TW201632251A - Separation and recovery method for hydrogen fluoride and separation and recovery apparatus for hydrogen fluoride - Google Patents

Abstract

The present invention aims at providing a separation and recovery method for hydrogen fluoride and a separation and recovery apparatus for hydrogen fluoride, which can efficiently recover hydrogen fluoride from the calcium fluoride discharged from various steps. The separation and recovery method of this invention includes the steps: a gas separation step in which a calcium fluoride-based raw material (recovered calcium fluoride) is filled in a closed type vertical reaction vessel R while adding sulfuric acid and the like thereto, using stirring blades 2a of a stirring mechanism 2 to stir up and down to separate out fluorine component as the hydrogen fluoride-based gas; a negative pressure generating step to use a pump P to make the water-based absorbing liquid stored in the recovery storage tank T circulate so as to generate a negative pressure in the ejector E; a gas recovery step to use the above negative pressure to suck the hydrogen fluoride-based gas generated in the vertical reaction vessel R and recover the gas to the recovery storage tank T; and a hydrogen fluoride concentration step by repeatedly carrying out the circulation of the above water-based absorbing liquid and the recovery of the generated hydrogen fluoride-based gas in a batch unit.

Description

Method for separating and recovering hydrogen fluoride and separation and recovery device for hydrogen fluoride

The present invention relates to a method for separating and recovering hydrogen fluoride and a hydrogen fluoride separation and recovery device therefor. The method for separating and recovering hydrogen fluoride can be obtained by precipitating a fluorine-containing effluent such as hydrogen fluoride or fluoroantimonic acid. The dehydrated solids are efficiently separated and recovered from hydrogen fluoride and hydrogen fluoride.

In a step of etching a glass or germanium wafer for a liquid crystal (LCD) panel, a step of treating a fluorine-containing organic substance such as a Freon substitute, a surface treatment of a metal, or a factory for producing various fluorinated derivatives, a high concentration is discharged. A discharge liquid (treatment liquid) such as hydrogen fluoride or fluoroantimonic acid. The aqueous solution containing hydrogen fluoride (hydrofluoric acid or hydrofluoric acid) as the effluent is classified as a poisonous substance for harmful substances and a harmful substance, so when it is discharged from the step or the factory, it is mixed with the above-mentioned effluent. A calcium compound such as calcium hydroxide, calcium oxide, calcium carbonate or calcium chloride is reacted to precipitate hydrogen fluoride or the like into a poorly soluble (water-insoluble) calcium fluoride or the like, and then removed and removed, and the remaining almost contains no hydrogen fluoride. The discharged liquid is discharged to the outside of the step.

In addition, the calcium fluoride-based soft aqueous solid material taken out from the above-mentioned discharge liquid is subjected to a dehydration operation such as compression or centrifugation to form a solid such as a cake or a plate, and then passed through a drying step, a pulverization step, or the like. It is a porous granule or a powder (sponge) which is generally 20% or less (preferably 10% or less), and is used as an industrial waste removal step (hereinafter, these wastes are referred to as "recovered calcium fluoride". "). In addition to the use of some of the raw materials (flux), cement raw materials, optical lens materials, etc., which are used for the recovery of calcium fluoride, it is generally treated by direct burial or the like.

On the other hand, attempts have been made to separate hydrogen fluoride from the recovered calcium fluoride and recover it as hydrofluoric acid (aqueous solution of hydrogen fluoride) for reuse. For example, in a conventional manufacturing step of industrially establishing hydrogen fluoride using fluorite (natural calcium fluoride mineral), a small amount (about several %) of recovered calcium fluoride powder is added (mixed) to the fluorite. Raw material (refer to Patent Document 1, etc.).

Further, Patent Document 2 discloses a method for producing hydrogen fluoride using calcium fluoride, which is a horizontal reaction furnace (a small rotary kiln having a cylindrical outer heating type inclined furnace), and is supplied from another step (factory). The recovered calcium fluoride is transported, followed by mixing concentrated sulfuric acid or fuming sulfuric acid, and rotating (stirring) the cylindrical furnace while heating to 250 ° C or lower (preferably 80 to 150 ° C) Slowly transported in the furnace (residence time: about 1 hour), hydrogen fluoride can be continuously produced in a temperature range of 40% or more without causing decomposition of sulfuric acid. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4316393 [Patent Document 2] Japanese Patent No. 4652948

[The problem that the invention wants to solve]

However, in the method of mixing the recovered calcium fluoride in the above-described manufacturing step of using hydrogen fluoride of the conventional fluorite, since the recovered calcium fluoride is a porous particle having a light specific gravity, the mixing state with the main raw material fluorite is poor, so that the furnace is poor. The internal fluidity is deteriorated, and there is a problem that volatilization or the like of sulfuric acid or the like increases due to prolonged intense heat (about 500 to 600 ° C).

Further, in the method for producing hydrogen fluoride described in Patent Document 2, since the calcium fluoride is recovered in the form of light particles and the production method is continuous, it is difficult to recover calcium fluoride, concentrated sulfuric acid, or the like. The mixing ratio is kept constant (the chances of maintaining contact with each other are equal), and the separation efficiency (recovery rate) of hydrogen fluoride is not easily improved. Therefore, we hope to improve the method of recovering and regenerating hydrogen fluoride from the recovery of calcium fluoride.

In view of the above, an object of the present invention is to provide a method for separating and recovering hydrogen fluoride and a hydrogen fluoride separation and recovery device which can efficiently recover hydrogen fluoride from calcium fluoride discharged from various steps. [Method of solving the problem]

In order to achieve the above object, a first object of the present invention is to provide a method for separating and recovering hydrogen fluoride, which comprises a closed vertical reaction vessel capable of sealing a gas generated in a reaction vessel, the reaction vessel comprising: a cylindrical reaction vessel a stirring mechanism for stirring the powder in the reaction vessel up and down; a recovery tank for storing the absorption liquid for absorbing the gas; and a gas suction mechanism for supplying the pump for supplying the negative pressure to the injector In the gas separation step, the method for separating and recovering hydrogen fluoride includes a step of filling a calcium fluoride-based raw material into the vertical reaction vessel, and simultaneously stirring the mixture with the stirring blade of the stirring mechanism while adding sulfuric acid. The calcium fluoride-based raw material separates the fluorine component as a hydrogen fluoride-based gas; the negative pressure generating step stores a water-based absorbent for absorbing the hydrogen fluoride-based gas in the recovery storage tank, and circulates the aqueous absorbent through the ejector by a pump To the recovery tank, so that the injector generates a negative pressure for gas suction; a gas recovery step using the injector Negative pressure, sucking the hydrogen fluoride-based gas generated in the vertical reaction vessel, mixing the gas into the water-based absorption liquid in the ejector, and recovering the mixed liquid to the recovery storage tank; and hydrogen fluoride concentration step, continuing The circulation of the water-based absorption liquid passing through the ejector of the pump and the hydrogen fluoride-based gas generated in the vertical reaction vessel are recovered until the concentration of the hydrogen fluoride-based component absorbed by the aqueous-based absorption liquid in the recovery storage tank reaches a predetermined concentration.

Further, a second aspect of the present invention provides a hydrogen fluoride separation and recovery apparatus comprising: a closed vertical reaction vessel having a hydrogen fluoride-based gas suction port at an upper portion thereof and a powder discharge port at the bottom portion after completion of the reaction a stirring mechanism for stirring the calcium fluoride-based raw material in the vertical reaction vessel; recovering the storage tank to store the aqueous absorption liquid for absorbing the hydrogen fluoride-based gas; and an ejector disposed in the vertical reaction vessel and the recovery storage tank Between the absorption liquid circulation flow path, the water absorption liquid in the recovery storage tank is returned to the recovery storage tank through the injector; the pump sends the water absorption hydraulic pressure in the recovery storage tank to the injector to be used as a negative The pressurized fluid and the gas recovery flow path are disposed between the suction port of the vertical reaction vessel and the ejector, and suck the hydrogen fluoride gas generated in the vertical reaction vessel.

That is, the inventors of the present invention conducted a number of elaborate studies in order to solve the above problems. As a result, it was found that the separation operation of the fluorine-based component (hydrogen fluoride) derived from calcium fluoride was carried out in a batch type rather than a continuous manner by using a vertical (vertical) reaction vessel excellent in powder mixing and mixing. It is known that the fluorine can be separated in a high yield in a short reaction time as compared with the continuous separation operation. Further, in the step of recovering the fluorine-based component (gas), it is also thought that the portion of the device that is in contact with the highly corrosive hydrogen fluoride or hydrofluoric acid (aqueous solution) is not required to be liquid-sealed by using the non-movable portion (axis) The ejector or pump or the like of the seal is formed by applying a resin lining article (or a resin article) to prevent the hydrogen fluoride from leaking out of the system and increasing the service life of the recovery step itself. As described above, in addition to the fact that hydrogen fluoride can be separated with high efficiency (energy saving) as described above, and it is believed that the initial equipment investment or operating cost of the entire separation and recovery step (device) of hydrogen fluoride can be reduced to a practical level, the present invention has been proposed.

In addition, the calcium fluoride-based raw material used in the present invention is a so-called "recovered calcium fluoride" obtained by treating a discharged liquid discharged from various steps using a fluorine-based component, and the form is a hydrous solid. The dried sponge or the powder obtained by pulverizing it (including the state in which the powder or the granule is secondarily agglomerated). Further, the "recovery" of the separation and recovery of the hydrogen fluoride includes the purpose of recovering the fluorine-based component in the "recovered calcium fluoride" for "recycling" or "recycling". [Effect of the invention]

The method for separating and recovering hydrogen fluoride according to the present invention comprises a gas separation step of filling a calcium fluoride-based raw material in a closed vertical reaction vessel capable of sealing the generated gas, and adding a sulfuric acid thereto, and a stirring mechanism The stirring blade is stirred up and down, and a fluorine component is separated from the calcium fluoride-based raw material as a hydrogen fluoride-based gas. Thereby, the calcium fluoride-based raw material filled in the vertical reaction vessel is stirred up and down in a batch mode by the mixing (reaction) method, so that the sulfuric acid (concentrated sulfuric acid, fuming) can be quickly and sufficiently added. The separation of the fluorine-based components (desorption of hydrogen fluoride) can be completed in a short time by mixing and contacting with sulfuric acid or the like. Further, the above reaction (separation of the fluorine-based component) does not require application of a high temperature as in the conventional production method such as a rotary kiln (more than 250 ° C above the decomposition temperature of sulfuric acid), and can be completed in a low temperature region of 150 ° C or lower, so that the reaction It is also advantageous from the point of view of energy (step operating expenses).

Further, the method for separating and recovering hydrogen fluoride according to the present invention includes a negative pressure generating step of circulating a water-based absorbent stored in the recovery tank to the recovery tank via an ejector, thereby causing the injector to generate a gas suction. a gas recovery step of sucking a hydrogen fluoride gas generated in the vertical reaction vessel by a negative pressure of the ejector, mixing the gas into the water absorbing liquid in the ejector, and recovering the mixed liquid to the above a recovery storage tank; and a hydrogen fluoride concentration step, which continuously recycles the water-based absorption liquid passing through the ejector of the pump and the hydrogen fluoride-based gas generated in the vertical reaction vessel until the water-based absorption liquid in the recovery storage tank absorbs The concentration of the hydrogen fluoride-based component reaches a predetermined concentration.

By the co-operation of the steps, the hydrogen fluoride-based gas generated in the vertical reaction vessel of the gas separation step can be quickly absorbed and concentrated by the aqueous absorbent. Further, in the above-described injector for generating a negative pressure, since the negative pressure generating mechanism has no movable portion or a shaft seal portion, the fear of causing the leakage of harmful liquid is low even by the highly corrosive hydrofluoric acid (aqueous solution). Further, there is an advantage that the hydrogen fluoride-based gas sucked from the vertical reaction vessel can be immediately mixed with and absorbed by the water-based absorbent sprayed in the ejector.

As described above, the method for separating and recovering hydrogen fluoride according to the present invention is continuous with the conventional effect by the effect of the effect obtained by the separation step of the hydrogen fluoride-based gas and the effect of the recovery (concentration) step from the hydrogen fluoride-based gas. In the production apparatus of the hydrogen fluoride type, the fluorine-based component (hydrogen fluoride) in the calcium fluoride-based raw material can be separated and recovered by a short reaction time, high efficiency, and low cost.

Further, the method for separating and recovering hydrogen fluoride according to the present invention is applicable to an inverted conical shape in which the inner surface of the vertical reaction vessel is gradually reduced in diameter from the upper portion to the lower portion, and the stirring blade of the stirring mechanism is along the inverted conical shape. The inner peripheral surface is subjected to coma movement. Further, it is preferable that at least the inner surface of the vertical reaction vessel which is in contact with the hydrogen fluoride, the inner surface of the recovery tank, the contact surface of the gas suction mechanism with the aqueous absorbent, and the inner surface of the piping through which the hydrogen fluoride gas passes are preferably resistant. Corrosive resin lining or resin film is covered.

Further, in the method for separating and recovering hydrogen fluoride according to the present invention, in particular, two or more gas recovery units including the recovery storage tank and the gas suction mechanism are provided, and the type of the hydrogen fluoride gas generated in the vertical reaction container is When the gas recovery unit connected to the vertical reaction vessel is switched to recover the concentration, the calcium fluoride-based raw material discharged from various steps is fluorinated in a mixed system having two or different fluorine contents. Raw materials such as calcium mixed materials can be classified (recycled) according to the type or concentration (purity) of the raw materials.

Next, the hydrogen fluoride separation and recovery apparatus of the present invention used in the above separation and recovery method includes a closed vertical reaction vessel having a hydrogen fluoride-based gas suction port at the upper portion and a powder discharge port at the bottom of the reaction. And a stirring mechanism that stirs the calcium fluoride-based raw material in the vertical reaction vessel up and down, and mixes the calcium fluoride-based raw material with sulfuric acid in the vertical reaction vessel to generate a hydrogen fluoride-based gas. As described above, the separation and recovery apparatus of the present invention can rapidly and sufficiently mix the calcium fluoride-based raw material filled in the vertical reaction vessel with the added sulfuric acid (concentrated sulfuric acid, fuming sulfuric acid, etc.). The phase-mixed contact can complete the separation of the fluorine-based component (the detachment of hydrogen fluoride) in a short time. Further, the above reaction (separation of the fluorine-based component) does not require application of a high temperature as in the conventional production method such as a rotary kiln (more than 250 ° C above the decomposition temperature of sulfuric acid), and can be completed in a low temperature region of 150 ° C or less. Energy saving.

Further, the separation and recovery device includes a recovery storage tank for storing a water-based absorption liquid for absorbing the hydrogen fluoride-based gas, an ejector disposed between the vertical reaction container and the recovery storage tank, and an absorption liquid circulation flow path for recovering the recovery The water-based absorption liquid in the storage tank is returned to the recovery storage tank through the ejector; the pump sends the water absorption hydraulic pressure in the recovery storage tank to the ejector as a fluid for generating a negative pressure; and the gas recovery flow path is provided at The hydrogen fluoride-based gas generated in the vertical reaction vessel is sucked between the suction port of the vertical reaction vessel and the ejector, and is sucked into the vertical reaction vessel by the negative pressure generated by the ejector. The hydrogen fluoride-based gas is absorbed and collected (concentrated) by the water-based absorbing liquid (the fluid in the ejector and the fluid for generating a negative pressure) circulating between the recovery tank and the ejector.

According to this configuration, the hydrogen fluoride-based gas generated in the vertical reaction vessel can be quickly and surely absorbed. Further, as described above, the ejector for generating the above-described negative pressure is different from the general suction (vacuum) pump or the like, and since the negative pressure generating mechanism has no movable portion and no shaft seal (liquid seal) portion, even if it passes through the high Corrosive hydrofluoric acid (aqueous solution) will not leak harmful liquids. Further, since the hydrogen fluoride-based gas sucked from the vertical reaction vessel is immediately mixed with and absorbed by the water-based absorbent in the (flow-through) ejector, in addition to the volume reduction due to absorption (dissolution), there is The negative pressure generated in this injector naturally rises (the negative pressure becomes high).

Further, in the apparatus for separating and recovering hydrogen fluoride according to the present invention, the inner surface of the vertical reaction vessel has an inverted conical shape which is gradually reduced in diameter from the upper portion to the lower portion, and the stirring blade of the stirring mechanism is along the inner peripheral surface of the inverted conical shape. The calculus exerciser, the calcium fluoride-based raw material (powder) and the concentrated sulfuric acid (liquid) stirred by the agitating blade are along the inner peripheral surface (reverse conical shape) of the vertical reaction vessel. The central portion of the bottom of the container flows intensively. Therefore, the mixing operation of the calcium fluoride-based raw material using the above-described vertical reaction vessel with sulfuric acid or the like (the separation operation of the hydrogen fluoride-based gas) is compared with the case of using a reaction vessel of another shape because of such calcium fluoride. The contact opportunity between the raw material and concentrated sulfuric acid is increased, so that the reaction can be completed in a shorter time.

Further, in the apparatus for separating and recovering hydrogen fluoride according to the present invention, in particular, at least the inner surface of the vertical reaction vessel which is in contact with the hydrogen fluoride, the inner surface of the recovery tank, the contact surface with the fluid in the interior of the ejector, and the circulation passage of the absorbing liquid When the inner surface of the piping with the gas recovery flow path is covered with a resin lining or a resin film having corrosion resistance, leakage of the fluid outside the system due to the corrosion of the hydrogen fluoride is less likely to occur, and the maintenance cost of the device can be reduced. Furthermore, it also has the advantage of extending the overall life of the device.

Further, the apparatus for separating and recovering hydrogen fluoride according to the present invention includes two or more gas recovery units including the recovery storage tank, the ejector, the absorption liquid circulation flow path, and the pump, and is provided at the unit side terminal of the gas recovery flow path. The calcium fluoride discharged from various steps is set in accordance with the change of the type and concentration of the hydrogen fluoride-based gas generated in the vertical reaction vessel and the recovery unit switching mechanism of the gas recovery unit connected to the gas recovery flow path. In the case of a raw material, even if the fluorine content is low, the amount of impurities is large, or a mixture of two or more types of calcium fluoride is used, the classification or concentration (purity) may be classified to be recovered (regenerated).

Next, an embodiment of the present invention will be described in detail based on the drawings. However, the present invention is not limited to this embodiment.

Fig. 1 is a schematic view showing a configuration of a method for separating and recovering hydrogen fluoride according to a first embodiment of the present invention, and Fig. 2 is a schematic configuration diagram of a vertical reaction container used in the separation and recovery method. Moreover, in the drawing, the storage tank (transfer piping), the support pipe (mounting base), the base, etc. which support the said vertical reaction container, and the storage tank of the raw materials (calcium fluoride, sulfur-

As shown in Fig. 1, the method for separating and recovering hydrogen fluoride according to the first embodiment includes a gas separation step of generating hydrogen fluoride (HF) gas in the vertical reaction vessel R and separating it, and a gas recovery step using the recovery tank T The inner absorbent (water: H ₂ O) circulates at a negative pressure generated by the ejector E, and the hydrogen fluoride gas generated as described above is sucked from the vertical reaction vessel R to mix (absorb) the gas into the absorbing liquid (water). Next, it is stored in the recovery tank T. The separation and recovery method of the hydrogen fluoride according to the present invention and the separation and recovery device are characterized in that the separation and recovery of the hydrogen fluoride gas are performed by using a vertical reaction vessel R having a different agitation property than a conventional horizontal kiln. Among them, the hydrogen fluoride gas is efficiently produced in a short time using a batch type.

Further, the absorption liquid in the recovery storage tank T contains water as a main component, and may contain a component such as an antifreeze.

Hereinafter, the separation and recovery process of the above hydrogen fluoride will be described in the order of device configuration. First, the gas separation step of generating hydrogen fluoride gas is carried out using a vertical reaction vessel R as shown in Fig. 2 on the left side of Fig. 1 and its enlarged view. The vertical reaction vessel R is a closed type in which corrosive hydrogen fluoride (HF) gas is enclosed, and the inner surface 1a of the vessel R is an inverted conical shape which is gradually reduced in diameter from the upper portion to the lower portion (bottom portion 1b).

Further, in the upper portion (upper surface) of the container body 1 of the vertical reaction vessel R, a powder inlet port 1w is provided for introducing a calcium fluoride-based material (main component CaF ₂ ) which is a gas generating raw material; 1x, for inputting sulfuric acid (H ₂ SO ₄ : concentrated sulfuric acid or fuming sulfuric acid, etc.) as a liquid raw material; and a gas suction port 1y for sucking hydrogen fluoride (HF) gas generated inside the above. In the lower portion (bottom portion 1b) of the container body 1, a powder discharge port 1z is provided for discharging residual anhydrous calcium sulfate produced by the reaction of the calcium fluoride-based raw material with concentrated sulfuric acid or the like (production of HF gas). (CaSO ₄ ) powder (so-called "anhydrous gypsum").

Further, the material of the container body 1 of the vertical reaction vessel R is not particularly limited. However, when the material is corroded by the hydrogen fluoride gas generated inside, the entire inner surface 1a of the container R is preferably corrosion-resistant in advance. It is preferable to coat the resin lining or the resin film (film). Further, a heating jacket 3 for heating and warming the entire container R is attached to the outer surface of the container body 1 of the vertical reaction vessel R (see FIGS. 1 and 2).

Further, in the vertical reaction vessel R (internal), a stirring mechanism 2 having two different rotating shafts (rotary shaft-revolving shaft) for supplying a calcium fluoride-based raw material (powder) as a raw material is provided. Or granules) are efficiently stirred with sulfuric acid or the like (liquid). This is also one of the features of the hydrogen fluoride separation and recovery apparatus of the present invention.

As shown in Fig. 2, the stirring mechanism 2 includes a stirring blade 2a (such as a spiral spiral blade or a spiral wing), and is driven by the motor M _{2 to} be inclined along the inner surface 1a of the vertical reaction vessel R. shaped self-rotation (rotation); and the arm rotation shaft 2b and 2C, this rotary stirring blades 2a (rotation) of the state, and rotated together with the motor M ₁ (rotation axis) along the inner surface of the container of R 1a Revolutionary movement [歳 difference movement (so-called "swirl movement")].

When the stirring mechanism 2 having the above configuration is actuated, the calcium fluoride-based raw material (not shown in Fig. 2) is introduced into the vertical reaction vessel R, and the stirring blade 2a (spiral blade) itself is rotated. The mixture is stirred upward from the bottom 1b of the container to the upper portion along the inner wall (inner surface 1a). In the state in which the agitating blade 2a is rotated, the whole is revolved along the inner surface 1a of the container (the squat movement), so that the calcium fluoride-based raw material and the concentrated sulfuric acid which is supplied from the upper liquid inlet 1x, It can be thoroughly stirred and mixed in a short time.

Further, the heating jacket 3 disposed on the outer surface of the vertical reaction vessel R is fluorinated by circulating a fluid (heat medium such as oil: about 100 to 150 ° C) flowing from the medium inlet 3b to the medium outlet 3a. During the stirring and mixing of the calcium-based raw material and concentrated sulfuric acid, the container R is kept warm and warmed as a whole. Further, the set temperature of the heating jacket 3 is generally 100 to 150 ° C, more preferably 110 to 130 ° C.

According to the method for separating and recovering hydrogen fluoride according to the embodiment of the present invention (gas separation step) and the apparatus, the configuration of the stirring mechanism 2 and the inner surface 1a of the vertical reaction vessel R are inverted conical shape. The mixing of the calcium fluoride-based raw material with concentrated sulfuric acid or the like and the separation of the fluorine-containing component (the separation of the hydrogen fluoride gas) are completed in a shorter period of time than the conventional method. Further, since calcium fluoride and the equivalent concentrated sulfuric acid are uniformly and rapidly mixed in the inside of the vessel, the production efficiency (yield) of hydrogen fluoride (HF) gas caused by the reactions can be enhanced.

Further, the configuration of the vertical reaction vessel R and the stirring mechanism 2, together with the shape of the inner surface 1a of the container R (inverted conical shape), has the advantage of reversing the agitating blade 2a (spiral blade). (Reverse rotation with the above-mentioned rotation direction), the anhydrous calcium sulfate (CaSO ₄ ) powder (anhydrous gypsum) produced by reacting the calcium fluoride-based raw material with concentrated sulfuric acid or the like, simply discharges the powder from the bottom 1b side 1z discharge.

Next, each step of sucking, recovering, and concentrating (storing) the hydrogen fluoride gas generated in the vertical reaction vessel R is composed of the following components: a recovery tank T of hydrogen fluoride gas shown on the right side of FIG. The E, the circulation pump P, and the absorption liquid circulation flow path 11 connecting the members; and the gas recovery flow path 10 for sucking hydrogen fluoride (HF) gas generated in the vertical reaction vessel R (directed to the injector E).

First, the step of pumping the hydrogen fluoride gas is a circulation pump P, and as shown in FIG. 1, the hydrogen fluoride absorption liquid (in this case, water: H ₂ O) stored in the recovery storage tank T is passed through the absorption liquid circulation flow path. 11. The pressure is sent to the passage of the fluid inlet 4 (upper side) of the ejector E, and the small hole (narrow portion or small hole or the like: omitted) passing through the inside of the ejector E is passed to the side of the fluid outlet 5 for passage. The lower side of the figure is circulated, and the suction fluid inflow port 6 connected to the side gas recovery flow path 10 generates a negative pressure for gas suction while causing the absorption liquid flowing out from the above-mentioned passage fluid outlet 5. It is recovered to the recycle recovery tank T via the absorption liquid circulation flow path 11. By the circulation of the absorbing liquid (water), the suction port (suction fluid inflow port 6) of the ejector E can continuously generate a negative pressure for the hydrogen fluoride gas suction.

Next, the step of recovering the hydrogen fluoride (HF) gas as described above, as shown in Fig. 1, is a hydrogen fluoride (HF) gas generated in the vertical reaction vessel R, from the upper gas suction port 1y, through the gas connected thereto. The recovery flow path 10 is sucked by the negative pressure generated by the ejector E, and is then sucked into the ejector E from the suction fluid inflow port 6 of the ejector E of the negative pressure generating source, through the small The hole (not shown) is collected in the recovery tank T in a state where it is mixed with the absorbing liquid (water) passing through the ejector E.

Further, the step of generating the negative pressure for gas suction and the step of sucking out the hydrogen fluoride gas to be absorbed (mixed) by the absorption liquid are continuous operation (production) until the absorption liquid (water) in the recovery storage tank T The concentration of the absorbed hydrogen fluoride (HF) component reaches a predetermined concentration, and the hydrogen fluoride taken out from the vertical reaction vessel R is concentrated in the recovery storage tank T (hydrogen fluoride concentration step).

The ejector E used in each of the above steps has a structure (shape) which is not different from that of a general versa, but is formed by using a resin which is resistant to hydrogen fluoride, or an ejector which is in contact with a hydrogen fluoride-based fluid. The E surface (mainly the inner surface) is coated with a resin lining (resin film) which is resistant to hydrogen fluoride as described above. This is also one of the features of the present invention.

The resin used for forming or lining the ejector E may be a synthetic resin such as Teflon (registered trademark) or polyethylene. Further, in addition to the ejector E formed of the above-mentioned Teflon (registered trademark) or polyethylene, an FRP product using carbon fiber or organic fiber (glass fiber may also be used) may be used.

According to the ejector E of the above-described configuration, since there is no movable portion (shaft seal portion) as compared with a conventional suction (vacuum) pump or the like, there is little concern that leakage of hydrogen fluoride is small, and the suction operation can be continuously performed safely. Moreover, since there is no doubt that the shaft seal portion or the hydrogen fluoride leaks out, the maintenance frequency of the injector E and the entire device is small, and the service life of the device can be extended.

Further, as shown in Fig. 1, the hydrogen storage recovery tank T used in each of the above steps is composed of a recovery tank 7 in which a filler (a filling material for gas-liquid contact) is disposed, and a degassing tank 8, and The recovered hydrogen fluoride (HF) is dissolved in a state in which the water is the main component of the absorbent.

Further, in order to prevent the leakage of hydrogen fluoride, the recovery storage tank T is also a closed structure, and the exhaust gas (containing a small amount of hydrogen fluoride) is sent to a dedicated exhaust gas device (not shown). Further, similarly to the above-described ejector E, it is preferable to apply a resin lining (resin film) which is resistant to hydrogen fluoride to the surface (mainly the inner surface) of the recovery tank T which the hydrogen fluoride-based fluid contacts. Further, a concentration detecting mechanism (not shown) capable of measuring (monitoring) the concentration of hydrogen fluoride in the absorption liquid in the recovery tank T (degassing tank 8) may be provided.

On the other hand, the circulation pump P used for circulating the absorption liquid (water) containing the above hydrogen fluoride must not cause the absorption water to leak. In the present embodiment, the electromagnetic system using the liquid-free seal (shaft seal) is used. Pumps (inductive electromagnetic pumps) or diaphragm pumps, piston pumps, etc. are preferred. Further, the form (type) of the pump is not particularly limited, but it is preferably the same as the injector E or the recovery tank T, and the inner portion of the pump or the piping portion, the rotor or the diaphragm, the piston, etc., which are in contact with the hydrogen fluoride, are preferably applied. Hydrogen fluoride has a corrosion-resistant resin lining (resin film). Further, the electromagnetic pump is not replaced by a general pressure feed pump composed of a corrosion-resistant metal (alloy) such as HASTELLOY (registered trademark).

Further, it is preferable that the inner surface of the pipe and the connecting portion of the absorbing liquid circulation flow path 11 connected to the circulation pump P or the gas recovery flow path 10 for sucking out hydrogen fluoride (HF) gas are similarly applied to hydrogen fluoride. Corrosion resistant resin lining. Thus, by making the device as a whole corrosion-resistant structure, the life of the device and the safety of the person who operates the device can be improved.

According to the above-described method for separating and recovering hydrogen fluoride (gas recovery/concentration step) and the apparatus, hydrogen fluoride can be prevented from being leaked out and safely absorbed by the absorption liquid (water). Further, by continuously circulating the above-mentioned absorption liquid and adding high efficiency of hydrogen fluoride (HF) gas in the gas separation step (vertical reaction vessel R), the concentration of hydrogen fluoride in the above-mentioned absorption liquid can be easily increased to be taken out as The concentration of the product (as hydrofluoric acid of the recycled product) (about 50 to 60% by weight). Therefore, according to the method and apparatus for separating and recovering hydrogen fluoride according to the present embodiment, the cost (operating cost) required for the regeneration (recycling) of hydrogen fluoride can be lowered to a level suitable for practical use.

Finally, the above-described method for separating and recovering hydrogen fluoride (regeneration of hydrogen fluoride) and a calcium fluoride-based material (recovery of calcium fluoride) used in the apparatus will be described.

In general, as the calcium fluoride recovered in the present embodiment, as described above, a fluorination treatment is carried out by discharging a liquid (treatment liquid) containing a high concentration of hydrogen fluoride or fluoroantimonic acid. Calcium (CaF ₂ ) or calcium fluoroantimonate [Ca[SiF ₆ ]: calcium hexafluoroantimonate] is obtained by dehydration and drying. The recovered calcium fluoride is firstly dried into a soft aqueous solid such as a cake by a dehydration operation such as compression or centripetal separation, and then subjected to a drying or pulverization step to have a general moisture content of 20% by weight or less (preferably 10% by weight or less of the sponge-like powder or granules agglomerate and is used as an industrial waste carrying-out step (factory).

In addition, as the recovered calcium fluoride used in the present embodiment, the purity (content ratio of calcium fluoride to other ash) is generally 70% by weight or more, preferably 80% by weight or more. The reason for this is that if the purity (content ratio) of the calcium fluoride is too low, the yield of each batch of hydrofluoric acid (recycled product) decreases, and the production efficiency tends to decrease. Further, since the purity of the anhydrous gypsum as the reaction residue is lowered, the use or the value of the use of the gypsum is lowered.

Further, when the moisture content of the recovered calcium fluoride is too high, when the sulfuric acid or the like is introduced (mixed), the water contained in the recovered calcium fluoride boils, and the hydrogen fluoride (HF) gas generated together is used by the injector E. The suction is suctioned from the recovery line (gas recovery flow path 10) into the circulation line (absorption liquid circulation flow path 11), and the concentration of hydrogen fluoride in the absorption liquid in the recovery storage tank T (degassing tank 8) is lowered.

However, in this case or when the purity of the calcium fluoride is low, if the fuming sulfuric acid is added to the concentrated sulfuric acid which recovers the calcium fluoride, the so-called "recycling tank T (degassing tank 8)" can be solved. The concentration of hydrogen fluoride in the absorption liquid is not easily increased (the efficiency and yield of each batch are poor). Further, the hydrofluoric acid concentration (target: about 50 to 60% by weight) as a product (recycled product) stored in the recovery storage tank T may be a series of steps of repeating the separation-recovering-concentration of the hydrogen fluoride (batch) The number of times) to modulate.

Next, a second embodiment of the present invention in which a plurality of hydrogen fluoride-based gases (in this case, hydrogen fluoride (HF) and fluoroantimonic acid (H ₂ [SiF ₆ ])) can be separately recovered will be described.

Fig. 3 is a block diagram showing the outline of a method for separating and recovering hydrogen fluoride according to a second embodiment of the present invention. Further, in the illustration, the support is omitted vertical reactor vessel of the support member (gantry) or a base, raw material storage tank or delivery pipe provided in each recovery tank T _1, T ₂ of the exhaust gas, drainage systems. The constituent elements having the same functions as those of the first embodiment are denoted by the same reference numerals, and the detailed description thereof will be omitted.

In the method (device) for separating and recovering hydrogen fluoride according to the second embodiment, calcium fluoroantimonate [Ca[SiF ₆ ]: calcium hexafluoroantimonate] is used as a calcium fluoride-based raw material, and is produced by mixing with sulfuric acid or the like. Fluoric acid (H ₂ [SiF ₆ ]) and hydrogen fluoride (HF) are recovered in two stages.

As shown in Fig. 3, the apparatus used for the separation (respective) recovery method of hydrogen fluoride differs from the first embodiment in that it has two groups (from the ejector E ₁ , the recovery sump T _{1 ,} and the circulation pump P _{1 ).} The first gas recovery step and the gas recovery step of the second gas recovery step consisting of the ejector E ₂ , the recovery storage tank T ₂ and the circulation pump P ₂ . The two sets of gas recovery steps are divided into two branches from the terminal of the gas recovery flow path 10 for sucking (directing the hydrogen fluoride-based gas generated in the vertical reaction vessel R) into two branches, and the branches are connected thereto. The point arrangement is: a flow regulating valve V ₁ ; and a switching valve V ₂ (three-way piston: a recovery unit switching mechanism) for switching the flow of the hydrogen fluoride gas flowing through the pipe of the gas recovery flow path 10.

Further, in the first gas recovery step (upper side in the drawings) in the gas recovery flow on path 10 ', the lower side of the second gas recovery step is not the ejector E ₁ (aperture) of the jamming inhibiting means 9 via the configuration at The upstream side of the injector E ₁ . The other configuration is the same as the gas recovery step (refer to FIG. 1) of the first embodiment, and the members corresponding to the members 4, 5, 6, 7, 8, and 11 of the first embodiment are respectively given. The symbols of 4', 5', 6', 7', 8', and 11' are omitted, and the description thereof is omitted. The second gas recovery step (lower side in the drawing) is the same as the gas recovery step in the first embodiment. In this way, the gas recovery flow path 10 immediately after the vertical reaction vessel R (gas suction port 1y) is disposed with a concentration detecting mechanism (not shown) for measuring (monitoring) the concentration of the hydrogen fluoride gas, which is instantaneous ( Timing) The composition (principal component) of the gas flowing through the gas recovery flow path 10 is measured.

In the separation and recovery method of hydrogen fluoride using the separation (respective) recovery apparatus of the above configuration, the calcium fluoroantimonate (Ca[SiF ₆ ]) powder is first introduced into the inner surface 1a into an inverted cone from the powder input port 1w. In the reaction vessel R, a concentrated sulfuric acid (or a mixture of concentrated sulfuric acid and fuming sulfuric acid) is added from the liquid inlet 1x while stirring by the stirring mechanism 2 having the stirring blade 2a, whereby a hydrogen fluoride-based gas is generated.

In the case of this reaction (mixing of calcium fluoroantimonate and concentrated sulfuric acid), according to the inventors' knowledge, it is known that high concentration of fluoroantimonic acid (H ₂ [SiF ₆ ]) is preferentially generated in the first half of the stirring and mixing. After substantially completely ending, a high concentration of hydrogen fluoride (HF) is then produced as a main component of the gas. Further, the inventors have empirically learned that the above-mentioned fluoroantimonic acid gas is more likely to precipitate (crystallize) than the hydrogen fluoride gas, so that the pores of the ejector are easily clogged.

Therefore, in the method for separating and recovering hydrogen fluoride according to the second embodiment, first, the first gas recovery step (the upper side of the figure) of the plugging prevention mechanism 9 is connected to the end of the gas recovery flow path 10 (switching valve V ₂ ). ), so that the precipitation of easily cause clogging fluoro silicic acid (H ₂ [SiF _6]) gas, E via the injector _1, the recovery tank and the recovery of the T _groove 7 'and degassing tank 8' is collected and concentration.

Then, when the concentration of the gas flowing through the gas recovery flow path 10 is checked by the concentration detecting means (not shown) of the hydrogen fluoride-based gas, the switching valve at the end of the gas recovery flow path 10 (three-way) The connection target of the piston) V ₂ is switched, and the gas generated in the vertical reaction vessel R (the hydrogen fluoride (HF) gas in the same manner as in the first embodiment at this point) is turned to the second gas on the lower side of the drawing. The recycling step flows. Thereby, the generated hydrogen fluoride is collected and concentrated in the recovery tank 7 and the degassing tank 8 of the recovery storage tank T ₂ .

In this way, it is repeated in batch units: generation of a hydrogen fluoride-based gas by the vertical reaction vessel R; switching of a gas recovery step (first ←→second) using gas component monitoring; and hydrogen fluoride-based gas The fluorononanoic acid and hydrogen fluoride generated from the above-mentioned calcium fluoroantimonate are separately recovered and concentrated, and are efficiently recovered.

Further, the concentration detecting means and the clogging preventing means 9 for measuring (monitoring) the gas concentration may be attached to the second gas collecting step having the same configuration as that of the first embodiment, and may be disposed before the branching gas. The recovery flow path 10 is halfway. [Examples]

Next, an example (positive test) carried out using the above-described hydrogen fluoride separation and recovery apparatus (Fig. 1) of the present invention will be described.

[Example 1] <Material: Recovering Calcium Fluoride> In a semiconductor manufacturing plant or the like, calcium hydroxide was added to the discharged hydrogen fluoride-containing discharge liquid, and the water content was 33% by weight by centrifugal dehydration and compression. Solids. Then, it was heated and dried and pulverized to obtain recovered calcium fluoride having a water content of 10% by weight (granular shape after secondary aggregation of calcium fluoride: average particle diameter: 5.4 μm, particle size distribution: 1 to 50 μm). Further, the constituent components of the above-mentioned recovered calcium fluoride (solid component for removing moisture) were: calcium fluoride 82.5 wt%; calcium sulfate 10 wt%; alumina 2 wt%; cerium oxide 1 wt%; and other ash 4.5 wt%. Further, the particle size (distribution) of the recovered calcium fluoride is measured according to the particle size measuring method specified in JIS M 8100 "Powder Mixture - Sampling Method General Principle"; the moisture content (water content) of the recovered calcium fluoride is determined JIS K 1468-1 "The fluorite analysis method for fluoric acid (quantification of the moisture content of the first batch)" is measured by the moisture content (after 105 ° C × 5 hours of absolute drying).

<Hydrogen fluoride separation step> 100 kg of the above-mentioned recovered calcium fluoride (water content: 10% by weight) was charged into a vertical reaction vessel R (refer to FIG. 1), and the oil heated to 110 ° C was circulated in the heating jacket 3 of the winding container R. And spare. Next, the stirring mechanism 2 is actuated, and calcium fluoride (powder) is stirred and recovered, and a predetermined amount (mole equivalent) of concentrated sulfuric acid is applied to the calcium fluoride (net weight: 74.25 kg) for 30 minutes. The fixed flow rate is slowly introduced (added) into the vertical reaction vessel R. Further, stirring was continued after the completion of the concentrated sulfuric acid supply, and the final stirring time was from the start of the injection of concentrated sulfuric acid until the end of the generation of the hydrogen fluoride gas, and it took 2 hours (1 batch = 2 hours).

<Hydrogen fluoride recovery step> Simultaneously with the start of the introduction of the concentrated sulfuric acid, the circulation pump P is actuated, and the negative pressure generated by the injector E is used in the vertical movement in the entire batch time (2 hours) of the above-mentioned batch. The gas (mainly hydrogen fluoride) generated in the reaction vessel R is absorbed by the absorption liquid (water: 30 kg) and recovered to the recovery storage tank T. Moreover, after the end of 2 hours in one batch, the gypsum remaining in the vertical reaction vessel R is taken out from the powder discharge port 1z at the lower portion of the vessel R, and the reaction vessel R is evacuated to carry out the next (next batch). ) Preparation.

<Hydrogen Fluoride Concentration Step> The above-mentioned "calcium fluoride injection - sulfuric acid supply - hydrogen fluoride recovery 1 cycle (1 batch)" was repeated three times to obtain a regenerated hydrofluoric acid (aqueous solution) having a hydrogen fluoride concentration of 56% by weight.

Further, the hydrogen fluoride concentration was 35.5% by weight at the end of the first batch, and was 48.8% by weight at the end of the second batch. The hydrofluoric acid having a concentration of 56% by weight (product shipment standard: 55 wt% or more) obtained in the third batch described above can be sufficiently used for industrial recycling. Further, analysis (X-ray fluorescence analysis) of the gypsum extracted from the lower portion of the vertical reaction vessel R was found to be an anhydrous gypsum for industrial use, which was 97% by weight of fluorine. Further, the above-mentioned regenerated hydrofluoric acid having a concentration of 56% by weight was used for glass etching, and it was found to be used smoothly.

[Example 2] <Material: Recovery of calcium fluoride> In the step of incineration (disposal) containing a fluorine compound, calcium hydroxide is added to the discharged hydrogen fluoride-containing discharge liquid, and centrifugal dehydration and compression are obtained. A soft solid having a moisture content of 33% by weight. Thereafter, the mixture was heated and dried and pulverized to obtain recovered calcium fluoride having a water content of 5% by weight (granular shape of calcium fluoride secondary aggregation: average particle diameter: 10.7 μm, particle size distribution: 1 to 100 μm). Further, the constituent components of the above-mentioned calcium fluoride (solid component for removing moisture) are: calcium fluoride 94% by weight; calcium sulfate 1% by weight; cerium oxide 1% by weight; and other ash 4% by weight. Further, as described above, the particle size (distribution) and water content (water content) of the recovered calcium fluoride are based on JIS M 8100 "Powder Mixture - Sampling Method General" and JIS K 1468-1 "Fluorine Fluoride" Measured by stone analysis method.

<Hydrogen fluoride separation step> 100 kg of the above-mentioned recovered calcium fluoride (water content: 5% by weight) was put into a vertical reaction vessel R (refer to FIG. 1), and the oil heated to 110 ° C was circulated in the heating jacket 3 of the winding container R. And spare. Next, the stirring mechanism 2 is actuated, and calcium fluoride (powder) is stirred and recovered, and a predetermined amount (mole equivalent) of concentrated sulfuric acid is applied to the calcium fluoride (net weight: 89.3 kg) to be used for 30 minutes. The fixed flow rate is slowly introduced (added) into the vertical reaction vessel R. Further, stirring was continued after the completion of the concentrated sulfuric acid supply, and the final stirring time was from the start of the injection of concentrated sulfuric acid until the end of the generation of the hydrogen fluoride gas, and it took 2 hours (1 batch = 2 hours).

<Hydrogen fluoride recovery step> Simultaneously with the start of the introduction of the concentrated sulfuric acid, the circulation pump P is actuated, and the negative pressure generated by the injector E is used in the vertical movement in the entire batch time (2 hours) of the above-mentioned batch. The gas (mainly hydrogen fluoride) generated in the reaction vessel R is absorbed by the absorption liquid (water: 30 kg) and recovered to the recovery storage tank T. Moreover, after the end of 2 hours in one batch, the gypsum remaining in the vertical reaction vessel R is taken out from the powder discharge port 1z at the lower portion of the vessel R, and the reaction vessel R is evacuated to carry out the next (next batch). ) Preparation.

<Hydrogen Fluoride Concentration Step> The above-mentioned "calcium fluoride injection - sulfuric acid supply - hydrogen fluoride recovery 1 cycle (1 batch)" was repeated three times to obtain a regenerated hydrofluoric acid (aqueous solution) having a hydrogen fluoride concentration of 64.8% by weight.

Further, the hydrogen fluoride concentration was 41.4% by weight at the end of the first batch, and was 56.8 wt% at the end of the second batch. The hydrofluoric acid having a concentration of 64.8 wt% (product shipment standard: 55 wt% or more) obtained in the third batch described above can be sufficiently used for industrial recycling. Further, analysis (X-ray fluorescence analysis) of the gypsum extracted from the lower portion of the vertical reaction vessel R was found to be an anhydrous gypsum for industrial use, which was 97% by weight of fluorine. Further, the above-mentioned regenerated hydrofluoric acid having a concentration of 64.8% by weight can be smoothly used for etching of glass. [Industry use possibility]

According to the method for separating and recovering hydrogen fluoride according to the present invention and the apparatus for separating and recovering hydrogen fluoride, hydrogen fluoride can be efficiently recovered from calcium fluoride discharged from various steps in a safe and maintenance-free manner. Therefore, the hydrogen fluoride recovery system is put into practical use at a sustainable low operating cost by providing a step or a factory for discharging the fluorine-containing discharge liquid or waste.

1‧‧‧ container body
1a‧‧‧ inside
1b‧‧‧ bottom
1w‧‧‧ powder input
1x‧‧‧ liquid input
1y‧‧‧ gas suction
1z‧‧‧ powder discharge
2‧‧‧Agitating mechanism
2a‧‧‧Agitating blades
2b‧‧‧arm
2c‧‧‧Rotary axis
3‧‧‧ heating jacket
3a‧‧‧Media exports
3b‧‧‧Media portal
4, 4'‧‧‧ fluid inlet
5, 5'‧‧‧ fluid outlet
6, 6'‧‧‧ suction fluid inlet
7, 7'‧‧‧Recycling tank
8, 8'‧‧‧ Degassing tank
9‧‧‧Clog prevention mechanism
10, 10'‧‧‧ gas recovery flow path
11, 11 '‧‧ ‧ absorption liquid circulation flow path
E, E ₁ , E ₂ ‧ ‧ ejector
M ₁ , M ₂ ‧ ‧ motor
P‧‧‧ pump
P ₁ , P ₂ ‧ ‧ circulation pump
R‧‧‧Vertical reaction vessel
T‧‧‧Recycled storage tank
T ₁ , T ₂ ‧ ‧ recycling tank
V ₁ ‧‧‧Flow adjustment valve
V ₂ ‧‧‧ switching valve

Fig. 1 is a block diagram showing the structure of a separation and recovery apparatus used in the method for separating and recovering hydrogen fluoride according to the first embodiment of the present invention. Fig. 2 is a structural view of a vertical reaction vessel used in the above-described apparatus for separating and recovering hydrogen fluoride. Fig. 3 is a block diagram showing the structure of a separation and recovery apparatus used in the method for separating and recovering hydrogen fluoride according to the second embodiment of the present invention.

1‧‧‧ container body

1a‧‧‧ inside

1b‧‧‧ bottom

1w‧‧‧ powder input

1x‧‧‧ liquid input

1y‧‧‧ gas suction

1z‧‧‧ powder discharge

2‧‧‧Agitating mechanism

2a‧‧‧Agitating blades

2b‧‧‧arm

2c‧‧‧Rotary axis

3‧‧‧ heating jacket

3a‧‧‧Media exports

3b‧‧‧Media portal

4‧‧‧ fluid inlet

5‧‧‧ fluid outlet

6‧‧‧Sucking fluid inlet

7‧‧‧Recycling tank

8‧‧‧ Degassing tank

10‧‧‧ gas recovery flow path

11‧‧‧ absorption liquid circulation flow path

E‧‧‧Injector

M ₁ , M ₂ ‧ ‧ motor

P‧‧‧ pump

R‧‧‧Vertical reaction vessel

T‧‧‧Recycled storage tank

Claims (8)

A method for separating and recovering hydrogen fluoride, which comprises a closed vertical reaction vessel capable of sealing a gas generated in a reaction vessel, the reaction vessel comprising: a cylindrical reaction vessel; and a stirring mechanism for stirring the powder in the reaction vessel up and down a recovery storage tank for storing an absorption liquid for absorbing gas; and a gas suction mechanism comprising an ejector and a pump for supplying a fluid for generating a negative pressure to the ejector, the method for separating and recovering hydrogen fluoride comprises: In the separation step, the calcium fluoride-based raw material is filled into the vertical reaction vessel, and while adding sulfuric acid, the stirring component of the stirring mechanism is used to stir the mixture up and down, and the fluorine component is separated from the calcium fluoride-based raw material as a hydrogen fluoride system. a gas; a negative pressure generating step of storing a water-based absorbing liquid for absorbing a hydrogen fluoride-based gas in the recovery sump, and circulating the water-based absorbing liquid to the recovery sump via the ejector by using a pump, so that the ejector generates gas pumping Negative pressure for suction; gas recovery step, using the negative pressure of the injector, sucking out the vertical reaction vessel a hydrogen fluoride-based gas generated, the gas is mixed into the water-based absorption liquid in the ejector, and the mixed liquid is recovered into the recovery storage tank; and the hydrogen fluoride concentration step is continued to carry out the water-based absorption liquid through the ejector using the pump The circulation and the hydrogen fluoride-based gas generated in the vertical reaction vessel are recovered until the concentration of the hydrogen fluoride-based component absorbed by the aqueous absorbent in the recovery storage tank reaches a predetermined concentration. The method for separating and recovering hydrogen fluoride according to claim 1, wherein the inner surface of the vertical reaction vessel has an inverted conical shape which gradually decreases in diameter from the upper portion to the lower portion, and the stirring blade of the stirring mechanism is along the inverted conical shape. The inner peripheral surface is subjected to coma movement. The method for separating and recovering hydrogen fluoride according to claim 1 or 2, wherein the inner surface of the vertical reaction vessel in contact with the hydrogen fluoride component, the inner surface of the recovery tank, and the contact surface of the water-based absorbent in the ejector and the pump The inner surface of the pipe through which the hydrogen fluoride-based gas passes is covered with a resin lining or a resin film having corrosion resistance. The method for separating and recovering hydrogen fluoride according to claim 1 or 2, wherein the gas recovery unit comprising the recovery tank and the gas suction mechanism is provided in two or more groups, and corresponds to hydrogen fluoride generated in the vertical reaction vessel. The gas recovery unit connected to the vertical reaction vessel is switched for recovery by changing the type and concentration of the gas. A hydrogen fluoride separation and recovery device comprising: a closed vertical reaction vessel having a hydrogen fluoride-based gas suction port at an upper portion thereof and a powder discharge port at the bottom of the reaction; and a stirring mechanism for the vertical reaction vessel The calcium fluoride-based raw material is stirred up and down; the storage tank is recovered, and the water-based absorption liquid for absorbing the hydrogen fluoride-based gas is stored; the ejector is disposed between the vertical reaction vessel and the recovery storage tank; and the absorption liquid circulates the flow path, so that The water-based absorption liquid in the recovery storage tank is returned to the recovery storage tank through the ejector; the pump sends the water absorption hydraulic pressure in the recovery storage tank to the ejector as a fluid for generating a negative pressure; and a gas recovery flow path, The hydrogen fluoride gas generated in the vertical reaction vessel is sucked between the suction port of the vertical reaction vessel and the ejector. The apparatus for separating and recovering hydrogen fluoride according to claim 5, wherein the inner surface of the vertical reaction vessel has an inverted conical shape which gradually decreases in diameter from the upper portion to the lower portion, and the stirring blade of the stirring mechanism is along the inverted conical shape. The squat movement is carried out on the circumference. The apparatus for separating and recovering hydrogen fluoride according to claim 5 or 6, wherein the inner surface of the vertical reaction vessel in contact with the hydrogen fluoride component, the inner surface of the recovery tank, the contact surface with the fluid in the injector and the pump, and The inner surface of the pipe for the absorption liquid circulation flow path and the gas recovery flow path is covered with a resin lining or a resin film having corrosion resistance. The apparatus for separating and recovering hydrogen fluoride according to claim 5 or 6, wherein the gas recovery unit comprising the recovery tank, the ejector, the absorption liquid circulation flow path, and the pump is provided in the gas recovery flow. The unit side terminal of the road is provided with a recovery unit switching mechanism that switches the gas recovery connected to the gas recovery flow path in accordance with the change in the type and concentration of the hydrogen fluoride gas generated by the vertical reaction vessel. unit.