JP2002301362A - Reactor and method for producing hydrogen iodide using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactor in which a solid is thrown in a liquid with good operability, particularly a reactor in which iodine as a starting material is added in the solid state when hydrogen iodide is produced from naphthalene hydride and iodine. SOLUTION: The reactor in which a solid is added to a liquid and reacted has a solid charger having two valves for controlling a flow of the solid in series, having a space having a mechanism with which the solid is held between the valves and can be quantitatively added and having an inlet for feeding a gas inert to the above reaction and an exhaust port for depressurizing the space between the first and second valves.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for introducing a solid into a liquid. Further, particularly with respect to an apparatus for producing hydrogen iodide by adding iodine to a naphthalene hydride and a method for producing hydrogen iodide using the same, a method for producing hydrogen iodide gas with a high yield, iodine as a raw material It relates to an apparatus for adding in a solid state.

[0002] Hydrogen iodide is a raw material for synthesizing various iodides,
It is an industrially useful substance that is used as a pharmaceutical intermediate or a reducing agent, and has recently been spotlighted as an etching agent in the field of semiconductors. Hydrogen halide is widely used as an etching agent, and among them, hydrogen iodide has attracted attention for its high etching performance.

[0003] The apparatus of the present invention is used, for example, when obtaining hydrogen iodide used in the semiconductor manufacturing field.

[0004]

BACKGROUND OF THE INVENTION It is an object of the present invention to provide a method for producing hydrogen iodide gas, which is free from the drawbacks which are problematic in conventional methods, and to provide an industrial method for producing hydrogen iodide gas. It is to provide a device suitable for a computer. Various methods are known as a method for producing hydrogen iodide gas. For example, US Pat. No. 4,357,309 describes a device for extracting hydrogen iodide gas by reacting solid iodine with tetralin. In this apparatus, solid iodine and tetralin are charged in advance, and solid iodine and tetralin are dissolved therein by facing each other, and then guided to a reactor to generate hydrogen iodide gas. Basically, it is a device intended to easily generate hydrogen iodide gas on a table, and does not aim at increasing the reaction yield or size. That is, the generation of hydrogen iodide gas is limited to the amount of iodine dissolved in tetralin at room temperature at the maximum, and there is a disadvantage that the conversion of tetralin is low.

[0005] Further, a method conventionally used industrially in the production of hydrogen iodide gas is to add a tetralin solution in which iodine is dissolved in a dissolving tank to a reactor containing a small amount of heated tetralin. To produce hydrogen iodide in a reactor. However, in this method, only a small amount of tetralin can be initially charged into the reactor, and when the tetralin solution in which iodine is dissolved is charged and the reactor is almost full, the reaction is terminated. There is a drawback that two units of a dissolving tank are required and the volumetric efficiency of the reactor is poor. Therefore, production by a more efficient production method has been desired.

[0006] Further, in the conventionally known method, the operation is sometimes limited in terms of the solubility of iodine in tetralin.

[0007]

Conventionally, when a solid substance is introduced into a reactor or the like from the outside and allowed to react, since the addition form by a pipe or the like cannot be taken, the reaction system usually generates pressure such as gas generation. In many cases, it is carried out when no problem occurs. In addition, even when gas is generated, the amount of the gas is relatively small, and is often limited to the case where the generated gas has no danger. However, when a solid is added to the reactor from the outside to generate gas and collect the generated gas, the generated solid may be scattered to the outside due to the generated pressure, or the generated gas may be discharged from the solid addition port. There are problems such as leakage and adverse effects on the environment. Furthermore, when the generated gas has corrosiveness, it is often difficult in terms of safety and working environment, and in this case, it is difficult to adopt a reaction mode in which solids are directly added to the reactor. .

The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a device for directly adding a solid in a controlled amount to a reaction system for generating a corrosive gas, for example, a hydride of naphthalene and iodine A device suitable for adding solid iodine, which is a raw material, to a system for generating hydrogen iodide gas by reacting with hydrogen was studied and arrived at the present invention.

[0009]

That is, the present invention comprises the following.

[0010] A reactor for adding a solid to a liquid and causing the two to react with each other, comprising a solid charging device provided for adding the solid to the liquid, the charging device comprising: At least two of the first valve and the second valve for controlling the flow of solids are provided in series, and the solids are quantitatively added to the liquid by sandwiching the solids between both valves An inert gas inlet for introducing an inert gas for the reaction between the first valve and the second valve, and an inert gas inlet between the first valve and the second valve; A reaction device comprising a degassing port for depressurizing between the second valves.

[0011] The reactor according to the above description, further comprising an apparatus having a function of quantitatively charging solids into the space.

An apparatus as described or described for adding a solid to a liquid and reacting the two to generate a gas.

[0013] At least a device having a function of quantitatively charging a solid substance into the space, and controlling the first valve and the second valve to quantitatively solidify the liquid within a certain period of time. The apparatus according to any one of-, wherein the substance is controlled to be added.

The liquid comprises a hydride of naphthalene,
The reactor according to any one of the above, wherein the solid substance is solid iodine and the generated gas is a hydrogen iodide gas.

[0015] A method for producing hydrogen iodide gas, comprising adding solid iodine to a liquid containing a hydride of naphthalene using the apparatus described in-.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the case of a reaction in which gas is generated from a reaction system, the inside of the system is at a positive pressure. Seal with inert gas to prevent gas leakage from solid inlet. The valve that is in direct contact with the reaction system is made of a corrosion-resistant material, and is compatible with corrosive gas. In addition, the material used is supported by a combination of resin, glass, and ceramic so that the solid can be charged even when it is a corrosive solid. As a result, a device capable of directly adding a solid to a reaction system in which corrosive gas is generated has been completed.

That is, the present invention provides, for example, a method for producing hydrogen iodide gas which does not have the drawbacks of conventionally known methods, and provides an industrially suitable apparatus for obtaining hydrogen iodide gas. It is characterized by providing. Generally, it is very difficult to add a solid to a place where a gas is generated in a reaction system. In this case, a method in which a solid is dissolved in a solvent and added in a liquid state is generally used. Furthermore, for example, in a system in which iodine and a hydride of naphthalene are reacted to synthesize hydrogen iodide gas, the iodine to be added has metal corrosiveness, and the generated hydrogen iodide gas also has metal corrosiveness, and it is harmful to humans. Toxic; caution is required against spills. In such a case, the material of the apparatus for quantitatively adding the solid used in the method of the present invention is a general-purpose resin such as glass, ceramic, vinyl chloride and polypropylene. These may be one kind or a combination of two or more kinds. The inert gas introduced into the solid addition device includes nitrogen, helium, argon and the like. These may be one kind or a combination of two or more kinds, but helium is particularly preferred. Hereinafter, specific examples of the reactor according to the present invention will be described in detail with reference to the drawings. FIG. 1 shows the basic configuration of the solid dosing apparatus of the present invention. The hopper 1 is located above a rotary valve 2 which is a quantitative addition device,
A solid to be added to the reaction system can be added. The rotary valve 2 is rotated at a constant speed by applying an arbitrary voltage, and a certain amount of solids per hour is supplied to the spacer 3.
Send to The valve 4 is opened for a certain period of time by an attached solenoid valve, and sends the solid matter to the spacer 7 to close it. At this time, since the gas is generated in the reactor, the reactor is in a positive pressure state.
Therefore, in order to make the inside of the spacer 7 a positive pressure before opening the valve 8, the valve 12 is opened and an inert gas is introduced into the spacer 7. At this time, the pressure inside the spacer 7 needs to be higher than the pressure of the reaction system. When the internal pressure of the spacer 7 becomes larger than the internal pressure of the reaction system, the valve 12 is closed. The internal pressure of the spacer 7 is set to be higher than the internal pressure of the reaction system by 0.001 to 10 MPa, and more preferably adjusted to be higher by 0.01 to 0.1 MPa. If the pressure difference is smaller than this, the gas of the reaction system infiltrates the inside of the spacer 7 and leaks from the addition port. On the other hand, if the pressure difference is larger than this, the production process will be inconvenient, such as affecting the pressure fluctuation inside the reaction system, which is not preferable. Next, valve 8 is opened and the solids are added into the reactor and closed. At this time, since the internal pressure of the spacer 7 is higher than the internal pressure of the reaction system as described above, it is possible to prevent the gas generated in the reaction system from entering the inside of the spacer 7. At this time, the internal pressure of the spacer 7 remains as high as the internal pressure of the reaction system. In order to release this pressure, the valve 13 is opened and closed. The valve 4 opens and closes again, and the above operation is repeated. A series of operations can be automated by opening and closing the solenoid valve with a timer. In addition, the rotary valve 2 enables the quantitative addition of solid matter. As described above, it is possible to directly add a solid to a reaction system that generates a gas with a simple device. The apparatus of the present invention can be used in a method for producing hydrogen iodide from a hydride of naphthalene (eg, tetralin, decalin) and iodine. In the method of the present invention, usually only one reactor is required, and a dissolution tank for iodine is not required. Further, in the present invention, the reactor can be charged almost completely with tetralin from the beginning and solid iodine can be added thereto, so that the volumetric efficiency of the reactor is improved by several times compared to the conventional method. Therefore, it became possible to manufacture efficiently. In the method for producing hydrogen iodide of the present invention, a reaction is carried out while adding iodine to a heated hydrogenated product of naphthalene. When adding solid iodine to the hydrogenated product of naphthalene, the shape of solid iodine is not particularly limited, and usually powdery, granular, or flake-like ones are frequently used, and in particular, flake-like or granular, Average particle size is 1 to 5 mm, preferably 2 to 3
mm is preferable as a solid having good fluidity.

The reaction pressure is not particularly limited and can be appropriately selected. Usually, the reaction pressure is frequently used because the operation at around normal pressure is easy. When the reaction is carried out under normal pressure, the reaction temperature is preferably from 120 to 210 ° C, more preferably from 15 to 210 ° C.
0-180 ° C. If the temperature is lower than 120 ° C., the progress of the reaction becomes extremely slow. Therefore, it is appropriate to carry out the reaction at a temperature in the range of 120 ° C. to the boiling point of the reaction solution (for example, about 210 ° C. when tetrahydronaphthalene is used). In this case, if the reaction temperature is lower than the above-mentioned reaction temperature, the rate of generation of hydrogen iodide becomes extremely low, which is not practical. When the reaction is carried out at a relatively high temperature, such as the boiling point of the reaction solution, the hydrogen adduct of naphthalene may evaporate from the reaction solution in addition to the generation of hydrogen iodide. These can be sufficiently separated by a known method such as ventilating the trap.

Further, for example, when tetrahydronaphthalene is used as the liquid, if the temperature is higher than the above-mentioned maximum temperature, the boiling point of tetrahydronaphthalene will be exceeded, and it will be very difficult to produce hydrogen iodide under normal pressure. Hydrogen iodide is also unfavorable because it tends to contain tetrahydronaphthalene. Of course, this reaction can be performed under pressure, but in this case, there is no concern about the above, and the reaction can be performed at a temperature exceeding 210 ° C.

In the method for producing hydrogen iodide according to the present invention,
When the amount of the hydrogenated product of naphthalene used in the reaction is less than the equivalent amount of the amount of iodine, unreacted iodine tends to be present in the hydrogenated product of naphthalene during the reaction, and in some cases, iodine Since it is conceivable that iodine vapor is generated in addition to hydrogen, the amount of use of the hydrogenated product of naphthalene is usually at least equivalent to iodine used in the reaction. In the present invention, even if the amount of the hydrogenated product of naphthalene is relatively large, there is no particular problem in achieving the object.

In the method of the present invention, the rate of addition of solid iodine to the hydrogenated product of naphthalene depends on the amount of the hydrogenated product of naphthalene used, the mode of addition, the reaction temperature, the production amount, or the shape of the reaction vessel. Although it is also unconditionally stated, usually, the object of the present invention can be sufficiently achieved as long as the color of the gas phase in the upper part of the reaction solution does not exhibit brown or purple.

Usually, iodine in the charged solid is usually added in an amount of 0.005 to 1.0 equivalent / mol of the hydrogenated product of naphthalene.
h, more preferably at an addition rate of 0.01 to 0.1 equivalent / h, and the reaction is carried out to generate hydrogen iodide from the reaction solution.

On the other hand, if the addition rate of iodine is lower than the above lower limit, it is not practical because the time efficiency is poor and naphthalene as a by-product is easily formed, and the reaction liquid is solidified when cooled. May occur. When the addition rate is higher than the above upper limit, the generation rate of the hydrogen iodide gas becomes large, and a considerable load is imposed on the heating capacity of the reactor and the cooling capacity of the hydrogen iodide holder, which is not practical.

After the completion of the addition of iodine, the reaction solution is preferably aged by stirring or the like to complete the reaction. The time required for this aging is not fixed depending on the temperature, but is usually 10 minutes or more, preferably 1 hour or more.

The thus reacted tetrahydronaphthalene can be consumed almost quantitatively.

[0026]

EXAMPLES Hereinafter, the method for producing hydrogen iodide in the present invention will be described in more detail with reference to examples. In the following, “%” is based on mass. The yield of hydrogen iodide was a value calculated based on the amount of iodine newly used at the time of the reaction, and the organic content was measured by high performance liquid chromatography. Example 1 An example of the operation of a reactor for producing hydrogen iodide is shown in FIG. Helium (400 ml / min.) Was flowed into the system by opening a valve 14 made of polyvinyl chloride (hereinafter PVC). Next, tetralin (90 kg, 0.681 kmol) was charged into a 100-liter glass-lined reactor, and stirring was started. The reactor internal temperature was raised to 170 ° C.

Solid iodine (22.8k
g) was charged and the PVC coated rotary valve was activated to add solid iodine at the specified rate (6.3 kg / h). Hereinafter, the valve opening / closing sequence is shown in FIG. PV
The solenoid valve of C valve 4 opens for 5 seconds, and solid iodine is
It was sent to the spacer 7 and closed. Since hydrogen iodide gas is usually generated in the reactor, a positive pressure state (0.003 MPa)
It is in. Next, the PVC valve 12 was opened for 10 seconds to introduce helium into the spacer 7. At this time, the pressure of helium was set to 0.01 Mpa. After closing the valve 12,
The ceramic valve 8 was opened for 2 seconds to add solid iodine into the tetralin in the reactor and closed. Next, the PVC valve 13 was opened for 5 seconds to release the residual pressure inside the spacer 7 and closed. The discharge destination of the residual pressure gas is usually an abatement apparatus, but an alkali trap was installed to monitor the hydrogen iodide gas component. A series of opening and closing of the valves was repeatedly and automatically performed as shown in FIG. 2, and solid iodine in the hopper was added in 3.6 hours. After the addition of solid iodine, stirring was continued for 1 hour at the same temperature. As a result, hydrogen iodide gas having a reaction yield of 99.7% was obtained. The generated hydrogen iodide gas is cooled to −25 ° C., liquefied, passed through molecular sieves to remove moisture, and then passed through activated carbon to remove accompanying organic components, resulting in purified hydrogen iodide gas. .

After a series of reactions, the concentration of hydrogen iodide gas in the gas released from the valve 13 was not detected. That is, the generated hydrogen iodide gas did not leak at all to the iodine hopper side. The addition device could be operated stably without any trouble.

Example 2 Using the apparatus shown in FIG. 1, 90 kg of tetrahydronaphthalene was charged into a reactor (manufactured by 100 liter glass lining), heated to 190 ° C. with stirring, and maintained at this temperature.
From the upper hopper, 284 kg of granular solid iodine was added for 8 hours by a rotary valve, and added to the reactor to react. At this time, the opening / closing cycle of each of the valves 4, 8, 12, and 13 shown in FIG. 1 was set as shown in FIG.

After the reaction, the hydrogen iodide gas from the reactor was brought into contact with molecular sieves to remove water, then contacted with activated carbon to remove organic components, and cooled to -50 ° C. Stainless steel (SUS
-304) collected in a holder. Next, hydrogen iodide in the holder was filled in a cylinder, and the components were analyzed and the yield was measured. As a result, the purity of the obtained hydrogen iodide was 99.99% or more, the yield was 281 kg, and the yield was 97.9%.

Example 3 The same operation as in Example 2 was carried out except that 284 kg of granular solid iodine was added by a rotary valve over 24 hours. As a result, the purity of the obtained hydrogen iodide was 99.99% or more, and the yield was 280 kg.
The yield was 97.5%.

Example 4 The same operation as in Example 2 was carried out except that 284 kg of granular solid iodine was added by a rotary valve over 63 hours. As a result, the purity of the obtained hydrogen iodide was 99.99% or more, and the yield was 283 kg.
The yield was 98.6%.

Example 5 The same operation as in Example 2 was carried out except that the reaction was carried out at 170 ° C. As a result, the purity of the obtained hydrogen iodide was 99.99% or more, the yield was 283 kg, and the yield was 9%.
It was 8.7%.

Example 6 The procedure of Example 2 was repeated, except that the reaction was carried out at 170 ° C., and 284 kg of granular solid iodine was added over 24 hours by a rotary valve. As a result, the purity of the obtained hydrogen iodide was 99.99% or more, the yield was 283 kg, and the yield was 98.7%.

Example 7 The procedure of Example 2 was repeated, except that the reaction was carried out at 170 ° C., and 284 kg of granular solid iodine was added over 63 hours by a rotary valve. As a result, the purity of the obtained hydrogen iodide was 99.99% or more, the yield was 283 kg, and the yield was 97.0%.

Example 8 Using the apparatus shown in FIG. 1, 92 kg of tetrahydronaphthalene was charged into a reactor (manufactured by 100 liter glass lining).
The mixture was heated to 170 ° C. with stirring, and while maintaining this temperature, 230 kg of granular solid iodine was added from the upper hopper to the reactor over 35 hours by adjusting the number of revolutions of a rotary valve, and allowed to react. At this time, 4, 8, 12 and 1 shown in FIG.
The setting of the open / close cycle of each valve of No. 3 is as shown in FIG.

The gas from the reactor accompanying the reaction was brought into contact with molecular sieves to remove water, and then contacted with activated carbon to remove organic components.
The sample was collected in a SUS-304 holder cooled to 0 ° C. Next, hydrogen iodide in the holder was filled in a cylinder, and the components were analyzed and the yield was measured. As a result, the obtained hydrogen iodide had a purity of 99.99% or more and a yield of 22
7 kg, and the yield was 97.9%.

[0038]

As described in detail above, by using the above-mentioned apparatus, a solid can be directly added to a reaction system for generating gas. Furthermore, quantitative addition is possible by a combination of rotary valves. In addition, by providing an inert gas inlet and a degassing port for feeding an inert gas between the first valve and the second valve arranged in series, the gas can be safely leaked without gas leakage. A solid addition operation can be performed.

[Brief description of the drawings]

FIG. 1 is an example of the reaction apparatus of the present invention.

FIG. 2 shows an example of an opening / closing cycle of various valves of the reactor of FIG.

[Explanation of symbols]

Reference Signs List 1 hopper (15L made of PVC) 2 Rotary valve 3, 5, 7 PVC spacer 4, 12, 13 PVC solenoid valve 6 Teflon (registered trademark) coated side glass 8 Ceramic solenoid valve 9 Teflon spacer 10 GL reducer 11 GL Nozzle 14 PVC solenoid valve 15 granular iodine 17 see-through window 18 reactor

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Eiichi Sagawa 1900 Togo, Mobara-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Tatsuo Kaiho 1900 Togo, Togo, Mobara-shi, Chiba F-term (reference) 4G068 AA02 AB22 AC03 AC11 AC13 AD01 AE01 AF09 AF15 AF22 AF36 DA01 DA04 DB11 DC01 DC05 DD11 DD15 4G075 AA05 AA53 AA62 AA63 AA70 BB04 BB05 BB07 BD16 CA03 CA57 CA63 EA01 EB01 EC10 ED09 FB04 FB06 FB12 FC02 FC09

Claims (6)

[Claims] Claims: 1. A reactor for adding a solid to a liquid and reacting the two with each other, the reactor comprising a solid charging device provided for adding the solid to the liquid. The inlet device is provided with at least two valves, a first valve and a second valve, in series for controlling the flow of the solid material. An inert gas inlet for introducing an inert gas to the reaction between the first valve and the second valve, and an inert gas inlet between the first valve and the second valve. A reactor comprising a deaeration port for depressurizing between a valve and a second valve. 2. The reactor according to claim 1, further comprising an apparatus having a function of quantitatively charging solids into the space. 3. The apparatus according to claim 1, wherein a solid substance is added to the liquid, and the two react to generate a gas. 4. A device having a function of at least quantitatively charging a solid substance into the space, and controlling the first valve and the second valve to quantitatively control the liquid within a certain period of time. The apparatus according to any one of claims 1 to 3, wherein the apparatus is controlled so that a solid substance is added to the apparatus. 5. The reactor according to claim 1, wherein the liquid contains a hydride of naphthalene, the solid is solid iodine, and the generated gas is hydrogen iodide gas. 6. A method for producing hydrogen iodide gas, comprising adding solid iodine to a liquid containing a hydride of naphthalene using the apparatus according to any one of claims 1 to 5.