阅读说明：本技术 一种熔盐提纯法制备精四氯化锆的方法及设备 (Method and equipment for preparing refined zirconium tetrachloride by molten salt purification method ) 是由 石玢 李小毅 于洋 徐玉坤 郑彦东 于 2021-10-20 设计创作，主要内容包括：本发明公开了一种熔盐提纯法制备精四氯化锆的方法及设备,包括以下步骤：S1：在低温容器中按比例配制氯化钾、氯化钠和粗四氯化锆,并在温度为235℃-350℃的条件下形成复合熔盐；S2：复合熔盐在温度为235℃-350℃的条件反应预设时间后,以4m～(3)/h-15m～(3)/h的流速输送至温度为350-480℃的高温容器中；S3：复合熔盐在350-480℃的高温容器内蒸发形成四氯化锆气体,对四氯化锆气体进行冷凝收集得到精四氯化锆,或者直接进入下一步骤；S4：复合熔盐从高温容器进入低温容器,同时向低温容器补充粗四氯化锆,并重复执行步骤S1～S4。本发明能够提高四氯化锆的纯度、产能并降低能耗。(The invention discloses a method and equipment for preparing refined zirconium tetrachloride by a molten salt purification method, which comprises the following steps: s1: preparing potassium chloride, sodium chloride and crude zirconium tetrachloride in proportion in a low-temperature container, and forming composite molten salt at the temperature of 235-350 ℃; s2: after the composite molten salt is reacted for a preset time at the temperature of 235-350 ℃, 4m 3 /h‑15m 3 The flow rate is conveyed to a high-temperature container with the temperature of 350-480 ℃; s3: evaporating the composite molten salt in a high-temperature container at 480 ℃ of 350-; s4: and (4) enabling the composite molten salt to enter the low-temperature container from the high-temperature container, simultaneously supplementing crude zirconium tetrachloride to the low-temperature container, and repeatedly executing the steps S1-S4. The method can improve the purity and the capacity of the zirconium tetrachloride and reduce the energy consumption.)

1. A method for preparing refined zirconium tetrachloride by a molten salt purification method is characterized by comprising the following steps:

s1: preparing potassium chloride, sodium chloride and crude zirconium tetrachloride in proportion in a low-temperature container, and forming composite molten salt at the temperature of 235-350 ℃;

s2: after the composite molten salt is reacted for a preset time at the temperature of 235-350 ℃, 4m³/h-15m³The flow rate is conveyed to a high-temperature container with the temperature of 350-480 ℃;

s3: evaporating the composite molten salt in a high-temperature container at 480 ℃ of 350-;

s4: and (4) enabling the composite molten salt to enter the low-temperature container from the high-temperature container, simultaneously supplementing crude zirconium tetrachloride to the low-temperature container, and repeatedly executing the steps S1-S4 until the purification is finished.

2. The method for preparing refined zirconium tetrachloride through the molten salt purification method according to claim 1, wherein in step S1, the mass ratio of potassium chloride to sodium chloride is 1: 1-1: 3, and the mass ratio of the sum of potassium chloride and sodium chloride to crude zirconium tetrachloride is 1: 9-7: 13.

3. The method for preparing refined zirconium tetrachloride according to the molten salt purification method of claim 1, wherein the preset time in the step S2 is 30min to 150 min.

4. The method for preparing refined zirconium tetrachloride according to the molten salt purification method of claim 1, characterized in that the collection of zirconium tetrachloride is performed by a condenser or a zirconium sponge reduction furnace in step S3.

5. The method for preparing refined zirconium tetrachloride according to claim 1, characterized in that the high-temperature container is an evaporation furnace with a baffled structure.

6. The method for preparing refined zirconium tetrachloride according to the molten salt purification method of claim 1, characterized in that the mass ratio of the crude zirconium tetrachloride supplemented in the step S4 to the refined zirconium tetrachloride collected in the step S3 is 1.05:1 to 1.2: 1.

7. The method for preparing refined zirconium tetrachloride according to the molten salt purification method of claim 1, wherein the flow rate of supplementing the crude zirconium tetrachloride in the step S4 is 1 ton/h to 4 tons/h.

8. The method for preparing refined zirconium tetrachloride according to claim 1, characterized in that the low-temperature container is a molten salt furnace with a baffled structure.

9. An apparatus for a method of preparing refined zirconium tetrachloride by a molten salt purification method according to any one of claims 1 to 7, comprising a low-temperature container, a high-temperature container, a condensing mechanism and a feeding mechanism;

a baffling structure is arranged in each of the low-temperature container and the high-temperature container;

the low-temperature container is provided with a first inlet, a first outlet and a material supplementing port for supplementing crude zirconium tetrachloride, the high-temperature container is provided with a second inlet, an overflow port and a condensation port, the first inlet is communicated with the overflow port, and the first outlet is communicated with the second inlet through the feeding mechanism;

the horizontal plane of the overflow port is higher than the horizontal plane of the first inlet, and the height difference is 1-1.5 m;

the condensation mechanism is arranged above the condensation port to condense and collect the fine zirconium tetrachloride.

Technical Field

The invention relates to the field of chemical raw material production, in particular to a method and equipment for preparing refined zirconium tetrachloride by a molten salt purification method.

Background

Zirconium tetrachloride can be used for preparing zirconium metal, pigment, textile waterproof agent, leather tanning agent, etc., can also be used for preparing zirconium compound and organic metal compound, can also be used as solvent and cleaning agent of remelting metal magnesium, and has the functions of deferrization and desilication.

At present, two methods of purifying zirconium tetrachloride mainly comprise hydrogen purification and molten salt purification. Most of the existing molten salt purification methods use intermittent molten salt purification methods, and related main equipment comprises a molten salt furnace and an evaporation furnace, molten salt is fully reacted in the molten salt furnace and then conveyed into the evaporation furnace for evaporation, the molten salt in the evaporation furnace is conveyed back into the molten salt furnace after the concentration of the molten salt is lower than a certain concentration, the crude zirconium tetrachloride is mixed again and then enters the evaporation furnace again for evaporation to prepare refined zirconium tetrachloride, but the intermittent molten salt purification methods have the problems of low productivity, zirconium energy consumption, complex operation and the like.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: provides a method and equipment for preparing refined zirconium tetrachloride by a molten salt purification method, and solves the problems of low productivity, high energy consumption and the like in the prior art.

In order to solve the technical problems, the invention adopts the technical scheme that:

a method for preparing refined zirconium tetrachloride by a molten salt purification method comprises the following steps:

s1: preparing potassium chloride, sodium chloride and crude zirconium tetrachloride in proportion in a low-temperature container, and forming composite molten salt at the temperature of 235-350 ℃;

s2: after the composite molten salt is reacted for a preset time at the temperature of 235-350 ℃, 8m³/h-15m³The flow rate is conveyed to a high-temperature container with the temperature of 350-480 ℃;

s3: evaporating the composite molten salt in a high-temperature container at 480 ℃ of 350-;

s4: and (4) enabling the composite molten salt to enter the low-temperature container from the high-temperature container, simultaneously supplementing crude zirconium tetrachloride to the low-temperature container, and repeatedly executing the steps S1-S4 until the purification is finished.

In order to solve the technical problem, the invention adopts another technical scheme as follows:

an apparatus for preparing refined zirconium tetrachloride by a molten salt purification method comprises a low-temperature container, a high-temperature container, a condensing mechanism and a feeding mechanism;

a baffling structure is arranged in each of the low-temperature container and the high-temperature container;

the low-temperature container is provided with a first inlet, a first outlet and a material supplementing port for supplementing crude zirconium tetrachloride, the high-temperature container is provided with a second inlet, an overflow port and a condensation port, the first inlet is communicated with the overflow port, and the first outlet is communicated with the second inlet through the feeding mechanism;

the horizontal plane of the overflow port is higher than the horizontal plane of the first inlet, and the height difference is 1-1.5 m;

the condensation mechanism is arranged above the condensation port to condense and collect the fine zirconium tetrachloride.

The invention has the beneficial effects that: according to the invention, after potassium chloride, sodium chloride and zirconium tetrachloride are prepared into the composite molten salt according to a specified ratio, the composite molten salt is collected in a flowing state to obtain the refined zirconium tetrachloride, the evaporation temperature of the high-temperature container and the discharge flow rate of the low-temperature container are controlled to keep the gas phase pressure of the zirconium tetrachloride constant, and after the composite molten salt containing low-concentration zirconium tetrachloride flows into the low-temperature container, the crude zirconium tetrachloride is quantitatively added into the low-temperature container, so that the continuous production is realized, the productivity is improved, and the energy consumption is reduced.

Drawings

FIG. 1 is a top view of an apparatus for preparing refined zirconium tetrachloride by a molten salt purification method according to the present invention;

FIG. 2 is a front view of an apparatus for preparing refined zirconium tetrachloride by a molten salt purification method according to the present invention.

Description of reference numerals:

1. a molten salt furnace; 11. a first inlet; 12. a first outlet; 13. a material supplementing port; 14. a molten salt evaporation channel;

2. an evaporation furnace; 21. a second inlet; 22. an overflow port; 23. a condensation port; 24. a molten salt backflow channel;

3. a material pipe is punched;

4. a screw feed pump; 5. a first separator; 6. a second separator.

Detailed Description

In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.

A method for preparing refined zirconium tetrachloride by a molten salt purification method comprises the following steps:

s1: preparing potassium chloride, sodium chloride and crude zirconium tetrachloride in proportion in a low-temperature container, and forming composite molten salt at the temperature of 235-350 ℃;

s2: after the composite molten salt is reacted for a preset time at the temperature of 235-350 ℃, 8m³/h-15m³The flow rate is conveyed to a high-temperature container with the temperature of 350-450 ℃;

s3: evaporating the composite molten salt in a high-temperature container at 480 ℃ of 350-;

s4: and (4) enabling the composite molten salt to enter the low-temperature container from the high-temperature container, simultaneously supplementing crude zirconium tetrachloride to the low-temperature container, and repeatedly executing the steps S1-S4 until the purification is finished.

The working principle of the invention is as follows:

the evaporation temperature of the high-temperature evaporation container and the discharge flow rate of the low-temperature container are controlled to realize flow rate control of the whole production process, so that the air pressure of zirconium tetrachloride is kept constant, the energy consumption is reduced while the productivity is improved, and after the low-concentration zirconium tetrachloride flows into the low-temperature container, crude zirconium tetrachloride is added into the low-temperature container to realize continuous production.

From the above description, the beneficial effects of the present invention are: according to the invention, after potassium chloride, sodium chloride and zirconium tetrachloride are prepared into the composite molten salt according to a specified ratio, the composite molten salt is collected in a flowing state to obtain the refined zirconium tetrachloride, the evaporation temperature of the high-temperature container and the discharge flow rate of the low-temperature container are controlled to keep the gas phase pressure of the zirconium tetrachloride constant, and after the composite molten salt containing low-concentration zirconium tetrachloride flows into the low-temperature container, the crude zirconium tetrachloride is quantitatively added into the low-temperature container, so that the continuous production is realized, the productivity is improved, and the energy consumption is reduced.

Further, in the step S1, the mass ratio of potassium chloride to sodium chloride is 1:1 to 1:3, and the mass ratio of the sum of potassium chloride and sodium chloride to crude zirconium tetrachloride is 1:9 to 7: 13.

Further, the preset time in the step S2 is 30min to 150 min.

Further, in the step S3, the zirconium tetrachloride is collected by a condenser or a zirconium sponge reduction furnace.

Further, the high-temperature container is an evaporation furnace with a baffling structure.

According to the above description, the evaporation furnace with the baffling structure is adopted, the residence time of the composite molten salt in the evaporation furnace is prolonged, and then the zirconium tetrachloride in the composite molten salt is fully evaporated and is conveyed back to the low-temperature container after reaching a certain concentration.

Further, the mass ratio of the crude zirconium tetrachloride supplemented in the step S4 to the refined zirconium tetrachloride collected in the step S3 is 1.05:1 to 1.2: 1.

Further, the flow rate of supplementing the crude zirconium tetrachloride in the step S4 is 1 ton/h to 4 tons/h.

From the above description, controlling the flow rate of crude zirconium tetrachloride can keep the dynamic balance of the whole production flow, realize continuous production and reduce energy consumption.

Further, the low-temperature container is a molten salt furnace with a baffling structure.

According to the description, the residence time of the composite molten salt in the molten salt furnace is prolonged by adopting the molten salt furnace with the baffling structure, so that the whole production process is kept in dynamic balance, the zirconium tetrachloride in the high-temperature container can be fully evaporated, and compared with the existing molten salt purification method, the zirconium tetrachloride in the composite molten salt is more fully evaporated, so that the effects of improving the productivity and reducing the energy consumption are achieved.

Example one

A method for preparing refined zirconium tetrachloride by a molten salt purification method comprises the following steps:

s1: in a volume of 15m³-20m³The potassium chloride, the sodium chloride and the crude zirconium tetrachloride in the molten salt furnace 1 form composite molten salt according to the mixture ratio of 7.5:7.5:85 at the temperature of 280-330 ℃;

s2: the composite molten salt reacts for 100min at the temperature of 235-350 ℃, and then 8m³/h-15m³The flow rate of the reaction solution is conveyed to the evaporation furnace 2 with the temperature of 360-420 ℃;

s3: evaporating the composite molten salt in an evaporation furnace 2 at the temperature of 350-450 ℃ to form zirconium tetrachloride gas, controlling the air pressure above the evaporation furnace 2 to be kept at 0.266MPa-0.399MPa, and condensing and collecting the zirconium tetrachloride gas to obtain refined zirconium tetrachloride;

s4: controlling the composite molten salt to 7m³/h-13m³The flow rate of/h is fed from the evaporation furnace 2 into the molten salt furnace 1, and at the same time, crude zirconium tetrachloride is replenished to the molten salt furnace 1 at a flow rate of 2-4 t/h, and steps S1-S4 are repeatedly performed.

Preferably, the evaporation furnace 2 and the molten salt furnace 1 are both the evaporation furnace 2 having a baffling structure.

Wherein the mass ratio of the crude zirconium tetrachloride supplemented in the step S4 to the refined zirconium tetrachloride collected in the step S3 is 1.05:1-1.2: 1. Preferably, the mass ratio of the crude zirconium tetrachloride supplemented in step S4 to the refined zirconium tetrachloride collected in step S3 is 1.05: 1.

In the embodiment, the aluminum content in the refined zirconium tetrachloride finally obtained by production is less than or equal to 0.002 percent, and the iron content is less than or equal to 0.004 percent. By adopting the traditional indirect molten salt purification method, 800 ℃ of electricity is consumed for producing 1 ton of the refined zirconium tetrachloride, while 700 ℃ of electricity is consumed for producing 1 ton of the refined zirconium tetrachloride in the embodiment, the energy consumption is reduced by 12.5%, and the yield in unit time is improved by 11.3%.

Example two

A method for preparing refined zirconium tetrachloride by a molten salt purification method comprises the following steps:

S1：in a volume of 15m³-20m³The potassium chloride, the sodium chloride and the crude zirconium tetrachloride in the molten salt furnace 1 form composite molten salt according to the ratio of 15:15:70 at the temperature of 330-350 ℃;

s2: the composite molten salt reacts for 70min at the temperature of 235-350 ℃, and then the reaction time is 5m³/h-10m³The flow rate of the reaction solution is conveyed to a blast furnace 2 with the temperature of 350-450 ℃;

s3: evaporating the composite molten salt in an evaporation furnace 2 at the temperature of 420-480 ℃ to form zirconium tetrachloride gas, controlling the air pressure above the evaporation furnace 2 to be kept at 0.133-0.266 Mpa, and condensing and collecting the zirconium tetrachloride gas to obtain refined zirconium tetrachloride;

s4: controlling the composite molten salt to be 4m³/h-8m³The flow rate of/h is fed from the evaporation furnace 2 into the molten salt furnace 1, while the molten salt furnace 1 is replenished with crude zirconium tetrachloride at a flow rate of 1 ton/h to 3 ton/h, and steps S1 to S4 are repeatedly performed.

Preferably, the evaporation furnace 2 and the molten salt furnace 1 are both the evaporation furnace 2 having a baffling structure.

Wherein the mass ratio of the crude zirconium tetrachloride replenished in the step S4 to the fine zirconium tetrachloride collected in the step S3 is 1.1: 1.

In the embodiment, the aluminum content in the refined zirconium tetrachloride finally obtained by production is less than or equal to 0.0015 percent, and the iron content is less than or equal to 0.003 percent. By adopting the traditional indirect molten salt purification method, 800-degree electricity is consumed for producing 1 ton of the refined zirconium tetrachloride, while 730-degree electricity is consumed for producing 1 ton of the refined zirconium tetrachloride in the embodiment, the energy consumption is reduced by 8.75%, and the yield in unit time is improved by 9.5%.

EXAMPLE III

Referring to fig. 1-2, an apparatus for preparing refined zirconium tetrachloride by a molten salt purification method comprises a molten salt furnace 1, an evaporation furnace 2, a condensing mechanism and a feeding mechanism; the molten salt furnace 1 and the evaporation furnace 2 are both provided with a baffling structure; the molten salt furnace 1 is provided with a first inlet 11, a first outlet 12 and a feeding port 13 for feeding coarse zirconium tetrachloride, the evaporation furnace 2 is provided with a second inlet 21, an overflow port 22 and a condensation port 23, the first inlet 11 is communicated with the overflow port 22, and the first outlet 12 is communicated with the second inlet 21 through a feeding mechanism; the level of the overflow port 22 is higher than that of the first inlet 11, and the height difference h is 1-1.5 m; the condensation mechanism is arranged above the condensation port 23 to condense and collect the fine zirconium tetrachloride. Specifically, the condensing mechanism is a condenser or a sponge zirconium reducing furnace; feeding mechanism includes molten salt pump and knockout pipe 3, and the molten salt pump is installed on knockout pipe 3 for the feeding velocity of flow of control knockout pipe 3, the both ends of knockout pipe 3 communicate with second import 21 and first export 12 respectively, and feed supplement mouth 13 facial make-up is equipped with screw rod feeding pump 4. Preferably, three condensation ports 23 are provided, and each condensation port 23 is provided with a condensation mechanism.

Specifically, all be provided with the baffling structure in molten salt stove 1 and the evaporating furnace 2, the baffling structure is including being the first baffle 5 of a font and the second baffle 6 that is L shape, first baffle 5 and second baffle 6 constitute molten salt evaporation passageway 14 in molten salt stove 1, first baffle 5 and second baffle 6 constitute molten salt return channel 24 in evaporating furnace 2, the both ends of molten salt evaporation passageway 14 communicate with second import 21 and overflow mouth 22 respectively, the both ends of molten salt return channel 24 communicate with first import 11 and first export 12 respectively.

A method for preparing refined zirconium tetrachloride by a molten salt purification method comprises the following steps:

s1: in a volume of 15m³-20m³The potassium chloride, the sodium chloride and the crude zirconium tetrachloride in the molten salt furnace 1 form composite molten salt according to the mixture ratio of 7.5:7.5:85 at the temperature of 280-330 ℃;

s2: the composite molten salt reacts in a molten salt furnace 1 at the temperature of 280-330 ℃ for 60-150 min and then 8m³/h-15m³The flow rate of the reaction solution is conveyed to the evaporation furnace 2 with the temperature of 360-420 ℃;

s3: evaporating the composite molten salt in an evaporation furnace 2 at the temperature of 350-450 ℃ to form zirconium tetrachloride gas, controlling the air pressure above the evaporation furnace 2 to be kept at 0.266MPa-0.399MPa, and condensing and collecting the zirconium tetrachloride gas to obtain refined zirconium tetrachloride;

s4: controlling the composite molten salt to 7m³/h-13m³The flow rate of/h is fed from the evaporation furnace 2 into the molten salt furnace 1, and at the same time, crude zirconium tetrachloride is replenished to the molten salt furnace 1 at a flow rate of 2-4 t/h, and steps S1-S4 are repeatedly performed.

Preferably, the evaporation furnace 2 and the molten salt furnace 1 are both the evaporation furnace 2 having a baffling structure.

Wherein the mass ratio of the crude zirconium tetrachloride supplemented in the step S4 to the refined zirconium tetrachloride collected in the step S3 is 1.05: 1.

In summary, according to the method and the equipment for preparing the refined zirconium tetrachloride by the molten salt purification method, the gas phase pressure can be kept constant by controlling the feeding flow rate, the reflux flow rate, the adding speed of the crude zirconium tetrachloride, the reaction temperature and the evaporation temperature, so that the continuous production is realized, the energy consumption is reduced, and the productivity and the purity of the zirconium tetrachloride can be greatly improved.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.