprising the steps of:
step 1, respectively introducing chlorination process waste gas and oxidation process waste gas in a chlorination-process titanium dioxide production process into an electromagnetic induction oxidation reactor, wherein the chlorination process waste gas comprises carbon dioxide, carbon monoxide, titanium tetrachloride and chlorine, the oxidation process waste gas comprises chlorine and carbon dioxide, and the chlorination process waste gas introduced into the electromagnetic induction oxidation reactor comprises the following components in percentage by weight: titanium tetrachloride (TiCl)4): 2.885%, silicon tetrachloride (SiCl)4): 0.036%, carbon dioxide (CO)2): 64.375%, carbon monoxide (CO): 3.203% of chlorine (Cl)2): 0.009%, oxygen (O)2): 2.810%, nitrogen (N)2): 26.466%, argon (Ar): 0.216 percent. Wherein the flow rate of titanium tetrachloride in the chlorination process waste gas is set to be 100kg/h, and the total flow rate of the chlorination process waste gas introduced into the electromagnetic induction oxidation reactor is 3466.20 kg/h;
step 2, introducing oxygen preheated to 850 ℃ into an electromagnetic induction oxidation reactor, and simultaneously adding a crystal form conversion agent into the electromagnetic induction oxidation reactor, wherein the crystal form conversion agent is aluminum trichloride, and the addition amount of the crystal form conversion agent is 3.26 kg; the adding amount of oxygen is related to the reaction of oxygen and titanium tetrachloride, the reaction of oxygen and a crystal form conversion agent and the reaction of oxygen and carbon monoxide, wherein 16.84kg/h of oxygen is required for the reaction of oxygen and titanium tetrachloride, 0.59kg/h of oxygen is required for the reaction of oxygen and the crystal form conversion agent, 63.69kg/h of oxygen is required for the reaction of oxygen and carbon monoxide, and the adding amount of oxygen is 81.12 kg/h;
step 3, carrying out an oxidation reaction on the chlorination process waste gas and the oxidation process waste gas and oxygen at 1750 ℃, reacting titanium tetrachloride in the waste gas and the oxygen to generate rutile type titanium dioxide, reacting carbon monoxide in the waste gas and the oxygen to generate carbon dioxide, and enabling rutile type titanium dioxide particles, gaseous carbon dioxide and gaseous chlorine to exist in reaction products;
step 4, the reaction product is sent into a gas-solid separation bag filter to separate rutile type titanium dioxide particles which can be directly sold, gaseous carbon dioxide and gaseous chlorine, and the separated rutile type titanium dioxide particles are collected and stored;
and 5, introducing the separated gaseous carbon dioxide and gaseous chlorine into the leaching tower, spraying water and 25% dilute hydrochloric acid in the leaching tower, absorbing the gaseous chlorine to form a dilute hydrochloric acid solution, discharging the gaseous carbon dioxide which is not easy to dissolve in the water and the dilute hydrochloric acid out of the leaching tower, and separating the dilute hydrochloric acid solution. The separated dilute hydrochloric acid solution can be sold for external use, and can also be sent to a chlorination-process titanium dioxide system for post-treatment and use;
and 6, introducing gaseous carbon dioxide discharged after spraying in the elution tower into a dry ice generator to prepare dry ice.
Introducing chlorination process waste gas generated in chlorination and oxidation procedures in the production process of titanium dioxide by a chlorination method into an electromagnetic induction oxidation reactor, and adding a proper amount of 850 ℃ oxygen and a crystal form conversion agent to enable TiCl contained in the waste gas to be in a TiCl-containing state4Oxidation to rutile TiO2Conversion of CO to CO2Formation of TiO2、Cl2And CO2The gas-solid mixture is subjected to gas-solid separation treatment to obtain rutile TiO2Is directly utilizable as valuable resource, wherein the conversion rate of rutile type titanium dioxide is 99.07%. Cl2And CO2The formed dilute hydrochloric acid can be recycled through acid leaching separation, and CO is2The gas is sent to a dry ice generator to be finally prepared into dry ice for sale. Fully recovering CO and CO in the waste gas discharged by the titanium white chloride process production2And Cl2。
Example 3
Preparation of rutile TiO by waste gas of titanium white process by chlorination process2And dry ice, comprising the steps of:
step 1, respectively introducing chlorination process waste gas and oxidation process waste gas in a chlorination-process titanium dioxide production process into an electromagnetic induction oxidation reactor, wherein the chlorination process waste gas comprises carbon dioxide, carbon monoxide, titanium tetrachloride and chlorine, the oxidation process waste gas comprises chlorine and carbon dioxide, and the chlorination process waste gas introduced into the electromagnetic induction oxidation reactor comprises the following components in percentage by weight: titanium tetrachloride (TiCl)4): 2.317%, silicon tetrachloride (SiCl)4): 0.045%, carbon dioxide (CO)2): 65.613%, carbon monoxide (CO): 3.092%, chlorine gas (Cl)2): 0.005% of oxygen (O)2): 3.237%, nitrogen (N)2): 25.373%, argon (Ar): 0.318 percent. Wherein the flow rate of titanium tetrachloride in the chlorination process waste gas is set to be 100kg/h, and the total flow rate of the chlorination process waste gas introduced into the electromagnetic induction oxidation reactor is 4315.93 kg/h;
step 2, introducing oxygen preheated to 950 ℃ into an electromagnetic induction oxidation reactor, and simultaneously adding a crystal form conversion agent into the electromagnetic induction oxidation reactor, wherein the crystal form conversion agent is aluminum trichloride, and the addition amount of the crystal form conversion agent is 3.26 kg; the adding amount of oxygen is related to the reaction of oxygen and titanium tetrachloride, the reaction of oxygen and a crystal form conversion agent and the reaction of oxygen and carbon monoxide, wherein 16.84kg/h of oxygen is required for the reaction of oxygen and titanium tetrachloride, 0.59kg/h of oxygen is required for the reaction of oxygen and the crystal form conversion agent, 76.55kg/h of oxygen is required for the reaction of oxygen and carbon monoxide, and the adding amount of oxygen is 93.98 kg/h;
step 3, carrying out oxidation reaction on the chlorination process waste gas and the oxidation process waste gas and oxygen at the temperature of 1550 ℃, reacting titanium tetrachloride in the waste gas and the oxygen to generate rutile type titanium dioxide, reacting carbon monoxide in the waste gas and the oxygen to generate carbon dioxide, and enabling rutile type titanium dioxide particles, gaseous carbon dioxide and gaseous chlorine to exist in reaction products;
step 4, the reaction product is sent into a gas-solid separation bag filter to separate rutile type titanium dioxide particles which can be directly sold, gaseous carbon dioxide and gaseous chlorine, and the separated rutile type titanium dioxide particles are collected and stored;
and 5, introducing the separated gaseous carbon dioxide and gaseous chlorine into the leaching tower, spraying water and 20% dilute hydrochloric acid in the leaching tower, absorbing the gaseous chlorine to form a dilute hydrochloric acid solution, discharging the gaseous carbon dioxide which is not easy to dissolve in the water and the dilute hydrochloric acid out of the leaching tower, and separating the dilute hydrochloric acid solution. The separated dilute hydrochloric acid solution can be sold for external use, and can also be sent to a chlorination-process titanium dioxide system for post-treatment and use;
and 6, introducing gaseous carbon dioxide discharged after spraying in the elution tower into a dry ice generator to prepare dry ice.
Introducing chlorination process waste gas generated in chlorination and oxidation procedures in the production process of titanium dioxide by a chlorination method into an electromagnetic induction oxidation reactor, and adding a proper amount of 950 ℃ oxygen and a crystal form conversion agent to enable TiCl contained in the waste gas to be in a TiCl-containing state4Oxidation to rutile TiO2Conversion of CO to CO2Formation of TiO2、Cl2And CO2The gas-solid mixture is subjected to gas-solid separation treatment to obtain rutile TiO2The method is a valuable resource which can be directly utilized, wherein the conversion rate of the rutile type titanium dioxide is 99.06 percent. Cl2And CO2The formed dilute hydrochloric acid can be recycled through acid leaching separation, and CO is2The gas is sent to a dry ice generator to be finally prepared into dry ice for sale. Fully recovering CO and CO in the waste gas discharged by the titanium white chloride process production2And Cl2。
The invention effectively recycles the waste gas generated in the industrial production of titanium white by a chlorination process to obtain hydrochloric acid solution and rutile TiO2And the dry ice can effectively control the greenhouse gas emission generated in the production of the titanium white process by the chlorination process, meets the requirements of China on carbon emission peak reaching and carbon neutralization standards, and the chlorination process titanium white process is strengthened by chemical processes, so that green production is really realized, and finally formed byproducts also have certain economic utilization value.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. Method for preparing rutile TiO by using waste gas of titanium white process by chlorination process2And dry ice, characterized in that it comprises: waste gas generated in the chlorination process in the production process of titanium dioxide by chlorination process andand (3) reacting the waste gas in the oxidation process with hot oxygen under the condition of a crystal conversion agent, separating a reaction product to obtain rutile titanium dioxide particles, spraying the separated gas to obtain a dilute hydrochloric acid solution, and preparing the gas subjected to spraying treatment into dry ice.
2. The process for preparing rutile TiO according to claim 1 using waste gas from titanium dioxide chloride process2And a dry ice method, which is characterized in that the chlorination process waste gas and the oxidation process waste gas in the chlorination process titanium dioxide production process react with hot oxygen under the condition of a crystal conversion agent, and the method comprises the following steps:
step 1, introducing the chlorination process waste gas and the oxidation process waste gas into an oxidation reactor;
step 2, introducing the hot oxygen into the oxidation reactor, and simultaneously adding a crystal form conversion agent into the oxidation reactor;
and 3, carrying out oxidation reaction on the chlorination process waste gas, the oxidation process waste gas and the hot oxygen at the temperature of 1550-1750 ℃, wherein rutile type titanium dioxide particles, gaseous carbon dioxide and gaseous chlorine exist in reaction products.
3. The process for preparing rutile TiO from the waste gas of titanium dioxide chloride process according to claim 22And dry ice, wherein the separating of the reaction product to obtain rutile titanium dioxide comprises: and (3) conveying the reaction product into a gas-solid separation bag filter to separate rutile type titanium dioxide particles, gaseous carbon dioxide and gaseous chlorine.
4. The process for preparing rutile TiO according to claim 3 using waste gas from titanium dioxide chloride process2And a method of dry ice, characterized in that the spraying of the separated gas to obtain a dilute hydrochloric acid solution comprises the following steps:
step a, introducing the separated gaseous carbon dioxide and gaseous chlorine into a leaching tower;
b, spraying water in the leaching tower, absorbing the gaseous chlorine to form a dilute hydrochloric acid solution, and discharging the gaseous carbon dioxide out of the leaching tower;
step c separating the dilute hydrochloric acid solution.
5. The method for preparing rutile TiO according to claim 4 by using waste gas of titanium dioxide process by chlorination process2And the method for preparing the dry ice is characterized in that the gas after the spraying treatment is prepared into the dry ice, and the method comprises the step of introducing gaseous carbon dioxide discharged after the spraying treatment in the elution tower into a dry ice generator to prepare the dry ice.
6. The process for preparing rutile TiO from the waste gas of titanium dioxide chloride process according to claim 22And dry ice, wherein the chlorination process off-gas comprises carbon dioxide, carbon monoxide, titanium tetrachloride, and chlorine.
7. The process for preparing rutile TiO from the waste gas of titanium dioxide chloride process according to claim 22And dry ice, wherein the oxidation process off-gas comprises chlorine gas and carbon dioxide.
8. The process for preparing rutile TiO from the waste gas of titanium dioxide chloride process according to claim 22And dry ice, characterized in that the hot oxygen is oxygen preheated to 850-950 ℃.
9. The process for preparing rutile TiO from the waste gas of titanium dioxide chloride process according to claim 22And dry ice, characterized in that the oxidation reactor is an electromagnetic induction oxidation reactor.
10. The method for preparing rutile TiO according to claim 4 by using waste gas of titanium dioxide process by chlorination process2And dry ice, characterized in that in step b, water and dilute hydrochloric acid are sprayed in the leaching tower to absorb gaseous chlorine.
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| CN113274865A (en) * | 2021-06-29 | 2021-08-20 | 蚌埠中瓷纳米科技有限公司 | Titanium tetrachloride tail gas treatment system and method |
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