CN109734129B - Method for producing refined zirconium tetrachloride and byproduct silicon tetrachloride by zirconium silicate ball-making boiling chlorination process - Google Patents
Method for producing refined zirconium tetrachloride and byproduct silicon tetrachloride by zirconium silicate ball-making boiling chlorination process Download PDFInfo
- Publication number
- CN109734129B CN109734129B CN201910214378.4A CN201910214378A CN109734129B CN 109734129 B CN109734129 B CN 109734129B CN 201910214378 A CN201910214378 A CN 201910214378A CN 109734129 B CN109734129 B CN 109734129B
- Authority
- CN
- China
- Prior art keywords
- zirconium
- tetrachloride
- silicon tetrachloride
- zirconium silicate
- boiling chlorination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Silicon Compounds (AREA)
Abstract
A method for producing refined zirconium tetrachloride and by-product silicon tetrachloride by a zirconium silicate ball-making boiling chlorination method comprises the steps of weighing raw materials of zirconium silicate, a reducing agent, a lubricating agent and an adhesive, putting the raw materials into a powerful ball-making machine to prepare zirconium silicate mixture particles, drying the zirconium silicate mixture particles, feeding the zirconium silicate mixture particles into a 680-1050 ℃ boiling chlorination furnace, introducing chlorine to carry out boiling chlorination reaction, filtering a product zirconium tetrachloride and silicon tetrachloride mixed gas after chlorination reaction by a metal filtering separator, feeding the zirconium tetrachloride and silicon tetrachloride mixed gas into a molten salt spray tower, spraying the zirconium tetrachloride and the silicon tetrachloride mixed gas by molten salt spraying, filtering the zirconium tetrachloride and the silicon tetrachloride mixed gas by the metal filtering separator, cooling the zirconium tetrachloride cooler, carrying out gas-solid separation by a cloth bag separator, and carrying out silicon tetrachloride freezing collection to respectively obtain. The advantages are that: the method has the advantages of simple process, easy operation, low cost, high purity of the target zirconium tetrachloride product, and capability of producing the organic silicon compound by using the byproduct silicon tetrachloride, realizing zero discharge of industrial production waste, saving energy and protecting environment.
Description
Technical Field
The invention relates to a method for producing refined zirconium tetrachloride, in particular to a method for producing refined zirconium tetrachloride and by-product silicon tetrachloride by using zirconium silicate powder to prepare balls and adopting a large-scale boiling chlorination method.
Background
The refined zirconium tetrachloride product has wide application, is an intermediate of a zirconium product, has large market demand, can produce zirconium oxychloride, has 90 percent of the production capacity of zirconium oxychloride in China all over the world, and has the capacity of about 24 million tons. However, because of limited capacity of zirconium tetrachloride, the zirconium oxychloride produced in China at present is produced by adopting a 'one acid and one alkali method' with zircon sand as a raw material, the process flow is long, the production cost is high, the discharge amount of NaCl-containing wastewater is large, the silicon slag is not digested and converted, the environmental pollution treatment difficulty is large, the product quality cannot directly reach the quality standard of the zirconium oxychloride, and high-grade zirconium oxide enterprises need to extract and remove impurities such as iron and the like or recrystallize the purchased zirconium oxychloride to reduce the content of the impurities, so that the production cost is increased.
The refined zirconium tetrachloride can also be directly used for producing industrial grade sponge zirconium, the annual output of the industrial grade sponge zirconium at the present stage of China is about 1500 tons, and the selling price is 23.5 ten thousand yuan per ton. As the high-speed railway wire of the train is more than 350 kilometers in particular, and the use amount of amorphous alloy is increased, the market demand is increased year by year, the demand of the raw material zirconium tetrachloride is increased, the crude zirconium tetrachloride is produced by boiling chlorination of the electric melting desilicated zirconium at the present stage, the cost of the electric melting desilicated zirconium raw material is high, and the selling price is about 3.4 ten thousand yuan/ton.
Silicon tetrachloride is a main raw material for producing an organic silicon compound, such as organic silicon resin, high-temperature insulating varnish, organic silicone oil, and silicone rubber. High-purity silicon tetrachloride is a material for manufacturing polycrystalline silicon, high-purity silicon dioxide, inorganic silicon compounds and optical fibers, and is also a good raw material for gas-phase-method silicon dioxide.
CN 104817110A discloses a method for producing high-purity zirconium oxychloride and co-producing silicon tetrachloride by a zircon sand boiling chlorination method, which adopts a flow-state chlorination reaction of a zircon sand boiling chlorination furnace, raw materials with different particle sizes are easy to layer after chlorine gas purging, the contact between the raw material zircon sand and a reducing agent is easy to be insufficient, so that the reaction speed is influenced, the reaction temperature of the whole process is high, the reaction speed is slow, and the reaction is insufficient.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for producing refined zirconium tetrachloride and by-product silicon tetrachloride by a zirconium silicate ball-making boiling chlorination method, which has the advantages of simple process, easy operation, low cost, high purity of the target zirconium tetrachloride product, and by-product silicon tetrachloride capable of being used for preparing organic silicon compounds, realizes zero discharge of industrial production wastes, and is energy-saving and environment-friendly.
The technical scheme adopted by the invention is as follows:
a method for producing refined zirconium tetrachloride and by-product silicon tetrachloride by zirconium silicate ball-making boiling chlorination comprises the following specific steps:
(1) weighing raw materials of zirconium silicate, a reducing agent, a lubricant and a bonding agent, wherein the reducing agent is carbon black fine powder or carburant fine powder; the lubricant is high-purity graphite powder; the binder is paper pulp, syrup, rice pulp, pectin or cellulose; wherein the mass ratio of the zirconium silicate to the reducing agent to the lubricant to the binder is 1: 0.1-1: 0.12, the mass ratio of the zirconium silicate to the reducing agent to the lubricant to the binder is 1: 0.08-1: 0.12, and the mass ratio of the zirconium silicate to the binder is 1: 0.05-1: 0.1;
(2) firstly, adding solid zirconium silicate, a reducing agent and a lubricating agent, and then adding a binder to a powerful ball making machine to prepare zirconium silicate mixture particles with the diameter of 0.3-3 mm; drying the spherulites after the spherulites are taken out of the machine by microwave oven drying equipment, wherein the drying temperature is not more than 380 ℃; directly conveying the dried zirconium silicate mixture particles to a metering and feeding bin in front of a boiling chlorination furnace;
(3) feeding materials when the boiling chlorination furnace reaches 680-1050 ℃, introducing chlorine into the boiling chlorination furnace at the gas velocity of 0.15-0.36 m/s, keeping the temperature at 680-1050 ℃ for boiling chlorination reaction, and slagging off when the pressure in the furnace reaches 6500 Pa; the mass ratio of the zirconium silicate to the chlorine gas is 1: 1.355-1: 1.375;
(4) after chlorination reaction, the product zirconium tetrachloride and silicon tetrachloride mixed gas is settled and cooled in an expansion section of a boiling chlorination furnace, so that the temperature of the mixed gas is 410-430 ℃;
(5) filtering zirconium tetrachloride and silicon tetrachloride mixed gas obtained by a boiling chlorination furnace through a metal filtering separator, entering a molten salt spray tower, spraying the zirconium tetrachloride and silicon tetrachloride mixed gas filtered by the metal filtering separator by using NaCl and KCl mixture molten salt with the mass ratio of 1:1 as spray liquid, controlling the temperature of the molten salt spray tower at 450 ℃, wherein the mass ratio of the zirconium tetrachloride and silicon tetrachloride mixed gas to the molten salt is 1: 6; then cooling by a zirconium tetrachloride cooler, carrying out gas-solid separation by a cloth bag separator, and carrying out freeze leaching and collection on the silicon tetrachloride to respectively obtain refined zirconium tetrachloride and crude silicon tetrachloride.
Furthermore, the adhesive is paper pulp, syrup or rice pulp, the paper pulp, syrup or pectin can play a role in bonding, the paper pulp, syrup or pectin is carbonized after being dried by microwaves to play a role in increasing the carbon, and meanwhile, moisture volatilizes and substances are carbonized and shrunk, so that a plurality of micro holes are formed in the ball beads, and the specific surface area of reactants is increased.
Further, the zirconium silicate is powder obtained by carrying out airflow crushing on the zirconium silicate for ceramic; the ash content of the high-purity graphite powder is less than or equal to 10 ppm; the powder fineness of the reducing agent is-400 meshes and is more than 90%, and the powder fineness of the lubricating agent is-300 meshes and is more than 90%.
Further, when the molten salt is sprayed, the gas velocity of the mixed gas of zirconium tetrachloride and silicon tetrachloride entering the molten salt spraying tower is 2 m/s.
Furthermore, when the metal filtering separator filters, the temperature of the metal filter is controlled to be 330-370 ℃, so that dust and mixed gas carried by the mixed gas of zirconium tetrachloride and silicon tetrachloride are separated.
Further, when the zirconium tetrachloride cooler is cooled, the outlet temperature of the zirconium tetrachloride cooler is controlled at 180 ℃, the zirconium tetrachloride is cooled to be solid, the solid is collected, and the gas is continuously sent into a cloth bag separator to separate zirconium tetrachloride powder carried in the silicon tetrachloride gas.
Furthermore, the inlet temperature of the cloth bag separator is controlled at 160 ℃, and the outlet temperature of the cloth bag separator is controlled at 100 ℃.
Furthermore, when the silicon tetrachloride is frozen and leached, the silicon tetrachloride is sprayed by silicon tetrachloride liquid at the temperature of-10 ℃ so as to liquefy the silicon tetrachloride gas.
Further, the mass ratio of the zirconium silicate to the reducing agent, the lubricant and the binder is 1: 0.1-1: 0.12, 1: 0.093-1: 0.12 and 1: 0.07-1: 0.1 respectively.
Furthermore, the inner diameter of the boiling chlorination furnace is 850 mm-1500 mm.
The invention has the beneficial effects that:
the invention takes zirconium silicate powder as main raw material, adds chemical reaction reducing agent (carbon black or carburant), and adds lubricant (graphite powder, also reducing agent) and binder (paper pulp, syrup, rice pulp, pectin, cellulose) to mix and force to make balls, after microwave drying, chloridizes by large boiling chlorination furnace to obtain mixed gas of zirconium tetrachloride, silicon tetrachloride and the like, and obtains high-purity refined zirconium tetrachloride solid and crude silicon tetrachloride liquid by advanced metal separation, molten salt spraying technology, rapid condensation and gas-solid separation, and has the advantages that:
1. the product obtained by the invention has good quality
Boiling chlorination comparison, as in table 1:
the content of the crude silicon tetrachloride is 90-92%. The grade of the silicon tetrachloride is much higher than that of 78 percent of crude silicon tetrachloride chloridized by zircon sand.
2. The production cost is low, and the obtained refined zirconium tetrachloride does not need to be reduced by recharging hydrogen or purified by fused salt.
3. The reaction area of the materials is increased by pelletizing the zirconium silicate fine powder, the carbon black, the graphite powder, the paper pulp and the like, the reaction speed is accelerated, the problem of layering due to the fact that the particle size of an oxide is not matched with that of a reducing agent does not exist in fixed particles of reactants, and the structure of the selected reducing agent carbon black or a carburant is better than that of petroleum calcined coke used for boiling chlorination of electric melting desiliconized zirconium and zircon sand, and the reaction speed is high.
4. The graphite powder is added to be the lubricant, so that the friction force between the reaction material and the graphite of the heating element is reduced, the service life of the heating element is prolonged, and the function of the reducing agent is realized.
5. The total carbon preparation amount is scientific and reasonable, the boiling chlorination does not need to frequently slag, the reaction speed is high, and the reaction temperature is low.
6. The gas velocity is higher under the same furnace diameter, so the invention has more material feeding and high productivity.
The method for producing the refined zirconium tetrachloride and the byproduct silicon tetrachloride can produce the refined zirconium tetrachloride product and the byproduct silicon tetrachloride, has the advantages of large profit, high added value of the product and no solid waste discharge, belongs to a clean production technology, can solve the problems of high production cost, low profit and difficult treatment of environmental pollution in the whole zirconium oxychloride industry, and improves the grade of the zirconium product.
Detailed Description
Example 1
The preparation method is implemented according to a process flow diagram, and comprises the following specific steps:
1) raw material preparation
Weighing raw materials of zirconium silicate powder, carbon black, high-purity graphite powder (ash content is less than or equal to 10ppm) and pulp according to the mass ratio of 1:0.1:0.096:0.07, adding the raw materials into a powerful ball making machine, adding the zirconium silicate powder, the carbon black and the graphite powder during feeding, adding a binder, making balls, preparing zirconium silicate mixture particles with the average particle size of 0.85mm, wherein the balling rate is more than 98.5%, then putting the particles into a microwave dryer, and drying the particles at the temperature of 360 +/-20 ℃;
the raw material components are required to be as follows: zirconium oxide and hafnium oxide combined amount (ZrHf) O in zirconium silicate powder2≥63.5％；
The particle size requirements of the raw materials are as follows: zirconium silicate powder D50≤2.0μmm，D98Less than or equal to 10.0 mu mm; carbon black of-400 mesh>90 percent; graphite powder-300 mesh>90％；
2) Chlorination reaction
Adding the dried zirconium silicate mixture particles into a stokehold bin, continuously adding the mixture particles into a boiling chlorination furnace with the inner diameter of 850mm through a screw conveyor, introducing chlorine at the bottom of the boiling chlorination furnace, reacting the chlorine with the zirconium silicate mixture particles to generate mixed gas of zirconium tetrachloride and silicon tetrachloride, controlling the reaction temperature to be 950 ℃, the introduction speed of the chlorine to be 0.236m/s, controlling the pressure of a hearth to be within the range of 3000 Pa-6500 Pa, and skimming when the pressure in the furnace reaches 6500Pa, wherein the mass ratio of the zirconium silicate mixture particles to the chlorine is 1: 1.375; the mixed gas of zirconium tetrachloride and silicon tetrachloride which is the product of chlorination reaction is settled and cooled in an expansion section of a boiling chlorination furnace, so that the cooling temperature of the mixed gas is 410 ℃;
3) purifying and separating zirconium tetrachloride and by-product crude silicon tetrachloride
Then, allowing the zirconium tetrachloride and silicon tetrachloride mixed gas to enter a metal filter, and performing gas-solid separation on dust and the mixed gas carried by the zirconium tetrachloride and silicon tetrachloride mixed gas through sedimentation and filtration of a metal sintering net in the metal filter, wherein the temperature of the metal filter is controlled at 330 ℃;
the gas separated by the metal filter enters a molten salt spray tower, NaCl and KCl molten salt with the mass ratio of 1:1 are sprayed, the tower temperature is controlled at 450 ℃, and the mixed gas of zirconium tetrachloride and silicon tetrachloride is washed by the molten salt, so that impurities containing Fe, Ti and Al and the molten salt form complex salt to be removed;
zirconium tetrachloride and silicon tetrachloride gas which are washed by molten salt spraying enter a zirconium tetrachloride cooler, the outlet temperature of the zirconium tetrachloride cooler is controlled at 180 ℃, the cooled zirconium tetrachloride is solid, the solid is collected to obtain refined zirconium tetrachloride, and the gas is continuously sent into a cloth bag separator;
the gas cooled by the zirconium tetrachloride cooler is silicon tetrachloride gas carrying a small amount of zirconium tetrachloride solid powder, and enters a cloth bag separator, the outlet temperature of the cloth bag separator is controlled at 100 ℃, the inlet temperature of the cloth bag separator is controlled at 160 ℃, so that the silicon tetrachloride gas and the zirconium tetrachloride solid powder are subjected to gas-solid separation by a cloth bag, and the solid is collected, namely the refined zirconium tetrachloride;
spraying and absorbing the silicon tetrachloride gas subjected to gas-solid separation by using a cloth bag separator by using silicon tetrachloride liquid at the temperature of below 10 ℃ below zero to obtain silicon tetrachloride liquid (SiCl)4) The purity of the silicon tetrachloride is detected>90％。
Example 2
The preparation method is implemented according to a process flow diagram, and comprises the following specific steps:
1) raw material preparation
Weighing raw materials of zirconium silicate powder, carbon black, high-purity graphite powder (ash content is less than or equal to 10ppm) and syrup according to the mass ratio of 1:0.11:0.093:0.07, adding the raw materials into a powerful ball making machine, adding the zirconium silicate powder, the carbon black and the graphite powder during feeding, adding a binder, making balls to prepare zirconium silicate mixture particles with the average particle size of 0.75mm, wherein the balling rate is more than 98.5%, then putting the zirconium silicate mixture particles into a microwave dryer, and drying the zirconium silicate mixture particles at the temperature of 360 +/-20 ℃;
the raw material components are required to be as follows: zirconium oxide and hafnium oxide combined amount (ZrHf) O in zirconium silicate powder2≥63.5％；
The particle size requirements of the raw materials are as follows: zirconium silicate powder D50≤2.0μmm，D98Less than or equal to 10.0 mu mm; carbon black of-400 mesh>90 percent; graphite powder-300 mesh>90％；
2) Chlorination reaction
Adding the dried zirconium silicate mixture particles into a stokehold bin, continuously adding the mixture particles into a boiling chlorination furnace through a screw conveyor, introducing chlorine at the bottom of the boiling chlorination furnace, reacting the chlorine with the zirconium silicate mixture particles to generate mixed gas of zirconium tetrachloride and silicon tetrachloride, controlling the reaction temperature to be 900 ℃, the introduction speed of the chlorine to be 0.258m/s, controlling the pressure of a hearth to be within the range of 3000-6500 Pa, and skimming when the pressure in the furnace reaches 6500Pa, wherein the introduced chlorine has the mass: the mass ratio of the zirconium silicate mixture particles to the chlorine gas is 1:1.355,
the mixed gas of zirconium tetrachloride and silicon tetrachloride which is the product of chlorination reaction is settled and cooled in an expansion section of a boiling chlorination furnace, so that the cooling temperature of the mixed gas is 410 ℃;
3) purifying and separating zirconium tetrachloride and by-product crude silicon tetrachloride
Then, allowing the mixed gas of zirconium tetrachloride and silicon tetrachloride to enter a metal filter, and performing gas-solid separation on dust carried by the mixed gas of zirconium tetrachloride and silicon tetrachloride and the mixed gas through sedimentation and filtration of a metal sintering net in the metal filter, wherein the temperature of the metal filter is controlled at 350 ℃;
the gas separated by the metal filter enters a molten salt spray tower, NaCl and KCl molten salt with the mass ratio of 1:1 are sprayed, the tower temperature is controlled at 450 ℃, and the mixed gas of zirconium tetrachloride and silicon tetrachloride is washed by the molten salt, so that impurities containing Fe, Ti and Al and the molten salt form complex salt to be removed;
zirconium tetrachloride and silicon tetrachloride gas which are washed by molten salt spraying enter a zirconium tetrachloride cooler, the outlet temperature of the zirconium tetrachloride cooler is controlled at 180 ℃, the cooled zirconium tetrachloride is solid, the solid is collected to obtain refined zirconium tetrachloride, and the gas is continuously sent into a cloth bag separator;
the gas cooled by the zirconium tetrachloride cooler is silicon tetrachloride gas carrying a small amount of zirconium tetrachloride solid powder, and enters a cloth bag separator, the outlet temperature of the cloth bag separator is controlled at 100 ℃, the inlet temperature of the cloth bag separator is controlled at 160 ℃, so that the silicon tetrachloride gas and the zirconium tetrachloride solid powder are subjected to gas-solid separation by a cloth bag, and the solid is collected, namely the refined zirconium tetrachloride;
spraying and absorbing the silicon tetrachloride gas subjected to gas-solid separation by using a cloth bag separator by using silicon tetrachloride liquid at the temperature of below 10 ℃ below zero to obtain silicon tetrachloride liquid (SiCl)4) The purity of the silicon tetrachloride is detected>90％。
Example 3
The preparation method is implemented according to a process flow diagram, and comprises the following specific steps:
1) raw material preparation
Zirconium silicate powder, carbon black, high-purity graphite powder (ash content is less than or equal to 10ppm) and pulp are mixed according to the mass ratio of 1:0.12: 0.093:0.07 weighing raw materials, adding into a powerful ball making machine, adding zirconium silicate powder, carbon black and graphite powder during feeding, adding a binder, making balls to prepare zirconium silicate mixture particles with the average particle size of 1.2mm, wherein the balling rate is more than 98.5%, then putting into a microwave dryer, and drying at 360 +/-20 ℃;
as described aboveThe raw material components are required to be as follows: zirconium oxide and hafnium oxide combined amount (ZrHf) O in zirconium silicate powder2≥63.5％；
The particle size requirements of the raw materials are as follows: zirconium silicate powder D50≤2.0μmm，D98Less than or equal to 10.0 mu mm; carbon black of-400 mesh>90 percent; graphite powder-300 mesh>90％；
2) Chlorination reaction
Adding the dried zirconium silicate mixture particles into a stokehold bin, continuously adding the mixture particles into a boiling chlorination furnace through a screw conveyor, introducing chlorine at the bottom of the boiling chlorination furnace, reacting the chlorine with the zirconium silicate mixture particles to generate mixed gas of zirconium tetrachloride and silicon tetrachloride, controlling the reaction temperature to be 1000 ℃, the introduction speed of the chlorine to be 0.296/s, controlling the hearth pressure to be within the range of 3000-6500 Pa, and slagging off when the pressure in the furnace reaches 6500Pa, wherein the introduced chlorine has the mass: the mass ratio of the zirconium silicate mixture particles to the chlorine gas is 1: 1.355; the mixed gas of zirconium tetrachloride and silicon tetrachloride which is the product of chlorination reaction is settled and cooled in an expansion section of a boiling chlorination furnace, so that the cooling temperature of the mixed gas is 430 ℃;
3) purifying and separating zirconium tetrachloride and by-product crude silicon tetrachloride
Then, allowing the mixed gas of zirconium tetrachloride and silicon tetrachloride to enter a metal filter, performing gas-solid separation on dust carried by the mixed gas of zirconium tetrachloride and silicon tetrachloride and the mixed gas through sedimentation and filtration of a metal sintering net in the metal filter, controlling the temperature of the metal filter to be 370 ℃, and preparing particles again from the separated solid and allowing the particles to enter a molten salt chlorination furnace for chlorination reaction;
the gas separated by the metal filter enters a molten salt spray tower, NaCl and KCl molten salt with the mass ratio of 1:1 are sprayed, the tower temperature is controlled at 450 ℃, and the mixed gas of zirconium tetrachloride and silicon tetrachloride is washed by the molten salt, so that impurities containing Fe, Ti and Al and the molten salt form complex salt to be removed;
zirconium tetrachloride and silicon tetrachloride gas which are washed by molten salt spraying enter a zirconium tetrachloride cooler, the outlet temperature of the zirconium tetrachloride cooler is controlled at 180 ℃, the cooled zirconium tetrachloride is solid, the solid is collected to obtain refined zirconium tetrachloride, and the gas is continuously sent into a cloth bag separator;
the gas cooled by the zirconium tetrachloride cooler is silicon tetrachloride gas carrying a small amount of zirconium tetrachloride solid powder, and enters a cloth bag separator, the outlet temperature of the cloth bag separator is controlled at 100 ℃, the inlet temperature of the cloth bag separator is controlled at 160 ℃, so that the silicon tetrachloride gas and the zirconium tetrachloride solid powder are subjected to gas-solid separation by a cloth bag, and the solid is collected, namely the refined zirconium tetrachloride;
spraying and absorbing the silicon tetrachloride gas subjected to gas-solid separation by using a cloth bag separator by using silicon tetrachloride liquid at the temperature of below 10 ℃ below zero to obtain silicon tetrachloride liquid (SiCl)4) The purity of the silicon tetrachloride is detected>90％。
Example 4
1) Preparing raw materials:
weighing raw materials of zirconium silicate powder, carbon black, high-purity graphite powder (ash content is less than or equal to 10ppm) and pulp according to the mass ratio of 1:0.1:0.08: 0.075; preparing zirconium silicate mixture particles with the average particle size of 0.3 mm;
2) chlorination reaction
The reaction temperature of the boiling chlorination furnace is 680 ℃, the introduction speed of chlorine is 0.15m/s, and the mass ratio of zirconium silicate mixture particles to chlorine is 1: 1.355; the mixed gas of zirconium tetrachloride and silicon tetrachloride which is the product of chlorination reaction is settled and cooled in an expansion section of a boiling chlorination furnace, so that the cooling temperature of the mixed gas is 410 ℃;
the rest is the same as in example 1.
Example 5
1) Raw material preparation
Weighing raw materials of zirconium silicate powder, carbon black, high-purity graphite powder (ash content is less than or equal to 10ppm) and pulp according to the mass ratio of 1:0.12:0.1: 0.1; preparing zirconium silicate mixture particles with the average particle size of 3 mm;
2) chlorination reaction
The reaction temperature of the boiling chlorination furnace is 1050 ℃, the introducing speed of chlorine is 0.36m/s, and the mass ratio of zirconium silicate mixture particles to the chlorine is 1: 1.355; the mixed gas of zirconium tetrachloride and silicon tetrachloride which is the product of chlorination reaction is settled and cooled in an expansion section of a boiling chlorination furnace, so that the cooling temperature of the mixed gas is 430 ℃;
the rest is the same as in example 1.
Comparative example 1
The method adopts petroleum coke as a reducing agent, and the mass ratio of zirconium silicate to the petroleum coke is 1: 0.24, the reaction temperature was 1150 ℃ and the gas velocity was 0.2165m/s, otherwise the same as in example 1.
Example yield control tables are shown in table 2:
TABLE 2
| Name (R) | Zirconium silicate powder, carbon black, graphite powder and paper pulp according to mass ratio | Raw material chlorine ratio | Reaction temperature C | Zirconium tetrachloride yield kg/h |
| Example 1 | 1：0.1：0.096：0.07 | 1：1.375 | 950 | 268 |
| Example 2 | 1：0.11：0.093：0.07 | 1：1.355 | 900 | 310 |
| Example 3 | 1：0.12：0.093：0.07 | 1：1.355 | 1000 | 326 |
| Example 4 | 1：0.1：0.12：0.75 | 1：1.355 | 680 | 219 |
| Example 5 | 1：0.12：0.1：0.1 | 1：1.355 | 1050 | 378 |
| Comparative example 1 | 1:0.24 | 1：1.24 | 1150 | 245 |
The indexes of zirconium tetrachloride products in examples 1 to 4 of the present invention are shown in Table 3
TABLE 3
The zirconium tetrachloride produced by the existing method does not need to be purified again. Can directly produce industrial grade sponge zirconium, and the direct cost of the sponge zirconium is reduced by about 25 percent.
Diameter 850 yields ratio as shown in table 4:
TABLE 4
| Method of producing a composite material | Temperature of | Raw material Kg/h | Air velocity m/S | Zirconium tetrachloride Kg/h |
| Boiling chlorination of zircon sand | 1150 | 248 | 0.236 | 239 |
| Example 1 | 950 | 340 | 0.236 | 268 |
| Example 2 | 900 | 313 | 0.258 | 310 |
| Example 3 | 1000 | 331 | 0.296 | 326 |
| Example 4 | 680 | 223.6 | 0.15 | 219 |
| Example 5 | 1050 | 387 | 0.36 | 378 |
| Comparative example 1 | 1150 | 254.5 | 0.2165 | 245 |
In the above table, zircon sand is boiled and chloridized to be prior art, wherein the reducing agent is petroleum coke.
The above description is only exemplary of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for producing refined zirconium tetrachloride and by-product silicon tetrachloride by zirconium silicate ball-making boiling chlorination is characterized by comprising the following steps:
the method comprises the following specific steps:
(1) weighing raw materials of zirconium silicate, a reducing agent, a lubricant and a binder, wherein the reducing agent is carbon black fine powder or carburant fine powder; the lubricant is high-purity graphite powder; the binder is paper pulp, syrup, rice pulp, pectin or cellulose; wherein the mass ratio of the zirconium silicate to the reducing agent to the lubricant to the binder is 1: 0.1-1: 0.12, the mass ratio of the zirconium silicate to the reducing agent to the lubricant to the binder is 1: 0.08-1: 0.12, and the mass ratio of the zirconium silicate to the binder is 1: 0.05-1: 0.1;
(2) firstly, adding solid zirconium silicate, a reducing agent and a lubricating agent, and then adding a binder to a powerful ball making machine to prepare zirconium silicate mixture particles with the diameter of 0.3-3 mm; drying the spherulites after the spherulites are taken out of the machine by microwave oven drying equipment, wherein the drying temperature is not more than 380 ℃; directly conveying the dried zirconium silicate mixture particles to a metering and feeding bin in front of a boiling chlorination furnace;
(3) feeding materials when the boiling chlorination furnace reaches 680-1050 ℃, introducing chlorine into the boiling chlorination furnace at the gas velocity of 0.15-0.36 m/s, keeping the temperature at 680-1050 ℃ for boiling chlorination reaction, and slagging off when the pressure in the furnace reaches 6500 Pa; the mass ratio of the zirconium silicate to the chlorine gas is 1: 1.355-1: 1.375;
(4) after chlorination reaction, the product zirconium tetrachloride and silicon tetrachloride mixed gas is settled and cooled in an expansion section of a boiling chlorination furnace, so that the temperature of the mixed gas is 410-430 ℃;
(5) filtering zirconium tetrachloride and silicon tetrachloride mixed gas obtained by a boiling chlorination furnace through a metal filtering separator, entering a molten salt spray tower, spraying the zirconium tetrachloride and silicon tetrachloride mixed gas filtered by the metal filtering separator by using NaCl and KCl mixture molten salt with the mass ratio of 1:1 as spray liquid, controlling the temperature of the molten salt spray tower at 450 ℃, wherein the mass ratio of the zirconium tetrachloride and silicon tetrachloride mixed gas to the molten salt is 1: 6; then cooling by a zirconium tetrachloride cooler, carrying out gas-solid separation by a cloth bag separator, and carrying out freeze leaching and collection on the silicon tetrachloride to respectively obtain refined zirconium tetrachloride and crude silicon tetrachloride.
2. The method for producing refined zirconium tetrachloride and silicon tetrachloride as a byproduct by the zirconium silicate ball boiling chlorination process as claimed in claim 1, which comprises the following steps: the binder is paper pulp, syrup or rice pulp.
3. The method for producing refined zirconium tetrachloride and silicon tetrachloride as a byproduct by the zirconium silicate ball boiling chlorination process as claimed in claim 1, which comprises the following steps: the zirconium silicate is powder obtained by carrying out airflow crushing on zirconium silicate for ceramic; the ash content of the high-purity graphite powder is less than or equal to 10 ppm; the powder fineness of the reducing agent is-400 meshes and is more than 90%, and the powder fineness of the lubricating agent is-300 meshes and is more than 90%.
4. The method for producing refined zirconium tetrachloride and silicon tetrachloride as a byproduct by the zirconium silicate ball boiling chlorination process as claimed in claim 1, which comprises the following steps: when molten salt is sprayed, the gas velocity of the zirconium tetrachloride and silicon tetrachloride mixed gas entering the molten salt spraying tower is 2 m/s.
5. The method for producing refined zirconium tetrachloride and silicon tetrachloride as a byproduct by the zirconium silicate ball boiling chlorination process as claimed in claim 1, which comprises the following steps: when the metal filtering separator filters, the temperature of the metal filter is controlled to be 330-370 ℃, so that dust carried by the mixed gas of zirconium tetrachloride and silicon tetrachloride is separated from the mixed gas.
6. The method for producing refined zirconium tetrachloride and silicon tetrachloride as a byproduct by the zirconium silicate ball boiling chlorination process as claimed in claim 1, which comprises the following steps: when the zirconium tetrachloride cooler is cooled, the outlet temperature of the zirconium tetrachloride cooler is controlled at 180 ℃, the zirconium tetrachloride is cooled to be solid, the solid is collected, and the gas is continuously sent into a cloth bag separator to separate zirconium tetrachloride powder carried in the silicon tetrachloride gas.
7. The method for producing refined zirconium tetrachloride and silicon tetrachloride as a byproduct by the zirconium silicate ball boiling chlorination process as claimed in claim 1, which comprises the following steps: the inlet temperature of the bag-type separator is controlled at 160 ℃, and the outlet temperature of the bag-type separator is controlled at 100 ℃.
8. The method for producing refined zirconium tetrachloride and silicon tetrachloride as a byproduct by the zirconium silicate ball boiling chlorination process as claimed in claim 1, which comprises the following steps: when the silicon tetrachloride is frozen and leached, the silicon tetrachloride is sprayed by silicon tetrachloride liquid with the temperature of minus 10 ℃ so as to liquefy the silicon tetrachloride gas.
9. The method for producing refined zirconium tetrachloride and silicon tetrachloride as a byproduct by the zirconium silicate ball boiling chlorination process as claimed in claim 1, which comprises the following steps: the mass ratio of the zirconium silicate to the reducing agent to the lubricant to the binder is 1: 0.1-1: 0.12, the mass ratio of the zirconium silicate to the reducing agent to the lubricant to the binder is 1: 0.093-1: 0.12, and the mass ratio of the zirconium silicate to the binder is 1: 0.07-1: 0.1.
10. The method for producing refined zirconium tetrachloride and silicon tetrachloride as a byproduct by the zirconium silicate ball boiling chlorination process as claimed in claim 1, which comprises the following steps: the inner diameter of the boiling chlorination furnace is 850 mm-1500 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910214378.4A CN109734129B (en) | 2019-03-20 | 2019-03-20 | Method for producing refined zirconium tetrachloride and byproduct silicon tetrachloride by zirconium silicate ball-making boiling chlorination process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910214378.4A CN109734129B (en) | 2019-03-20 | 2019-03-20 | Method for producing refined zirconium tetrachloride and byproduct silicon tetrachloride by zirconium silicate ball-making boiling chlorination process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109734129A CN109734129A (en) | 2019-05-10 |
| CN109734129B true CN109734129B (en) | 2021-02-09 |
Family
ID=66371051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910214378.4A Active CN109734129B (en) | 2019-03-20 | 2019-03-20 | Method for producing refined zirconium tetrachloride and byproduct silicon tetrachloride by zirconium silicate ball-making boiling chlorination process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109734129B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240196B (en) * | 2019-07-31 | 2020-11-13 | 辽宁华祥新材料有限公司 | Method for preparing zirconium tetrachloride by zircon sand boiling chlorination method and zirconium tetrachloride |
| CN110846935A (en) * | 2019-11-29 | 2020-02-28 | 湖北淡雅香生物科技股份有限公司 | Preparation method of tipping base paper for flexographic printing |
| CN111268683B (en) * | 2019-12-30 | 2023-10-27 | 武汉新硅科技潜江有限公司 | Reaction ignition device and ignition method for preparing silicon tetrachloride by chlorination of silicon powder |
| CN113184904B (en) * | 2021-06-15 | 2023-02-14 | 辽宁华锆新材料有限公司 | Method and equipment for purifying zirconium tetrachloride |
| CN115744975B (en) * | 2022-10-31 | 2024-05-07 | 新疆晶硕新材料有限公司 | Zirconium tetrachloride apparatus for producing |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5091592A (en) * | 1973-12-17 | 1975-07-22 | ||
| KR20130076195A (en) * | 2011-12-28 | 2013-07-08 | 주식회사 포스코 | Method for preparing zirconium tetrachloride of high purity and zirconium sponge |
| CN105174307A (en) * | 2015-08-25 | 2015-12-23 | 王卓 | Method for cooling zirconium tetrachloride produced through fluidizing chlorination method |
| CN105565377A (en) * | 2015-12-31 | 2016-05-11 | 淄博广通化工有限责任公司 | Method for preparing zirconium tetrachloride through fluidizing chlorination of zircon sand with silicon tetrachloride as byproduct |
| CN109252057A (en) * | 2018-09-25 | 2019-01-22 | 李梅 | A kind of fused salt chlorimation extracting method of low-grade zircon concentrate |
-
2019
- 2019-03-20 CN CN201910214378.4A patent/CN109734129B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5091592A (en) * | 1973-12-17 | 1975-07-22 | ||
| KR20130076195A (en) * | 2011-12-28 | 2013-07-08 | 주식회사 포스코 | Method for preparing zirconium tetrachloride of high purity and zirconium sponge |
| CN105174307A (en) * | 2015-08-25 | 2015-12-23 | 王卓 | Method for cooling zirconium tetrachloride produced through fluidizing chlorination method |
| CN105565377A (en) * | 2015-12-31 | 2016-05-11 | 淄博广通化工有限责任公司 | Method for preparing zirconium tetrachloride through fluidizing chlorination of zircon sand with silicon tetrachloride as byproduct |
| CN109252057A (en) * | 2018-09-25 | 2019-01-22 | 李梅 | A kind of fused salt chlorimation extracting method of low-grade zircon concentrate |
Non-Patent Citations (1)
| Title |
|---|
| 锆英砂直接氯化工艺;白鸿等;《沈阳化工》;20000930;第29卷;第146-151页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109734129A (en) | 2019-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109734129B (en) | Method for producing refined zirconium tetrachloride and byproduct silicon tetrachloride by zirconium silicate ball-making boiling chlorination process | |
| CN103130279B (en) | A kind of method of chlorination production high purity vanadic anhydride | |
| CN102515213A (en) | Integrated utilization method of low grade magnesite | |
| CN108046302B (en) | Method for producing high-purity hydrated lime from carbide slag | |
| CN101746765B (en) | Method and device for separating and purifying silicon dioxide micropowder from electric furnace dust | |
| CN105693250B (en) | A method of preparing boron carbide Ultramicro-powder with sapphire smooth grinding slug | |
| CN106747497A (en) | The method for preparing corundum-mullite composite diphase material | |
| CN103088208A (en) | Method for treating manganese-containing and phosphorus-containing hematite | |
| CN111057850B (en) | Method for preparing high-purity lithium metal by vacuum thermal reduction method | |
| CN101462767A (en) | Preparation of crude titanic chloride | |
| CN103818966A (en) | Large-specific surface area superfine powdery iron oxide red spray roasting method | |
| CN108588316A (en) | A method of recycling sintering machine head end electro-precipitating dust | |
| CN108906316A (en) | A method of desulfurizing agent is prepared using carbide slag | |
| CN113215394B (en) | Treatment method of stone coal | |
| CN105217589A (en) | The power-economizing method of yellow phosphorus coproduction sylvite, sodium carbonate and aluminum oxide | |
| CN113787085A (en) | Method for extracting Fe, Zn and Pb from electric furnace dust removal ash and realizing high-value utilization | |
| CN113753864A (en) | Method for co-production of mineral cotton fiber by using high-impurity phosphogypsum to prepare sulfuric acid | |
| CN109665817A (en) | A kind of metallurgical slag resource comprehensive utilization method | |
| CN103014196A (en) | Application method of blast furnace slag fine stuff | |
| CN110629054B (en) | Preparation device of manganese-rich slag | |
| CN102242282A (en) | Alkaline reduction smelting method for vanadium polymetallic ore | |
| CN210065203U (en) | System for producing refined zirconium tetrachloride by ball-making zirconium silicate boiling chlorination method | |
| CN110681868B (en) | Efficient and environment-friendly production method of high-performance forged manganese | |
| CN214600935U (en) | Electric smelting white alundum cooling dust collector | |
| CN110980753B (en) | Process for producing high-quality sodium silicate by adopting high-silicon iron ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |