Preparation method and production device of trifluoro vanadium oxide

Abstract

The invention relates to a preparation method and a production device of trifluorovanadium oxide, and belongs to the technical field of inorganic fluorine chemical industry. The preparation method comprises the following steps: (1) introducing a fluorinating agent into a reactor filled with vanadium pentoxide to prepare trifluoro vanadium oxide, and controlling the reaction temperature to be 200-600 DEG C and the reaction pressure to be 0-0.1 MPa; and (2) condensing and collecting the product generated by the reaction to obtain the trifluorovanadium oxide. Wherein the fluorinating agent is mixed gas of nitrogen and one of nitrogen trifluoride, fluorine or hydrogen fluoride. According to the preparation and collection method and device for the trifluorovanadium oxide, the synthesis route is short and safe, operation is easy, the material taking mode is faster and more efficient, the product yield and purity are higher, then economic benefits are improved, and the production requirements of chemical enterprises for safety, environmental protection, high efficiency and circular economy are met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of inorganic fluorine chemical industry, and particularly relates to a preparation method and production device of trifluorovanadate. BACKGROUND

[0002] Trifluorovanadate (VOF3, CAS: 13709-31-4) is a yellowish white or light yellow volatile solid, which has the characteristics of high hygroscopicity, generates yellow smoke in humid air, and corrodes glass when heated. It can form 3MF·2VOF3 complex salt with potassium, sodium and other metal fluorides. In organic synthesis, it is mainly used as intramolecular or intermolecular oxidative coupling reaction of phenol or phenolic ether compounds. At present, there are mainly two methods for preparing trifluorovanadate: (1) Dry oxygen and vanadium trifluoride powder are used for thermal reaction. However, the stability of the raw material vanadium trifluoride is poor, which is easy to combine with water to generate other products, the consumption of the raw material reduces the generation rate of trifluorovanadate, and it has strong irritability, which easily causes irritation of skin, eyes or respiratory tract.

[0003] (2) Chlorine trifluoride (ClF3) and vanadium trichloride monoxide (VOCl3) are used for reaction synthesis. However, it is very difficult to obtain the above two raw materials, among which the chlorine trifluoride is mainly imported, and the preparation of vanadium trichloride monoxide needs to avoid water vapor and metal. And the two will produce harmful gases such as chlorine gas in the reaction, so it is very difficult to synthesize trifluorovanadate.

[0004] For the problems existing in the above two routes, some technologies use vanadium pentoxide and fluorine gas to obtain trifluorovanadate. In the patent CN119349631A, a preparation method of trifluorovanadate is disclosed. Vanadium pentoxide powder and fluorine gas are used to generate trifluorovanadate crude product under the action of catalyst γ-Cr2O3, and finally the product is obtained by magnetic separation through the magnetic property of trifluorovanadate. However, the product yield of the patent CN119349631A is only about 45%, and strong magnetic separation is used, which needs special equipment for this operation. The relative preparation cost is high, and it is not suitable for industrial production. SUMMARY

[0005] In view of the problems of low product yield and the need for special equipment to purify the product in the existing preparation method of trifluorovanadate, the present application provides a preparation method and production device of trifluorovanadate to solve the above problems.

[0006] The technical scheme of the present application is as follows: In a first aspect, the present application provides a preparation method of trifluorovanadate, comprising the following steps: (1) into the reactor containing vanadium pentoxide fluorination agent preparation trifluoro vanadium oxide, control the reaction temperature is 200 ℃~600 ℃, the reaction pressure is 0 MPa~0.1 MPa; (2) the reaction product condensation collection, get trifluoro vanadium oxide.

[0007] Among them, the fluorinating agent is one of nitrogen trifluoride, fluorine gas or hydrogen fluoride.

[0008] Further, the fluorinating agent includes carrier gas, the carrier gas is nitrogen, the fluorinating agent concentration in the mixed gas after mixing carrier gas is 5 %~100 %; preferably, the fluorinating agent concentration in the mixed gas after mixing carrier gas is 20 %~50 %.

[0009] Further, the non-condensable gas in the condensation process is discharged through the tail gas treatment system.

[0010] Further, the reaction temperature of vanadium pentoxide and fluorinating agent is 300 ℃~400 ℃.

[0011] Further, the reaction pressure of vanadium pentoxide and fluorinating agent is 0 MPa~0.05 MPa.

[0012] Further, the condensation collection temperature is-80 ℃~20 ℃, preferably-30 ℃~10 ℃.

[0013] The second aspect, the present application provides a kind of trifluoro vanadium oxide production device, including reaction device and condensing device;The reaction device includes reactor;The reactor is horizontally placed, and a circle of heating furnace is arranged outside;One end of the reactor is equipped with gas inlet, gas inlet connects gas inlet pipe, the gas inlet pipe is inserted into reactor, and a plurality of gas outlets two are arranged on the side wall of gas inlet pipe;The other end of the reactor is equipped with gas outlet one, and the bottom of the reactor is equipped with tray;The sieve plate is arranged at the gas outlet one;The condensing device includes collector, and the collector is vertically placed;The gas outlet one is connected with the feed inlet in the bottom of collector;The condensing device is equipped with jacket outside, and the jacket is equipped with refrigerant inlet and refrigerant outlet;The condensing device is equipped with rotating shaft inside, and a plurality of scrapers are arranged on the rotating shaft;The collector is equipped with discharge outlet in the bottom, and is equipped with gas outlet three in the top.

[0014] Further, the diameter of the gas outlet two is 0.5 mm~20 mm.

[0015] Further, the discharge outlet is connected with polytetrafluoroethylene bottle.

[0016] Further, the gas outlet three is connected with tail gas treatment device.

[0017] The beneficial effects of the present application are: The application provides a preparation and collection method and device of vanadium trifluoride oxide, and the synthesis route is short and safe, easy to operate, and the material taking mode is more fast and efficient, the product yield and purity are higher, and thus economic benefits are improved, and the production requirements of safety, environmental protection, high efficiency and circular economy of a chemical enterprise are met. BRIEF DESCRIPTION OF DRAWINGS

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description, and obviously, other drawings can be obtained by those skilled in the art without any creative effort on the premise of not paying any creative effort.

[0019] Figure 1 is a structural schematic diagram of a reactor in the embodiment 1 of the present application.

[0020] Figure 2 is a structural schematic diagram of a condensing device in the embodiment 1 of the present application.

[0021] In the figure, 1 is a heating furnace, 2 is a sieve plate, 3 is an air outlet one, 4 is a tray, 5 is an air inlet, 6 is an air inlet pipe, 7 is a reactor, 8 is a rotating shaft, 9 is a coolant outlet, 10 is a scraper, 11 is a feeding port, 12 is a discharging port, 13 is a coolant inlet, 14 is a jacket, 15 is a collector, 16 is an air outlet two, and 17 is an air inlet three. DETAILED DESCRIPTION

[0022] In order to make the person skilled in the art better understand the technical solutions in the present application, the following will combine the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application, and obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without any creative effort should belong to the protection scope of the present application.

[0023] In order to solve the problems of low product yield and the need of special equipment to purify the product in the prior art method for preparing vanadium trifluoride oxide, the present application provides a preparation method of vanadium trifluoride oxide, comprising the following steps: (1) a fluorinating agent is introduced into a reactor containing vanadium pentoxide to prepare vanadium trifluoride oxide, and the reaction temperature is controlled to be 200 ℃-600 ℃, and the reaction pressure is controlled to be 0 MPa-0.1 MPa; (2) the product generated in the reaction is condensed and collected to obtain vanadium trifluoride oxide.

[0024] The fluorinating agent is one of nitrogen trifluoride, fluorine gas or hydrogen fluoride.

[0025] In a preferred embodiment, the reaction temperature of the vanadium pentoxide and the fluorination agent is 200 °C to 600 °C, for example 200 °C, 250 °C, 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C or 600 °C. Preferably, the reaction temperature is 300 °C to 400 °C.

[0026] In a preferred embodiment, the reaction pressure of the vanadium pentoxide and the fluorination agent is 0 MPa to 0.1 MPa. For example 0 Mpa, 0.01 MPa, 0.02 MPa, 0.03 MPa, 0.04 Mpa, 0.05 Mpa, 0.06 Mpa, 0.07 Mpa, 0.08 Mpa, 0.09 Mpa or 0.10 Mpa. Preferably, the reaction pressure is 0 MPa to 0.05 Mpa.

[0027] In a preferred embodiment, the condensation collection temperature is -80 °C to 20 °C. For example -80 °C, -70 °C, -60 °C, -50 °C, -40 °C, -30 °C, -20 °C, -10 °C, 0 °C, 10 °C or 20 °C. Preferably, the condensation collection temperature is -30 °C to 10 °C.

[0028] Example 1 A production device of vanadium trifluoride oxide comprises a reaction device and a condensation device; the reaction device comprises a reactor 7; the reactor 7 is horizontally placed and externally provided with a heating furnace 1; one end of the reactor 7 is provided with an air inlet 5, the air inlet 5 is connected with an air inlet pipe 6, the air inlet pipe 6 extends into the reactor 7, and the side wall of the air inlet pipe 6 is provided with a plurality of air outlets 16; the other end of the reactor 7 is provided with an air outlet 3, and the bottom of the reactor 7 is provided with a tray 4; the air outlet 3 is provided with a sieve plate 2; the condensation device comprises a collector 15, and the collector 15 is vertically placed; the air outlet 3 is connected with a feeding port 11 at the bottom of the collector 15; the condensation device is externally provided with a jacket 14, and the jacket 14 is provided with a coolant inlet 13 and a coolant outlet 9; the inside of the collector 15 is provided with a rotating shaft 8, and the rotating shaft 8 is provided with a plurality of scrapers 10; the bottom of the collector 15 is provided with a discharging port 12, and the discharging port 12 is connected with a polytetrafluoroethylene bottle; the top of the collector 15 is provided with an air outlet 17, and the air outlet 17 is connected with a tail gas treatment device.

[0029] The gas inlet pipe 6 extends into the reactor 7, so that the gas inlet pipe 6 can be replaced after long-time use. The side wall of the gas inlet pipe 6 is provided with a plurality of gas outlets 16 with a diameter of 0.5 mm to 20 mm, so that the contact area of the fluorinating agent and vanadium pentoxide can be maximized, thereby achieving more sufficient reaction and higher product yield. The sieve plate 2 is arranged at the gas outlet 3 of the reactor 7, so that the unreacted solid raw materials can be effectively prevented from entering the collector together with the product gas, thereby affecting the product purity. The temperature and pressure measuring devices are further arranged on the reactor 7, so that the changes of the reaction temperature and pressure can be better monitored, thereby ensuring the safety of personnel operation and the reaction under the optimal process conditions.

[0030] The working principle of the production device used in the application is as follows: The fluorinating agent mixed gas entering the gas inlet 5 of the reactor 7 is sprayed from the gas outlet 16 to the tray 4 and contacts the vanadium pentoxide on the tray 4, so that the gaseous vanadium oxytrifluoride generated by the reaction under the heating condition is transferred to the collector 15 together with the unreacted fluorinating agent mixed gas. After being cooled, the vanadium oxytrifluoride sublimes into solid and is attached to the side wall of the collector 15. The solid is scraped off by the scraper 10 driven by the rotating shaft 8 and falls into the bottom of the collector 15. When the accumulated amount reaches a certain amount, the solid is discharged from the discharge port 12 and is stored in a polytetrafluoroethylene bottle. The tail gas enters the tail gas treatment device for treatment, wherein the tail gas is purified by passing through a charcoal adsorption tank, a lime absorption tank, an alkali washing tower and the like.

[0031] Example 2 Vanadium oxytrifluoride is prepared in the production device in Example 1, and the specific steps are as follows: 600 g of vanadium pentoxide is evenly laid on the tray and placed in the reactor, then 50% nitrogen trifluoride / nitrogen mixed gas is introduced at a flow rate of 100 L / h, and the fluorination reaction is carried out at a temperature of 350 ℃ to 400 ℃ and a pressure of 0.02 MPa, and the temperature of the collector is controlled at -20 ℃ to -30 ℃. The fluorination reaction is completed after 8 hours, nitrogen gas is introduced to replace the gas in the reactor and the collector, the replacement gas is discharged into the tail gas treatment system, and the polytetrafluoroethylene bottle is removed from the glove box to take the material for detection. A total of 345.5 g of vanadium oxytrifluoride is obtained, the product purity is 99.92%, and the yield is 84.5%.

[0032] Example 3 Vanadium oxytrifluoride is prepared in the production device in Example 1, and the specific steps are as follows: Put 600 g of vanadium pentoxide on the tray, put it into the reactor, then pass in 40% nitrogen trifluoride / nitrogen mixed gas, gas flow rate 100 L / h, fluorination reaction under the condition of temperature 320 ℃~380 ℃, pressure 0.02 MPa, collector temperature control at -20 ℃~ -30 ℃. After 10 hours, the fluorination reaction is completed; pass nitrogen to replace the gas in the reactor and the collector, and the replacement gas is discharged into the tail gas treatment system; remove the polytetrafluoroethylene bottle and put it into the glove box to detect the material. A total of 333.6 g of trifluoride vanadium oxide is obtained, the detection product purity is 99.94%, and the yield is 81.6%.

[0033] Example 4 Prepare trifluoride vanadium oxide in the production device in Example 1, the specific steps are as follows: Put 400 g of vanadium pentoxide on the tray, put it into the reactor, then pass in 30% fluorine / nitrogen mixed gas, gas flow rate 100 L / h, fluorination reaction under the condition of temperature 300 ℃~330 ℃, pressure 0.01 MPa, collector temperature control at -20 ℃~ -30 ℃. After 6 hours, the fluorination reaction is completed; pass nitrogen to replace the gas in the reactor and the collector, and the replacement gas is discharged into the tail gas treatment system; remove the polytetrafluoroethylene bottle and put it into the glove box to detect the material. A total of 214.8 g of trifluoride vanadium oxide is obtained, the detection product purity is 99.81%, and the yield is 78.8%.

[0034] Comparative Example Prepare trifluoride vanadium oxide in the production device in Example 1, the specific steps are as follows: Put 400 g of vanadium pentoxide on the tray, put it into the reactor, then pass in 30% fluorine / nitrogen mixed gas, gas flow rate 100 L / h, fluorination reaction under the condition of temperature 300 ℃~330 ℃, pressure 0.01 MPa, collector temperature control at -20 ℃~ -30 ℃. After 6 hours, the fluorination reaction is completed; pass nitrogen to replace the gas in the reactor and the collector, and the replacement gas is discharged into the tail gas treatment system; remove the polytetrafluoroethylene bottle and put it into the glove box to detect the material. A total of 214.8 g of trifluoride vanadium oxide is obtained, the detection product purity is 99.81%, and the yield is 78.8%.

[0035] Although the present application has been described in detail by referring to the preferred embodiments thereof, it is apparent that the present application is not limited to the foregoing examples. It will be appreciated that those skilled in the art can make various modifications or replacements to the embodiments of the present application without departing from the spirit and scope of the present application, and these modifications or replacements should be within the scope of the present application. Any person skilled in the art within the technical scope disclosed in the present application can easily think of changes or replacements, which should be covered within the protection scope of the present application.

Claims

1. A process for the preparation of vanadium trifluoride oxide, characterized in that, The method comprises the following steps: (1) introducing a fluorinating agent into a reaction device containing vanadium pentoxide to prepare trifluorovanadate, controlling the reaction temperature to be 200-600 DEG C, and controlling the reaction pressure to be 0-0.1 MPa; (2) condensing and collecting the product generated in the reaction to obtain trifluorovanadate; The fluorinating agent is nitrogen trifluoride, fluorine gas or hydrogen fluoride.

2. A process for the preparation of vanadium trifluoride oxide as claimed in claim 1, characterized in that, The fluorinating agent contains a carrier gas, and the carrier gas is nitrogen.

3. A process for the preparation of vanadium trifluoride oxide as claimed in claim 1 or 2, characterized in that, The fluorinating agent concentration in the mixed gas after mixing the carrier gas is 5-100%.

4. The method for preparing vanadium trifluoride as described in claim 1, characterized in that, The fluorinating agent concentration in the mixed gas after mixing the carrier gas is 20-50%.

5. A process for the preparation of vanadium oxytrifluoride as claimed in claim 1, wherein the process is carried out at a temperature in the range of 0°C to 10°C. Non-condensable gas in the condensation process is discharged through a tail gas treatment system.

6. A process for the preparation of vanadium oxytrifluoride as claimed in claim 1, wherein, The reaction temperature of vanadium pentoxide and the fluorinating agent is 300-400 DEG C.

7. A process for the preparation of vanadium oxytrifluoride as claimed in claim 1, wherein the process is carried out at a temperature in the range of 0°C to 10°C. The reaction pressure of vanadium pentoxide and the fluorinating agent is 0-0.05 MPa.

8. An apparatus for carrying out the process for producing vanadium trifluoride oxide as claimed in claim 1, characterized by, The condensation and collection temperature is -80-20 DEG C.

9. The production apparatus according to claim 8, characterized by The reaction device comprises a reactor, which is horizontally placed and externally provided with a heating furnace; one end of the reactor is provided with a gas inlet connected with a gas inlet pipe, the gas inlet pipe extends into the reactor, and the sidewall of the gas inlet pipe is provided with a plurality of gas outlets two; the other end of the reactor is provided with a gas outlet one, and the bottom of the reactor is provided with a tray; the gas outlet one is provided with a sieve plate; the condensing device comprises a collector, which is vertically placed; the gas outlet one is connected with a feeding port at the bottom of the collector; the condensing device is externally provided with a jacket provided with a coolant inlet and a coolant outlet; the condensing device is internally provided with a rotating shaft provided with a plurality of scrapers; the bottom of the collector is provided with a discharging port, and the top of the collector is provided with a gas outlet three.

10. The production apparatus according to claim 8, wherein The diameter of the gas outlet two is 0.5-20 mm. The discharging port is connected with a polytetrafluoroethylene bottle.

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