WO2009096446A1 - ヨウ素化合物製造システムおよび製造方法 - Google Patents
ヨウ素化合物製造システムおよび製造方法 Download PDFInfo
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- WO2009096446A1 WO2009096446A1 PCT/JP2009/051421 JP2009051421W WO2009096446A1 WO 2009096446 A1 WO2009096446 A1 WO 2009096446A1 JP 2009051421 W JP2009051421 W JP 2009051421W WO 2009096446 A1 WO2009096446 A1 WO 2009096446A1
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- hydrogen iodide
- iodine
- gas
- hydrogen
- iodine compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/13—Iodine; Hydrogen iodide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/13—Iodine; Hydrogen iodide
- C01B7/135—Hydrogen iodide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/22—Oxygen compounds of iodine
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B9/00—General methods of preparing halides
- C01B9/06—Iodides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/12—Iodides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
Definitions
- the present invention relates to an iodine compound production system and method, and more particularly, to a system and method for producing a high purity iodine compound by a simple method.
- Patent Document 1 discloses a method of reducing iodine with aluminum or zinc by adding iodine to an alkaline aqueous solution to cause reaction.
- Patent Document 2 discloses a method in which iodine is added to an alkaline aqueous solution and then reduced with hydrogen sulfide.
- Patent Document 3 discloses a method of reducing iodine or iodate with an alkali metal amalgam under alkali or neutrality.
- Patent Document 4 discloses a method in which an organic reducing agent such as formic acid, oxalic acid, or malonic acid is acted on an alkali hydroxide aqueous solution of iodine.
- Patent Document 5 discloses a method in which iodine is added to a potassium hydroxide solution and formic acid is added thereto as a reducing agent.
- Patent Document 6 discloses a method of reacting iodine with potassium hydroxide or alkali carbonate using hydrazine as a reducing agent.
- Patent Document 7 discloses a method in which formic acid is added to a potassium hydroxide solution and neutralized, and then a larger amount of iodine than the stoichiometric amount is added to react with the solution, and the free iodine in the product is treated with potassium sulfide. It is disclosed.
- Patent Document 8 discloses a method for producing hydrogen iodide in which a hydrogen-containing gas and gaseous iodine are reacted by catalytic reduction using a platinum group catalyst highly dispersed in oxide or activated carbon, and the produced hydrogen iodide gas Is disclosed in which water is recovered with water or an aqueous alkali solution.
- Non-Patent Document 1 describes a method of passing a hydrogen stream saturated with iodine on platinum heated to 100 ° C.
- Non-Patent Document 2 discloses a method for producing potassium iodide by mixing and neutralizing hydroiodic acid with potassium bicarbonate and treating unreacted iodine with hydrogen sulfide in a weakly alkaline state.
- Non-Patent Document 3 discloses a method for crystallizing and removing potassium iodate produced as a by-product in synthesizing potassium iodide from iodine and potassium hydroxide, and decomposing it by heating to a temperature of 600 ° C. Yes.
- Patent Document 9 discloses a method for producing hydroiodic acid from iodine using an aqueous solution such as phosphorous acid or pyrophosphoric acid as a reducing agent.
- Patent Document 10 discloses a method for producing hydroiodic acid from water, sulfur dioxide and iodine.
- Patent Document 11 discloses a production method for producing hydrogen iodide from ammonia and iodine in the presence of an iron catalyst.
- Patent Document 12 discloses a production method for producing anhydrous hydrogen iodide by a reaction of an aqueous phosphoric acid solution, diphosphorus pentoxide, and a metal iodide.
- Patent Document 13 discloses a production method for producing hydrogen iodide from iodine and tetrahydronaphthalene.
- Patent Document 8 discloses a production method for producing hydrogen iodide by catalytic reduction of a hydrogen-containing gas and gaseous iodine in the presence of a catalyst.
- Patent Documents 14 to 16 disclose production methods for producing high-purity hydrogen iodide using an electrochemical technique.
- Patent Document 1 Patent Document 7
- Non-Patent Document 3 have a problem that by-products must be removed after the reaction.
- Patent Document 2 Patent Document 3 and Patent Document 6, there is a problem that a reducing agent that is difficult to handle must be used.
- Patent Document 4 and Patent Document 5 an easy-to-handle reducing agent such as formic acid or oxalic acid is used, but the reduction rate is slow, and iodine obtained with respect to iodine charged into the reaction system There is a problem that the amount of the compound is small (that is, the yield is low).
- Non-Patent Document 1 does not disclose a specific method for producing hydrogen iodide
- Patent Document 8 only discloses a method for producing hydrogen iodide by a catalytic reduction reaction. . There is no specific disclosure of iodide in general.
- the present invention has been made in view of the above-mentioned problems, and its main object is to provide a production method and a production system capable of producing an iodine compound that is simple, efficient, and inexpensive. That is.
- a method for removing unreacted iodine generally, a method of cooling and removing a gas containing hydrogen iodide, or a method of reducing a solution containing hydrogen iodide using a reducing agent.
- these treatment methods are very complicated and the treatment conditions are extremely strict, and the loss of hydrogen iodide is large, so that they are not efficient. Therefore, it is difficult to efficiently obtain high-purity hydrogen iodide by using these treatment methods.
- Patent Document 9 it is necessary to remove by-products by distillation and reduction or to remove unreacted iodine by activated carbon.
- Patent Document 10 it is necessary to perform a removal treatment to remove by-produced sulfuric acid and unreacted iodine.
- Patent Document 11 it is necessary to perform removal treatment for removing unreacted iodine and ammonia by passing the produced hydrogen iodide, unreacted iodine and ammonia through potassium hydroxide.
- Patent Document 12 it is necessary to perform a removal treatment to remove the by-produced metal phosphate.
- the method described in Patent Document 13 requires a removal process for removing naphthalene, which is a generated byproduct.
- Patent Document 8 it is necessary to perform a removal treatment for removing unreacted iodine.
- the zeolite used in the method described in Patent Document 17 is relatively expensive and needs to be regenerated and reused, and has the problem that the zeolite itself is attacked by strongly acidic hydrogen iodide.
- the present invention has also been made in view of the above-mentioned problems, and the object thereof is to produce highly pure hydrogen iodide very easily and efficiently.
- dissolved the said hydrogen iodide in water are also provided.
- the iodine compound production system is An iodine compound production system for producing an iodine compound using hydrogen iodide gas, the crude hydrogen iodide gas produced by bringing hydrogen gas and gaseous iodine into contact with each other in the presence of a catalyst, Hydrogen iodide purification equipped with a purifier to obtain hydrogen iodide gas by contacting a purified solution that dissolves substances other than hydrogen iodide contained in the crude hydrogen iodide gas and does not dissolve hydrogen iodide. It is characterized by having a unit.
- the hydrogen iodide purification unit in the above configuration performs purification by gas-liquid contact between gas and liquid. Therefore, the separation process of the purified substance after purification, which is necessary when the substance to be purified and the purified substance are in the same state (gas and gas or liquid and liquid), is not required. Therefore, purified hydrogen iodide can be obtained very easily as compared with the conventional hydrogen iodide purification unit.
- high purity hydrogen iodide means that there is an adverse effect in a further reaction process using the side reaction product generated in the reaction for generating crude hydrogen iodide gas and hydrogen iodide obtained by the hydrogen iodide purification step. It refers to hydrogen iodide containing almost no substance to be given.
- a raw material adjusting unit further comprising an iodine storage tank that stores liquid iodine obtained by melting and liquefying solid iodine, and a hydrogen supplier that supplies a hydrogen-containing gas containing hydrogen.
- the hydrogen-containing gas supplied from the hydrogen supply device is supplied to at least one of liquid iodine stored in the iodine storage tank and gaseous iodine obtained by vaporizing the liquid iodine.
- a hydrogen iodide generator having a raw material adjusting unit for obtaining a mixed gas containing gaseous iodine and hydrogen, and a catalyst part comprising a catalyst using the mixed gas obtained in the raw material adjusting unit as a crude hydrogen iodide gas
- a hydrogen iodide production unit comprising the hydrogen iodide gas obtained in the hydrogen iodide purification unit, By contacting the reactants reactive with c hydrogen gas, preferably further comprises iodine compound producing unit having iodine compound generator for generating iodine compound.
- hydrogen iodide can be generated in a gas phase catalytic reduction reaction using gaseous iodine and hydrogen.
- a gas phase reaction for the synthesis of hydrogen iodide generation of by-products in the liquid phase reaction can be suppressed, and hydrogen iodide can be generated easily and efficiently.
- the molar ratio of hydrogen to gaseous iodine in the gas phase catalytic reduction reaction can be easily set to a desired ratio. This also brings about an effect of synthesizing hydrogen iodide with almost no unreacted substance generated in the gas phase catalytic reduction reaction.
- the iodine storage tank further includes an iodine storage tank heater for heating the iodine storage tank.
- the iodine can be maintained as a liquid without being gasified.
- the iodine since an amount of iodine corresponding to the temperature of the iodine and the amount of gas to be contacted can be gasified, there is an effect that a desired amount of gaseous iodine can be easily obtained.
- the hydrogen iodide generating unit further includes a catalyst part heater for heating the catalyst part.
- the temperature of the mixed gas in the hydrogen iodide generator in the hydrogen iodide generating unit can be maintained at a suitable value.
- hydrogen and gaseous iodine are activated, and it is possible to prevent the generated crude hydrogen iodide gas from being insufficiently desorbed from the catalyst surface.
- the effect that the fall of the yield of the crude hydrogen iodide gas by the fall of the conversion rate of iodine and the fall of catalyst activity can also be suppressed is also show
- the hydrogen iodide purification unit further includes a circulation mechanism for circulating a purified solution for removing unreacted iodine from the crude hydrogen iodide gas.
- the mechanism preferably includes a cooler that cools the purified solution returned to the purifier.
- the iodine compound generator is further provided with a flow path for flowing the reaction raw material solution, and a gas nozzle for introducing the hydrogen iodide gas into the flow path.
- a flow path for flowing the reaction raw material solution
- a gas nozzle for introducing the hydrogen iodide gas into the flow path.
- the iodine compound can be produced with high productivity and the iodine compound can be produced efficiently.
- the raw material adjusting unit further includes a gas mixer that makes the composition of the gaseous iodine and the hydrogen in the mixed gas uniform.
- the composition of gaseous iodine and hydrogen in the mixed gas can be made uniform, and the mixed gas having a uniform composition can be sent to the hydrogen iodide generator. Therefore, there is an effect that the synthesis of hydrogen iodide in the hydrogen iodide generating unit can be suitably advanced.
- the raw material adjusting unit further includes a mixed gas heater for heating the mixed gas.
- the temperature of the mixed gas can be set to a temperature suitable for the reaction before the reaction is started in the hydrogen iodide generating unit.
- synthesis of hydrogen iodide can be started at the most suitable temperature state.
- the mixed gas heater is provided integrally with the gas mixer.
- the composition of gaseous iodine and hydrogen in the mixed gas is made uniform in the gas mixer, and the effect of being heated to a suitable temperature in the reaction in the hydrogen iodide generator is achieved.
- the iodine compound production system according to the present invention can be reduced in size and weight.
- the mixed gas heater and the gas mixer are provided integrally with the hydrogen iodide generator.
- the iodine compound production system according to the present invention can be reduced in size and weight.
- the material of the raw material adjustment unit is preferably at least one selected from hastelloy, glass, ceramic, metal tantalum, platinum, and polytetrafluoroethylene. .
- the material of the hydrogen iodide generating unit is at least one selected from hastelloy, heat resistant glass, ceramic, and platinum.
- the hydrogen iodide purification unit and the iodine compound generation unit are made of hastelloy, glass, ceramic, metal tantalum, platinum, polyvinyl chloride, and polytetrafluoroethylene. It is preferable to consist of at least one selected from
- each unit is corroded by corrosive iodine and hydrogen iodide. Can be prevented. Thereby, there is an effect that the lifetime of the iodine compound production system according to the present invention can be extended.
- the hydrogen iodide generating unit by using the above-mentioned material for the hydrogen iodide generating unit, it is possible to prevent the unit from being damaged by the mixed gas and the crude hydrogen iodide gas heated to a temperature of about 350 ° C. Thereby, there is an effect that the lifetime of the iodine compound production system according to the present invention can be further extended.
- the purifier in the hydrogen iodide purification unit further includes a packed tower packed with a packing, and the packed tower includes the crude hydrogen iodide gas and It is preferable that an inlet for introducing a purified solution for removing unreacted iodine from the crude hydrogen iodide gas is provided.
- the purifier in the hydrogen iodide purification unit further includes a purification tank for storing a purification solution for removing unreacted iodine from the crude hydrogen iodide gas, and the purification And a feeder for supplying the crude hydrogen iodide gas to the tank.
- the iodine compound production method provides: An iodine compound production method for producing an iodine compound using hydrogen iodide gas, wherein the crude hydrogen iodide gas produced by bringing hydrogen gas and gaseous iodine into contact with each other in the presence of a catalyst Including a hydrogen iodide purification step for obtaining hydrogen iodide gas by contacting a purified solution that dissolves substances other than hydrogen iodide contained in the crude hydrogen iodide gas and does not dissolve hydrogen iodide. It is a feature.
- the purified solution in the hydrogen iodide purification step is preferably a saturated hydrogen iodide solution.
- the solvent of the saturated hydrogen iodide solution is preferably at least one of water, ketones, ethers, alcohols, and aromatic compounds. .
- the crude hydrogen iodide gas and the purified solution may be brought into gas-liquid contact in a packed tower packed with a packing. preferable.
- the crude hydrogen iodide gas is blown into the purified solution for gas-liquid contact.
- the catalyst is a catalyst in which at least one platinum group element is dispersed and supported on at least one of oxide and activated carbon.
- iodine and hydrogen can be activated.
- the production rate of hydrogen iodide can be improved even at a relatively low reaction temperature.
- the liquid iodine obtained by heating solid iodine is further brought into contact with a gas containing at least one of a gas inert to the liquid iodine and hydrogen.
- Gaseous iodine production step for obtaining iodine, catalytic reduction of the mixed gas containing gaseous iodine and hydrogen in the presence of a catalyst to produce crude hydrogen iodide gas, and the hydrogen iodide purification step It is preferable to further include an iodine compound production step of producing an iodine compound using the hydrogen iodide gas obtained in the above.
- generation process is produced
- the molar ratio of hydrogen to gaseous iodine in the mixed gas is further set within a range of 0.5 to 10 before the hydrogen iodide producing step. It is preferable.
- the molar ratio is less than 0.5, the amount of hydrogen gas relative to iodine gas is small, so that the productivity of hydrogen iodide is lowered and a process for recovering expensive iodine is required.
- the molar ratio exceeds 10, wasteful hydrogen is used, which increases the cost required for producing hydrogen iodide, which is disadvantageous.
- the hydrogen iodide gas is brought into contact with the inorganic base compound solution in the iodine compound production step.
- the iodine compound production method according to the present invention preferably further includes a drying step of drying the inorganic iodide aqueous solution obtained in the iodine compound generation step.
- a solution containing the hydrogen iodide gas or the hydrogen iodide gas as a solute with respect to the alcohol-containing solution or the aromatic diazonium solution is preferably brought into contact.
- the hydrogen iodide gas and the alcohol-containing solution or the aromatic diazonium solution can be brought into gas-liquid contact, so that the contact efficiency of the reaction raw material can be improved. Therefore, there is an effect that the productivity of organic iodide can be improved.
- the iodine compound production method according to the present invention preferably further includes an organic iodide purification step of purifying the organic iodide solution obtained in the iodine compound generation step.
- hydrogen iodide obtained in the hydrogen iodide production step in the iodine compound production method according to the present invention is also included in the category of the present invention.
- the content of iodine contained in the hydrogen iodide is preferably at least 2% by weight or less when the weight of all components contained in the hydrogen iodide is 100% by weight.
- hydroiodic acid obtained by dissolving the above hydrogen iodide in water is also included in the scope of the present invention.
- Embodiment 1 One embodiment of the method for producing an iodine compound according to the present invention will be described below.
- the method for producing an iodine compound mainly includes four steps of a gaseous iodine generation step, a hydrogen iodide generation step, a hydrogen iodide purification step, and an iodine compound generation step. Each of these four steps will be described below.
- hydrogen iodide and “hydrogen” in this specification and the like refer to gaseous hydrogen iodide and gaseous hydrogen, that is, hydrogen iodide gas and hydrogen gas.
- “crude hydrogen iodide” means unreacted iodine remaining in the hydrogen iodide production reaction, iodine produced by decomposition of hydrogen iodide, or a reaction that produces hydrogen iodide. It means that the gas contains impurities that are by-products generated in the process.
- iodine and “hydrogen” refer to an iodine molecule (I 2 ) and a hydrogen molecule (H 2 ), respectively, unless otherwise specified.
- the gaseous iodine generation step is a step of heating at least a part of the solid iodine to gaseous iodine.
- Iodine is a sublimable substance having a melting point of 113.7 ° C. and a boiling point of 184.5 ° C. Therefore, in the gaseous iodine production step, solid iodine may be heated so as to be in the temperature range of the melting point to the boiling point. Thereby, gaseous iodine can be produced from solid iodine.
- the molar ratio of hydrogen to gaseous iodine in the mixed gas obtained by mixing gaseous iodine and hydrogen is preferably in the range of 0.5 to 10, More preferably, it is in the range of 0.5-6.
- the molar ratio of hydrogen to gaseous iodine can be produced with high productivity. That is, when the molar ratio is less than 0.5, since the amount of hydrogen gas relative to iodine gas is small, iodine consumption is reduced and the productivity of hydrogen iodide is reduced. Moreover, the process of collect
- the heating temperature of solid iodine is preferably in the range of the melting point of iodine (about 114 ° C.) to 150 ° C., and more preferably in the range of 120 to 150 ° C.
- Liquid iodine produces gaseous iodine in an amount that depends on the gas flow rate and liquid iodine temperature when in contact with the hydrogen-containing gas. That is, the amount of iodine gas to be vaporized can be adjusted by adjusting the gas flow rate of the hydrogen-containing gas to be contacted and the liquid iodine temperature.
- the amount of hydrogen contained in the hydrogen-containing gas brought into contact with liquid iodine is preferably such an amount that the molar ratio of hydrogen to gaseous iodine becomes the above-described predetermined ratio, but is not limited thereto. It is not a thing. That is, hydrogen may be further added so that a predetermined ratio is obtained after liquid iodine is changed to gaseous iodine.
- the hydrogen-containing gas may contain a gas (gas) other than hydrogen as long as a desired amount of gaseous iodine can be generated.
- the gas other than hydrogen contained in the hydrogen-containing gas is preferably a gas inert to iodine.
- nitrogen, argon, helium, etc. can be mentioned.
- the mixed gas obtained by mixing gaseous iodine and hydrogen is uniformly mixed before the hydrogen iodide production step.
- the hydrogen and gaseous iodine are mixed before the mixed gas is uniformly mixed.
- the molar ratio is preferably a predetermined molar ratio. Since the configuration in which the mixed gas is uniform will be described in detail in Embodiment 2, the description thereof is omitted here.
- the purity of solid iodine used is preferably 90% or more, more preferably 95% or more, and further preferably 99% or more.
- the hydrogen to be used is obtained by a hydrogen-containing gas obtained by reforming methane with at least one of pure hydrogen, water vapor, and carbon dioxide, hydrogen separated from the hydrogen-containing gas, and a partial oxidation reaction of methane.
- a hydrogen-containing gas, a hydrogen-containing gas obtained by steam reforming methanol, a hydrogen-containing gas obtained by decomposition of methanol, or the like can be used.
- hydrogen obtained by a gasification process using coal, petroleum coke, and heavy residual oil as raw materials may be used as a hydrogen source.
- hydrogen obtained by separating and recovering unreacted hydrogen contained in the gas at the outlet of the hydrogen iodide production tower may be recycled and used.
- the hydrogen iodide production step is a step of producing a crude hydrogen iodide gas containing hydrogen iodide as a main component, obtained by vapor phase catalytic reduction of iodine.
- the “main component” means a component exceeding 50% by weight among all components contained in the crude hydrogen iodide gas or hydrogen iodide.
- the hydrogen iodide production step can be performed using a conventionally known method.
- crude hydrogen iodide gas can be produced by gas phase catalytic reduction of gaseous iodine and hydrogen in the presence of a catalyst.
- the catalyst in the gas phase catalytic reduction reaction using gaseous iodine and hydrogen gas is preferably a catalyst in which a platinum group element is dispersed and supported on at least one of oxide and activated carbon.
- Iodine and hydrogen can be activated by dispersing and supporting the platinum group element on at least one of oxide and activated carbon.
- platinum group elements include platinum (Pt), palladium (Pd), ruthenium (Ru), osmium (Os), iridium (Ir), and rhodium (Rh).
- oxides include magnesium oxide, titanium oxide, silica, alumina, cordierite, zirconia, silica alumina, and zeolite.
- activated carbon include wood chips, wood powder, coconut shells and Plant-based activated carbon activated from walnut shells, mineral activated carbon activated from peat, coal coke and tar, and natural materials such as regenerated fiber and rayon, and synthetic materials such as phenolic resin and acrylic resin Examples of the activated carbon include activated carbon.
- the shape of the catalyst (that is, the shape of the support on which platinum group elements are dispersedly supported) is not particularly limited.
- the support may be in a powder state, and may be previously formed into a ring shape (ring shape), a spherical shape, or a honeycomb shape, and a platinum group element may be supported thereon, or the support may be made of platinum. After supporting the group element, it may be formed into a ring (ring shape), a spherical shape, or a honeycomb shape. Further, a powder in which a platinum group element is supported on an oxide powder may be supported on silicon carbide (SiC) or nitride formed into a ring shape, a spherical shape, or a honeycomb shape.
- SiC silicon carbide
- platinum group element used as the catalyst only one kind of the above-described platinum group elements may be used, or two or more kinds may be mixed and used.
- oxide and activated carbon used as a support for the platinum group element only one kind may be used, or two or more kinds may be mixed and used.
- oxides and activated carbon may be used alone or in combination.
- the reaction temperature in the gas phase catalytic reduction reaction is preferably in the range of 200 to 1000 ° C., more preferably in the range of 250 to 900 ° C., and still more preferably in the range of 250 to 850 ° C. .
- the “gas space velocity” in this specification and the like means the ratio of the reaction gas volume and the catalyst volume per unit time in the standard state.
- the reaction pressure is preferably in the range of normal pressure to 10 MPa.
- the hydrogen iodide purification step is a step of removing substances other than hydrogen iodide (hereinafter also referred to as impurities) in the crude hydrogen iodide gas mainly composed of hydrogen iodide generated in the hydrogen iodide generation step. In other words, this is a step of bringing the purified solution not dissolving hydrogen iodide and the crude hydrogen iodide gas into gas-liquid contact, which dissolves impurities contained in the crude hydrogen iodide gas.
- the hydrogen iodide purification step is a gas-liquid contact between a crude hydrogen iodide gas in a gas state and a purified solution that is in a liquid state
- the purification is performed in the same state, for example, a liquid and a liquid as in the past.
- purification is not required. That is, it is possible to purify only hydrogen iodide from the crude hydrogen iodide gas containing impurities very efficiently and to obtain high-purity hydrogen iodide.
- the hydrogen iodide purification step is such that the iodine content in the hydrogen iodide after purification is at least 2% by weight or less when the weight of all components contained in the hydrogen iodide is 100% by weight.
- the treatment is performed so that the amount is 1% by weight or less, more preferably, the treatment is performed so that the amount is 0.5% by weight or less, and the treatment is performed so that the amount is 0.1% by weight or less. Most preferred.
- the high-purity hydrogen iodide obtained has an iodine weight of at least 2% by weight, more preferably 1% by weight or less, when the weight of all components contained in hydrogen iodide is 100% by weight. More preferably, it is 0.5% by weight or less, and most preferably 0.1% by weight or less.
- the high-purity hydrogen iodide gas obtained in this hydrogen iodide purification step can be absorbed into water to obtain high-purity hydrogen iodide of any concentration, and by cooling, high-purity liquid hydrogen iodide Is obtained.
- “all components” contained in hydrogen iodide means all components of hydrogen iodide excluding inert gases such as hydrogen and nitrogen.
- “high purity hydrogen iodide” in this specification and the like means that the weight of iodine is in the above-mentioned range when the weight of “all components” of hydrogen iodide is 100% by weight. ing.
- “high-purity hydrogen iodide” means that the weight of "impurities” is in the above-mentioned range when the weight of "all components” of hydrogen iodide is 100% by weight. .
- the purified solution is not particularly limited as long as it dissolves impurities contained in the crude hydrogen iodide gas but does not dissolve hydrogen iodide. Among these, it is preferable that the solution is capable of removing unreacted iodine which is difficult to separate from hydrogen iodide and which causes a problem when the produced hydrogen iodide is used for other reactions.
- Examples of the purified solution having the above-described properties include a saturated hydrogen iodide solution.
- a saturated hydrogen iodide solution is a solution that dissolves iodine very well, but hydrogen iodide is in a saturated state and hardly dissolves.
- the case where a saturated hydrogen iodide solution is used as the purification solution will be described below as an example.
- a saturated hydrogen iodide solution can be prepared by dissolving hydrogen iodide in a solvent until it becomes saturated.
- the solvent for preparing the saturated hydrogen iodide solution is not particularly limited as long as it is a solvent capable of dissolving hydrogen iodide. Examples thereof include solvents such as water, ketones, halogen compounds, aromatic compounds, ethers and alcohols. Alternatively, an aqueous solution containing an alkali metal iodide or an aqueous solution containing an alkaline earth metal iodide may be used.
- the solvent include distilled water, acetone, chloroform, carbon tetrachloride, benzene, toluene, xylene, petroleum ether, dioxane, ethyl ether, methanol, potassium iodide aqueous solution and barium iodide aqueous solution.
- water an aqueous solution containing an alkali metal iodide, ketones, and aromatic compounds are preferable, and water that can be easily and inexpensively obtained is more preferable.
- the temperature of the saturated hydrogen iodide solution need not be strictly controlled. Originally, when hydrogen iodide is dissolved in a saturated solution, heat is generated due to the heat of dissolution, but in the hydrogen iodide purification step according to the present invention, crude hydrogen iodide gas is in gas-liquid contact with the saturated hydrogen iodide solution. This is because sometimes hydrogen iodide does not dissolve.
- the present invention can omit the complicated process of controlling the temperature of the solution used in the hydrogen iodide purification step, and can obtain highly pure hydrogen iodide very easily.
- the temperature of the saturated hydrogen iodide solution is more preferably 100 ° C. or less, further preferably 50 ° C. or less, and most preferably 20 ° C. or less.
- a part of hydrogen iodide purified by the hydrogen iodide purification step may be used as a solute of a saturated hydrogen iodide solution.
- the iodine compound production step is a step of producing various iodine compounds using the high purity hydrogen iodide gas obtained in the hydrogen iodide purification step described above.
- the iodine compound production step is a step of producing various iodine compounds using the high purity hydrogen iodide gas obtained in the hydrogen iodide purification step described above.
- the use of hydrogen iodide obtained through each of the above steps is not limited to the production of the above-mentioned iodine compound, and can be suitably used in other reactions using hydrogen iodide as a raw material. .
- the hydrogen iodide gas used in the iodine compound production step according to the present invention is a gas containing hydrogen iodide gas. That is, in the iodine compound generation step, the hydrogen iodide gas is not limited to the case where the entire capacity is hydrogen iodide gas.
- the iodine content in the hydrogen iodide gas is preferably 2% by weight or less based on the total weight.
- the hydrogen iodide gas preferably has an impurity content of 2% by weight or less when the total weight is 100%. That is, in this embodiment, the high purity hydrogen iodide gas may be a hydrogen iodide gas having an impurity content of 2% by weight or less when the total weight is 100%.
- Inorganic iodide can be produced by contacting hydrogen iodide with an inorganic base compound.
- the inorganic base compound used in the present embodiment is a compound capable of causing a neutralization reaction with hydrogen iodide.
- it is a compound that generates a hydroxide ion (OH-) by causing a dissociation or equilibrium reaction in an aqueous solution.
- inorganic base compounds include metal hydroxides such as alkali metals, alkaline earth metals, rare earth elements, transition metals, hydroxides of typical elements such as aluminum and zinc, and basic oxidation of metals.
- Metal carbonates such as alkali metal carbonates, metal hydrogen carbonates such as alkali metal hydrogen carbonates, and ammonia.
- alkali metal or alkaline earth metal hydroxide and ammonia because they are inexpensive and easily available.
- the inorganic base compound is subjected to the reaction in a solid state, an aqueous solution completely dissolved in a solvent such as water, or a slurry dispersed in water.
- a solvent such as water
- a slurry dispersed in water it is preferable to use for reaction in the state of the aqueous solution dissolved in water. This point will be described in detail in the description of the reaction described later.
- the target inorganic iodide is obtained by causing a neutralization reaction in which hydrogen iodide gas is brought into contact with the inorganic base compound.
- the reaction follows the following reaction formula (1).
- inorganic base solution a liquid inorganic base compound
- the concentration when inorganic iodide is used as a solution depends on the solubility of the solute in the solvent, but is generally preferably in the range of 1 to 95% by weight, and in the range of 5 to 90% by weight. More preferably, it is more preferably in the range of 10 to 80% by weight.
- concentration of the inorganic iodide solution within the above range, the raw material cost is reduced and the energy required for separating and recovering the inorganic iodide from the reaction solution is reduced. Therefore, the cost required for the production of inorganic iodide can be reduced.
- a solvent it is preferable to use water and alcohols, and it is more preferable to use water.
- the reaction temperature in the inorganic iodide formation reaction is not particularly limited as long as the reaction can proceed.
- the pH value of the reaction system can be controlled by appropriately adding an acidic compound or an alkaline compound to the reaction system according to the measured pH value. For example, when the pH value is less than 1.50, an inorganic base solution may be added, and when the pH value exceeds 11.00, hydrogen iodide or an organic acid may be added.
- a reducing acid as the organic acid to be added.
- organic acids include formic acid, hydrazine, sulfurous acid, phosphorous acid and the like.
- stabilization of potassium iodide can be aimed at by adjusting pH using the acid which has reducibility.
- this acid plays the role of removal of an unreacted iodine and the release
- a reduction treatment may be performed as necessary to remove unreacted iodine molecules.
- This reduction treatment can be performed by a conventionally known reduction treatment such as addition of a reducing agent exemplified by formic acid and oxalic acid.
- high purity inorganic iodide can be produced simply and efficiently by bringing hydrogen iodide gas into contact with an inorganic base compound.
- a high-purity inorganic iodide can be produced without obtaining a separate purification step after obtaining an inorganic iodide.
- inorganic iodide when inorganic iodide is produced as an inorganic iodide solution by gas-liquid contact, the inorganic iodide is obtained as a solid by passing through a drying step in which the solvent is distilled off and the inorganic iodide crystals are dried. Can do.
- a conventionally known drying process can be adopted as the drying process used at this time.
- solid inorganic iodide can be obtained in a short time by employing, for example, vacuum concentration drying using an evaporator or freeze drying.
- the aliphatic iodide in this specification etc. means alkyl iodide. That is, the target aliphatic iodide can be obtained by bringing hydrogen iodide gas into contact with an alcohol-containing solution. The production of the aliphatic iodide is almost the same as the production of the inorganic iodide described above.
- reaction when the alcohol-containing solution is methanol, the reaction follows the following reaction formula (2).
- the alcohol-containing solution to be contacted with hydrogen iodide gas is preferably an alcohol having about 1 to 8 carbon atoms, and more preferably an alcohol having about 1 to 6 carbon atoms.
- alcohols that can be suitably used in the production of aliphatic iodides may be linear or have a branched chain.
- alcohols that can be suitably used are not limited to monohydric alcohols, and may be polyhydric alcohols. Specific examples of the alcohol solution that can be used more suitably among these include methanol, ethanol, and isopropanol.
- the alcohol solution is not limited to one whose total volume is made of alcohol. That is, for example, an organic solvent other than moisture or alcohols may be contained. Any alcohol solution containing 50% or more of alcohol can be suitably used in the production of aliphatic iodide.
- a solution in which hydrogen iodide gas is dissolved as a solute may be used instead of hydrogen iodide gas.
- hydrogen iodide solution examples include hydroiodic acid in which hydrogen iodide is dissolved in water.
- the iodine content contained in the hydrogen iodide obtained in the hydrogen iodide purification step described above is 100% of all components of the hydrogen iodide solution. It is preferable to purify so that it may become 2 weight% or less, and it is more preferable to refine
- the aliphatic iodide can be obtained as a highly pure liquid or solid through a purification process for purifying the aliphatic iodide solution produced as described above.
- a purification step used in this case, a conventionally known purification step such as distillation can be employed.
- the target aromatic iodide can be obtained by bringing hydrogen iodide gas into contact with an aromatic diazonium solution. That is, the diazonium group bonded to the aromatic ring is substituted with iodine to obtain an aromatic iodide.
- the production of the aromatic iodide is almost the same as the production of the inorganic iodide described above. Therefore, regarding the production of aromatic iodide, the contents described in the production of inorganic iodide are omitted, and only the points different from the production of inorganic iodide will be described below.
- aromatic diazonium solution that can be suitably used in the production of aromatic iodide is not particularly limited as long as it has a diazonium group (N ⁇ N +-) in its side chain.
- diazonium groups You may have the substituent of.
- Specific examples include compounds represented by the following general formula (1).
- R in the above formula (1) is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, a carboxyl group, an alkoxycarboxyl A group selected from a group, an alkoxycarbonylalkyl group, an amino group, an acylamino group, a carbamoyl group, a carbonyl group, a nitrile group, a nitro group and a halogen atom.
- the alkyl group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
- the alkyl group may be linear or may have a branched chain. Furthermore, it may be annular. Specific examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl. Examples include groups.
- the alkoxy group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of such an alkoxy group include a methoxy group and an ethoxy group.
- aromatic diazonium having the above substituents one selected from an alkyl group having 1 to 4 carbon chains, a carboxyl group, and a halogen atom can be preferably used.
- examples of the further substituent include alkenyl groups such as vinyl group, 1-propenyl group, allyl group and butenyl group, alkyl-carbonyl groups having 1 to 6 carbon atoms such as formyl group, acetyl group and propionyl group, Acyl group such as aryl-carbonyl group including benzoyl group, acyloxy group having 1 to 6 carbon atoms such as formyloxy group, acetyloxy group and propionyloxy group, mono- or dialkyl such as methylamino group, dimethylamino group and diethylamino group Examples thereof include amino groups including amino groups, acylamino groups having 1 to 6 carbon atoms such as formylamino group and acetylamino group, albamoyl groups, substituted carbamoyl groups, carbonyl groups and nitrile groups.
- alkenyl groups such as vinyl group, 1-propenyl group, allyl group and butenyl group
- a hydrogen iodide solution may be used instead of hydrogen iodide gas, as in the case of aliphatic iodide.
- organic iodide in this specification and the like is a general term for an iodide including an aliphatic iodide and an aromatic iodide.
- FIG. 1 is a block diagram showing an outline of an iodine compound production system according to the present invention. Therefore, FIG. 1 does not accurately show the shape of the line connecting the units in the iodine compound production system, the size of each unit, and the like. These can be appropriately changed when manufacturing the device.
- the same terms as those in the first embodiment are used as the same meaning unless otherwise specified.
- the iodine compound production system 100 mainly includes four units: a raw material adjustment unit 1, a hydrogen iodide production unit 10, a hydrogen iodide purification unit 20, and an iodine compound production unit 30. ing.
- the raw material adjustment unit 1 and the hydrogen iodide production unit 10, the hydrogen iodide production unit 10 and the hydrogen iodide purification unit 20, and the hydrogen iodide purification unit 20 and the iodine compound production unit 30 are each physically connected via lines. It is connected.
- Each unit will be described below.
- the raw material adjustment unit 1 is a unit for adjusting a raw material for generating hydrogen iodide used for production of an iodine compound. More specifically, it is a unit for adjusting gaseous iodine and hydrogen to have a predetermined molar ratio and temperature.
- the raw material adjustment unit 1 includes a hydrogen-containing gas supply device (hydrogen supply device) 2, an iodine melting pot (gaseous iodine generator) 4, and a mixer unit (gas mixer, mixed gas heater) 8. It has.
- the hydrogen-containing gas supply device 2 stores hydrogen used for the synthesis of hydrogen iodide.
- an inert gas is used to generate gaseous iodine
- (Iodine melting pot 4) In the iodine melting pot 4, the hydrogen-containing gas supplied from the hydrogen-containing gas supply device 2 via the line 3 is brought into contact with the liquid iodine 5 obtained by heating solid iodine to a melting point of about 150 ° C. Gaseous iodine is produced. The produced gaseous iodine is sent to the mixer section 8 via the line 6.
- the iodine melting pot 4 includes a heater (iodine storage tank heater) for melting solid iodine into liquid iodine.
- the heater include a jacket portion for flowing a heated heat medium such as hot air, superheated steam or oil, an electric heater for heating the iodine melting pot 4 filled with solid iodine from the outside, or solid iodine
- a heater iodine storage tank heater
- the heater include a jacket portion for flowing a heated heat medium such as hot air, superheated steam or oil, an electric heater for heating the iodine melting pot 4 filled with solid iodine from the outside, or solid iodine
- An infrared or far-infrared irradiation device that irradiates infrared rays or far-infrared rays can be given.
- the iodine melting pot 4 has a mechanism for generating gaseous iodine from the liquid iodine 5.
- the mechanism for generating gaseous iodine is not particularly limited as long as it is a mechanism capable of contacting the hydrogen-containing gas as described above.
- a mechanism for blowing a hydrogen-containing gas into the iodine melting pot 4 or a hydrogen-containing gas with respect to liquid iodine 5 that is pressurized or spontaneously dropped by a gas for example, a hydrogen-containing gas or an inert gas. It is good also as gaseous iodine by making it contact.
- a necessary amount of liquid iodine 5 may be supplied using a pump made of a material that is not corroded by iodine, and the supplied iodine may be changed to gaseous iodine.
- the hydrogen-containing gas to be blown may be blown into the liquid iodine 5 or blown so as to be in contact with the surface of the liquid iodine 5. You may do it.
- the iodine melting pot 4 may be provided with a stirring mechanism for stirring the liquid iodine 5 such as a stirring blade.
- a stirring mechanism for stirring the liquid iodine 5 such as a stirring blade.
- a heat medium such as hot air, water vapor, or oil may be passed through the stirring blade, and a heat source for melting solid iodine may be used.
- the iodine melting pot 4 is preferably arranged in parallel to the production line in order to obtain gaseous iodine continuously for a long time. Thereby, even if it is a case where solid iodine is lost in any of the iodine melting pots, the lines can be switched as necessary. For this reason, gaseous iodine can be continuously supplied without interruption.
- solid iodine may be made into liquid iodine 5 by dissolving it in a solvent.
- the solvent for dissolving solid iodine include benzene, methanol, ethanol, diethyl ether and the like.
- the mixer unit 8 includes a gas mixer that mixes gaseous iodine produced in the iodine melting kettle 4 with hydrogen so that the composition of iodine and hydrogen is uniform, and a mixed gas of 120 to 350. It has a heater that heats to about °C. The mixed gas heated in the mixer unit 8 is sent to the hydrogen iodide production unit 10 via the line 14.
- the gas mixer is preferably a filling tube filled with a filler.
- the filler that can be suitably used in the gas mixer is not particularly limited as long as it is made of a material that is not corroded by iodine. Specific examples include hastelloy, glass, and magnetic ceramic.
- the shape of the filler is not particularly limited, and examples thereof include a spherical shape, a cylindrical shape (cylinder shape), and an annular shape (ring shape). As the filling material, only those having the same shape may be used, or those having different shapes may be used in combination.
- the heater is not particularly limited as long as it can heat the mixed gas to about 120 to 350 ° C., preferably about 250 to 350 ° C.
- a heating wire may be wound around the filling tube and heated, or a jacket portion through which the heated heat medium flows may be provided.
- the gas is produced before the mixer unit 8.
- Hydrogen is preferably replenished from line 7 so that the molar ratio of hydrogen to gaseous iodine is in the range of 0.5-10.
- the mixer unit 8 in which the gas mixer and the heater are integrated is described as an example.
- the present invention is not limited to this, and the gas mixer and the heater are not limited thereto. May be provided independently.
- the mixer unit 8 in which the gas mixer and the heater are integrated is suitable for the reaction in the hydrogen iodide generator while making the composition of gaseous iodine and hydrogen in the mixed gas uniform in the gas mixer. Can be heated to temperature.
- the iodine compound production system 100 itself can be reduced in size and weight.
- the hydrogen iodide production unit 10 includes a hydrogen iodide production tower 12 that reacts hydrogen with gaseous iodine.
- the hydrogen iodide production tower 12 includes a catalyst layer (catalyst portion) 12a therein. Hydrogen gas and gaseous iodine are supplied from the lower part of the hydrogen iodide production tower 12 via a line 14. Then, crude hydrogen iodide gas is obtained from the upper part of the hydrogen iodide production tower 12. The generated crude hydrogen iodide gas is sent to the hydrogen iodide purification unit 20 via the line 16.
- the catalyst layer 12a is filled with the catalyst described in the first embodiment. Further, a catalyst layer heater (catalyst portion heater) 13 (for example, an electric furnace, an oil bath, etc.) is provided on the outer surface of the hydrogen iodide production tower 12.
- the hydrogen iodide production unit 10 is not limited to a mode in which raw materials are supplied from the lower part of the hydrogen iodide production tower 12 and a product is obtained from the upper part of the hydrogen iodide production tower 12.
- the hydrogen gas and gaseous iodine may be supplied from the top of the tower, or the hydrogen iodide production tower 12 (especially the catalyst layer 12a) may be installed horizontally, and the hydrogen gas and The form which supplies gaseous iodine may be sufficient.
- the catalyst layer heater 13 can heat the object to be heated in a range of 100 to 1000 ° C. However, the catalyst layer heater 13 is usually heated so that the temperature of the catalyst layer 12a is in the range of 200 to 850 ° C. By making the surface temperature of the catalyst layer 12a in the range of 200 to 850 ° C., the gaseous iodine and hydrogen in the mixed gas are activated and the generated crude hydrogen iodide gas is not sufficiently desorbed from the catalyst surface. Can be prevented. As a result, a decrease in the yield of hydrogen iodide and a decrease in the catalytic activity can be suppressed.
- the hydrogen iodide production tower 12 may be integrated with the mixer unit 8 described above. That is, you may make it provide the mixer part 8 before the catalyst layer 12a in the hydrogen iodide production tower 12.
- FIG. By configuring the hydrogen iodide production tower 12 in such a configuration, the hydrogen iodide production tower 12 is maintained in a state in which the mixed gas heated to a suitable temperature in the reaction in the hydrogen iodide production tower 12 is maintained at a suitable temperature.
- the catalyst layer 12a can be supplied.
- the iodine compound manufacturing system 100 can be reduced in size and weight.
- the hydrogen iodide purification unit 20 includes a packed tower 22 filled with a packing material and a tank 24 in which a purified solution is stored.
- the packed tower 22 is a gas-liquid contact between the crude hydrogen iodide gas produced by the hydrogen iodide production unit 10 and supplied via the line 16 and the purified solution. Since the purified solution has been described in Embodiment 1, the description thereof is omitted here.
- the hydrogen iodide refining unit 20 causes the purified solution to flow down from a line 28 connected to the top of the packed column 22, and a line 16 connected to crude hydrogen iodide gas containing impurities downstream of the column. Or a co-current gas-liquid contact device that introduces both the purified solution and the crude hydrogen iodide gas from the upstream of the column.
- FIG. 1 shows an example in which the hydrogen iodide purification unit 20 is a countercurrent gas-liquid contact device.
- the purified solution that has absorbed impurities such as iodine is cooled by the cooler when the line 28 is returned to the upper portion of the packed tower 22 using a circulation pump that is not easily eroded by iodine, hydrogen iodide, and hydriodic acid. It is preferable to do. Thereby, the water in the hydrogen iodide gas obtained can be further reduced.
- the packing to be packed in the packed tower 22 is a material that is not eroded or hardly eroded by iodine, hydrogen iodide, and hydrogen iodide solution, and increases the contact area between the purified solution and the crude hydrogen iodide gas. If it is a thing, it will not specifically limit.
- Specific examples of the material of the filler include Hastelloy, various ceramics, and glass.
- it does not specifically limit about the shape of a filling material For example, shapes, such as spherical shape, cylindrical shape (cylinder shape), and cyclic
- the filling material only those having the same shape may be used, or those having different shapes may be used in combination.
- the material of the packed tower is a material which is not eroded or hardly eroded by iodine, hydrogen iodide and hydrogen iodide solution, similarly to the material of the packed material.
- the size of the packed column 22 is preferably set as appropriate depending on the amount of crude hydrogen iodide gas to be purified. Further, the amount of the purification solution to be used and the flow rate are preferably set as appropriate based on the size of the packed column 22 to be used, that is, the amount of crude hydrogen iodide gas to be purified.
- the hydrogen iodide purification unit 20 can mention the case of the apparatus using a batch type refinement
- the amount of the purified solution stored in the storage tank, the speed of blowing the crude hydrogen iodide gas, and the amount of blowing are appropriately determined depending on the amount of the crude hydrogen iodide gas to be purified. Can be set.
- the iodine compound generation unit 30 collects the iodine compound generation tower 32 that makes the hydrogen iodide gas supplied via the line 26 and the reaction raw material solution supplied via the line 38 contact, and the product obtained by the reaction. And a recovery tank 34.
- the “reaction raw material solution” in the present embodiment is a term that generically refers to the inorganic base compound aqueous solution, the alcohol-containing solution, and the aromatic diazonium solution described in the first embodiment. Further, as described in the first embodiment, the production of aliphatic iodide and aromatic iodide may use a hydrogen iodide solution, but in this embodiment, a case of using hydrogen iodide gas is taken as an example. I will give you a description.
- the reaction raw material solution is introduced into the iodine compound generation tower 32 through the line 38 from the upstream.
- hydrogen iodide gas is introduced into the iodine compound generation tower 32 so as to be orthogonal to the flow path of the reaction raw material solution. These are brought into gas-liquid contact in the iodine compound generation tower 32, thereby causing a reaction.
- the obtained iodine compound is recovered as a solution in the recovery tank 34 via the line 36. It is preferable that a temperature control mechanism, for example, a cooling mechanism is provided outside the iodine compound generation tower 32 in order to control the temperature of the reaction system.
- the target iodine compound can be obtained as a solid.
- a conventionally known device can be used. Specific examples include an evaporator and a freeze dryer.
- the iodine compound generation unit 30 may be configured to blow hydrogen iodide gas directly into the tank in which the reaction raw material solution is stored.
- the residual gas in the hydrogen iodide reaction (including the inert gas used in some cases) is taken out from the iodine compound production system 100 through the line 39.
- the extracted hydrogen gas may be reused in the hydrogen iodide reaction.
- the member that contacts the iodine, hydrogen iodide, and hydrogen iodide solution is not corroded by iodine, hydrogen iodide, and hydroiodic acid, or is not easily corroded.
- it consists of.
- Examples of such materials include hastelloy, glass, various ceramics, metal tantalum, platinum, polyvinyl chloride, and polytetrafluoroethylene.
- the raw material adjusting unit 1 and the hydrogen iodide generating unit 10 are not corroded or hardly corroded by iodine and hydrogen iodide. It is preferable to be made of a material having all durability.
- the raw material adjustment unit 1 is heated to about 200 ° C. at the maximum in melting solid iodine, it is preferably made of a material resistant to a temperature of about 200 ° C. Examples of such materials include hastelloy, glass, various ceramics, metal tantalum, platinum, and polytetrafluoroethylene.
- the hydrogen iodide generating unit 10 since the hydrogen iodide generating unit 10 is exposed to a mixed gas or a crude hydrogen iodide gas heated to about 350 ° C. in a hydrogen iodide synthesis reaction, it has resistance to a temperature of 350 ° C. or higher. It is preferable to consist of a material.
- Hastelloy various ceramics, heat resistant glass, and platinum.
- the iodine melting pot 4 in the raw material adjustment unit 1 has a surface in contact with iodine (liquid or gaseous) made of a material selected from Hastelloy, heat-resistant glass, ceramic, metal tantalum, platinum, and polytetrafluoroethylene, for example.
- iodine liquid or gaseous
- a lining process or a coating process may be performed.
- the packed tower 22 (or purification tank), tank 24, and iodine compound generation tower 32 in the hydrogen iodide purification unit 20 and iodine compound generation unit 30 have a surface contacting with iodine and hydrogen iodide, hastelloy, glass, Depending on the material selected from ceramic, metal tantalum, platinum, polyvinyl chloride and polytetrafluoroethylene, for example, lining treatment or coating treatment may be performed. Further, the hydrogen iodide generating unit 10 may use only a material selected from hastelloy, heat-resistant glass, ceramic and platinum only for the hydrogen iodide generating tower 12, and the catalyst layer heater 13 uses the above-mentioned materials. It does not have to be.
- each line connected to each unit is preferably made of the same material as each connected unit.
- each line in the iodine compound manufacturing system 100 is heated to a temperature higher than the dew point temperature of iodine and hydrogen iodide in order to prevent clogging of the line due to precipitation and solidification of iodine.
- the iodine compound production system and method according to the present invention produces crude hydrogen iodide gas in a gas phase catalytic reduction reaction using gaseous iodine and hydrogen.
- the iodine compound production system and method according to the present invention produces crude hydrogen iodide gas in a gas phase catalytic reduction reaction using gaseous iodine and hydrogen.
- Example 1 (Melting solid iodine)
- a glass-lined container with an inner volume of 2 L was used as the iodine melting pot 4.
- the vessel was provided with a blowing tube for blowing a hydrogen-containing gas into the molten iodine solution and a discharge tube for the hydrogen-containing gas and gaseous iodine.
- the obtained mixed gas of hydrogen and gaseous iodine was introduced into a Hastelloy cylinder (mixer unit 8) having an inner diameter of 20 mm and a length of 50 mm filled with glass balls having a particle diameter of 3 mm, and adjusted to a uniform mixed gas.
- a sheathed heater is provided outside the mixer unit 8 so that the temperature of the mixed gas inside the mixer unit 8 is maintained at 200 ° C.
- the line which connects the mixer part 8 and the iodine melting pot 4 was heat-retained from the outside so that iodine condensation might not occur.
- Catalytic reduction reaction A homogeneous mixed gas adjusted in the mixer section 8 with a hydrogen flow rate of 450 ml / min and a gaseous iodine flow rate of 75 ml / min was subjected to a gas phase catalytic reduction reaction in the hydrogen iodide generation section 10 to generate hydrogen iodide.
- the catalyst used at this time is a platinum group catalyst in which 1 g / L of platinum is supported on spherical alumina having a particle diameter of 3 mm (indicating that the amount supported per liter of carrier is 1 g). Further, the catalyst was used by being filled in an externally heated Hastelloy cylinder. Further, the temperature of the catalyst was 350 ° C.
- the inlet of the catalyst layer 12a was filled with glass spheres having a particle size of 5 mm, and the uniform mixed gas was preheated.
- the conversion rate of iodine was 98.0%
- the yield of hydrogen iodide was 98.0%
- the weight ratio of unreacted iodine to produced hydrogen iodide was 0.01 / 99.99. there were.
- it was confirmed that unreacted iodine can be sufficiently removed from the crude hydrogen iodide gas.
- potassium iodide was produced using a batch-type apparatus. In a 200 ml four-necked flask, 20.1 g of a 48 wt% potassium hydroxide aqueous solution prepared using 96 wt% of potassium hydroxide and 100 g of ion-exchanged water were prepared. Then, purified hydrogen iodide gas was blown into the four-necked flask to neutralize hydrogen iodide and potassium hydroxide. The hydrogen iodide gas was blown while tracking the pH value of the reaction solution using a pH meter, and ended when the pH value of the reaction solution reached 5.72 to produce a high purity potassium iodide solution. did.
- the reaction solution was fully concentrated by a rotary evaporator, and then sufficiently dried and taken out as solid potassium iodide. As a result of analysis, the purity was 99.8% by weight.
- Example 1 for the comparison with Comparative Example 1, the production method of the potassium iodide aqueous solution was exemplified by a batch method. However, the iodine compound generation tower is filled with a packing material to improve the gas-liquid contact efficiency.
- the potassium iodide aqueous solution can be continuously produced by adjusting the concentration and supply rate of the potassium hydroxide aqueous solution and controlling the pH value of the reaction solution. In such a continuous production method, the productivity of the aqueous potassium iodide solution can be further improved as compared with the batch production method.
- Example 2 (Method for producing hydrogen iodide-containing gas) A mixed gas having a hydrogen flow rate of 450 ml / min and a gaseous iodine flow rate of 75 ml / min was brought into contact with a platinum group catalyst in which 1 g of platinum was supported per liter of support on spherical alumina having a particle diameter of 3 mm heated to 350 ° C. A hydrogen-containing gas (crude hydrogen iodide gas) was produced. The weight ratio of unreacted iodine to generated hydrogen iodide in the hydrogen iodide-containing gas was 2/98 (the rest was hydrogen gas).
- a vertical glass absorption tube (hereinafter also simply referred to as an absorption tube) in which a 20 ml filling tube is filled with a ring-shaped magnetic filler is prepared, and a saturated hydrogen iodide aqueous solution is transferred from the upper portion to the lower portion of the absorption tube using a pump. Circulation was made to flow down. The flow rate of the saturated aqueous solution of hydrogen iodide was 50 ml / min. Subsequently, the produced hydrogen iodide-containing gas was introduced from the lower part of the absorption tube, and unreacted iodine was absorbed into the saturated hydrogen iodide aqueous solution.
- the hydrogen iodide-containing gas that is, hydrogen iodide
- the amount of iodine and hydrogen iodide in the recovered aqueous solution of hydrogen iodide were measured by titration analysis using an aqueous solution of sodium thiosulfate and an aqueous solution of sodium hydroxide, respectively.
- the ratio of iodine to hydrogen iodide contained in the hydrogen iodide aqueous solution was 0.01 / 99.99.
- the generated hydrogen iodide-containing gas was absorbed in water, and the iodine amount and hydrogen iodide amount in the hydrogen iodide-containing gas were measured by titration analysis with sodium thiosulfate and sodium hydroxide, respectively. As a result, the ratio of iodine to hydrogen iodide in the hydrogen iodide-containing gas was 0.9 / 99.1.
- a vertical glass absorption tube (hereinafter also simply referred to as an absorption tube) in which a 20 ml filling tube is filled with a ring-shaped magnetic filler is prepared, and a saturated hydrogen iodide aqueous solution is transferred from the upper portion to the lower portion of the absorption tube using a pump. Circulation was made to flow down. The flow rate of the saturated aqueous solution of hydrogen iodide was 50 ml / min. Subsequently, the produced hydrogen iodide-containing gas was introduced from the lower part of the absorption tube, and unreacted iodine was absorbed into the saturated hydrogen iodide aqueous solution.
- the hydrogen iodide-containing gas that is, hydrogen iodide
- the amount of iodine and hydrogen iodide in the recovered aqueous solution of hydrogen iodide were measured by titration analysis using an aqueous solution of sodium thiosulfate and an aqueous solution of sodium hydroxide, respectively.
- the ratio of iodine to hydrogen iodide contained in the hydrogen iodide aqueous solution was 0.01 / 99.99.
- Example 4 Except for changing the solvent of the saturated hydrogen iodide solution from water to acetone, it can be obtained by producing hydrogen iodide using the same method as in Example 2 and dissolving the produced hydrogen iodide in water. The amount of iodine contained in the hydrogen iodide aqueous solution was measured.
- the ratio of iodine to hydrogen iodide contained in hydrogen iodide was 0.01 / 99.99. As a result, it was shown that highly pure hydrogen iodide can be obtained very easily and efficiently.
- Example 5 Hydrogen iodide was produced using the same method as in Example 2 except that the solvent of the saturated hydrogen iodide solution was changed from water to a saturated aqueous solution of hydrogen iodide containing 10% by weight of potassium iodide. The amount of iodine contained in a hydrogen iodide aqueous solution obtained by dissolving hydrogen iodide in water was measured.
- the ratio of iodine to hydrogen iodide contained in hydrogen iodide was 0.01 / 99.99. As a result, it was shown that highly pure hydrogen iodide can be obtained very easily and efficiently.
- Example 6 Except for changing the solvent of the saturated hydrogen iodide solution from water to tetrahydrofuran, it can be obtained by producing hydrogen iodide using the same method as in Example 2 and dissolving the produced hydrogen iodide in water. The amount of iodine contained in the hydrogen iodide aqueous solution was measured.
- the ratio of iodine to hydrogen iodide contained in hydrogen iodide was 0.01 / 99.99. As a result, it was shown that highly pure hydrogen iodide can be obtained very easily and efficiently.
- Example 7 Except for changing the solvent of the saturated hydrogen iodide solution from water to toluene, it can be obtained by producing hydrogen iodide using the same method as in Example 2 and dissolving the produced hydrogen iodide in water. The amount of iodine contained in the hydrogen iodide aqueous solution was measured.
- the ratio of iodine to hydrogen iodide contained in hydrogen iodide was 0.01 / 99.99. As a result, it was shown that highly pure hydrogen iodide can be obtained very easily and efficiently.
- Example 2 Hydrogen iodide was produced using the same method as in Example 2 except that the saturated hydrogen iodide solution was changed to ion-exchanged water.
- the ratio of iodine to hydrogen iodide contained in hydrogen iodide is determined by the amount of iodine contained in ion-exchanged water one hour after introducing the hydrogen iodide-containing gas into the absorption tube, and the amount of hydrogen iodide. Measurement and calculation were performed in the same manner as in Example 2.
- the ratio of iodine to hydrogen iodide contained in hydrogen iodide was 2/98. That is, there was no change in the purity of hydrogen iodide.
- crude hydrogen iodide gas is generated in a gas phase catalytic reduction reaction using gaseous iodine and hydrogen.
- the iodine compound can be obtained easily and efficiently, and the price of the iodine compound can be reduced. Play.
- gas-liquid contact is performed between a hydrogen iodide-containing gas and a purification solution that dissolves substances other than hydrogen iodide contained in the hydrogen iodide-containing gas but does not dissolve hydrogen iodide.
- hydrogen iodide is purified from the hydrogen iodide-containing gas.
- the iodine compound production system according to the present invention can produce a high-purity iodine compound simply, efficiently, and inexpensively. Therefore, the high purity iodine compound obtained by the production system according to the present invention can be suitably used in various reactions using it as a raw material.
- high purity hydrogen iodide can be produced with high efficiency, which is suitable for industrial production of hydrogen iodide.
- the obtained high-purity hydrogen iodide or hydroiodic acid can be very suitably applied to further reaction using hydrogen iodide or hydroiodic acid.
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Abstract
Description
ヨウ化水素ガスを用いてヨウ素化合物を製造するヨウ素化合物製造システムであって、水素ガスとガス状ヨウ素とを触媒の存在下で接触させることにより生成される粗ヨウ化水素ガスに対して、当該粗ヨウ化水素ガスに含有されるヨウ化水素以外の物質を溶解し、かつ、ヨウ化水素を溶解しない精製溶液を接触させることにより、ヨウ化水素ガスを得る精製器を備えたヨウ化水素精製ユニットを備えていることを特徴としている。
ヨウ化水素ガスを用いてヨウ素化合物を製造するヨウ素化合物製造方法であって、水素ガスとガス状ヨウ素とを触媒の存在下で接触させることにより生成される粗ヨウ化水素ガスに対して、当該粗ヨウ化水素ガスに含有されるヨウ化水素以外の物質を溶解し、かつ、ヨウ化水素を溶解しない精製溶液を接触させることにより、ヨウ化水素ガスを得るヨウ化水素精製工程を含むことを特徴としている。
2 水素含有ガス供給器(水素供給器)
4 ヨウ素溶融釜(ヨウ素貯留槽)
5 液体ヨウ素
8 ミキサー部(ガス混合器、混合ガス加熱器)
10 ヨウ化水素生成ユニット
12 ヨウ化水素生成塔(ヨウ化水素生成器)
12a 触媒層(触媒部)
13 触媒層加熱器(触媒部加熱器)
20 ヨウ化水素精製ユニット
22 充填塔(精製器)
24 タンク
30 ヨウ素化合物生成ユニット
32 ヨウ素化合物生成塔(ヨウ素化合物生成器)
34 回収槽
100 ヨウ素化合物製造システム
本発明に係るヨウ素化合物の製造方法の一実施形態について、以下に説明する。
本実施形態では、ヨウ素化合物の製造方法として、ヨウ素の気相接触還元反応を用いて生成したヨウ化水素を用いてヨウ素化合物を製造する場合を例にあげて説明する。本実施形態に係るヨウ素化合物の製造方法は、主として、ガス状ヨウ素生成工程、ヨウ化水素生成工程、ヨウ化水素精製工程、ヨウ素化合物生成工程の4つの工程を含んでいる。これら4つの工程について、以下にそれぞれ説明する。
まず、ガス状ヨウ素生成工程について以下に説明する。ガス状ヨウ素生成工程は、固体のヨウ素を加熱することにより、その少なくとも一部をガス状ヨウ素とする工程である。
次に、ヨウ化水素生成工程について以下に説明する。ヨウ化水素生成工程は、ヨウ素を気相接触還元して得られる、ヨウ化水素を主成分として含有する粗ヨウ化水素ガスを生成する工程である。なお、本明細書等において「主成分」とは、粗ヨウ化水素ガスまたはヨウ化水素に含まれる全成分のうち、50重量%を越える成分であることを意味している。
ガス状ヨウ素および水素ガスを用いた気相接触還元反応における触媒としては、白金族元素を酸化物および活性炭の少なくともいずれか一方に分散担持させた触媒であることが好ましい。白金族元素を酸化物および活性炭の少なくともいずれか一方に分散担持させることによって、ヨウ素と水素とを活性化させることができる。これによって、比較的低い温度においてもヨウ化水素の生成速度を向上できる。また、ヨウ素の転化率および生成するヨウ化水素の収率も併せて向上できる。
気相接触還元反応における反応温度は、200~1000℃の範囲内であることが好ましく、250~900℃の範囲内であることがより好ましく、250~850℃の範囲内であることがさらに好ましい。また、ガス空間速度は。300~10000hr-1の範囲内であることが好ましく、500~4000hr-1の範囲内であることがより好ましい。なお、本明細書等における「ガス空間速度」とは、標準状態において単位時間当たりの反応ガス容積と触媒容積との比率を意味している。さらに、反応圧力は、常圧から10MPaの範囲内であることが好ましい。
次に、ヨウ化水素精製工程について以下に説明する。ヨウ化水素精製工程は、ヨウ化水素生成工程において生成した、ヨウ化水素を主成分とする粗ヨウ化水素ガスにおけるヨウ化水素以外の物質(以下、不純物とも称する)を除去する工程である。すなわち、粗ヨウ化水素ガスに含有される不純物を溶解するが、ヨウ化水素を溶解しない精製溶液と、粗ヨウ化水素ガスとを気液接触させる工程である。
精製溶液は、粗ヨウ化水素ガスに含有される不純物を溶解するが、ヨウ化水素を溶解しない溶液であれば、特に限定されるものではない。それらの中でも、ヨウ化水素からの分離が困難であり、かつ生成したヨウ化水素を他の反応に用いる場合に問題となる未反応のヨウ素を除去できる溶液であることが好ましい。
次に、ヨウ素化合物生成工程について以下に説明する。ヨウ素化合物生成工程は、上述したヨウ化水素精製工程において得られた高純度のヨウ化水素ガスを用いて様々なヨウ素化合物を製造する工程である。本実施形態では、一例として、無機ヨウ化物、脂肪族ヨウ化物および芳香族ヨウ化物を製造する場合について、それぞれ説明する。なお、上記の各工程を経て得られたヨウ化水素の用途は、上述のヨウ素化合物の製造に限定されるものではなく、ヨウ化水素を原料とするその他の反応においても好適に用いることができる。
まず、無機ヨウ化物の製造について、以下に説明する。無機ヨウ化物は、ヨウ化水素と無機塩基化合物との接触により製造することができる。ここで、本実施形態において用いられる無機塩基化合物は、ヨウ化水素との間に中和反応を起こすことができる化合物である。言い換えれば、水溶液中で解離または平衡反応を起こして、水酸化物イオン(OH-)を生じる化合物である。
本実施形態に係る無機ヨウ化物の製造では、ヨウ化水素ガスと、無機塩基化合物とを接触させる中和反応を起こすことにより目的とする無機ヨウ化物を得る。例えば、無機塩基化合物が、水酸化カリウムである場合、反応は、下記の反応式(1)に従う。
無機ヨウ化物の製造において、ヨウ化水素ガスと無機塩基化合物との接触は、液体の無機塩基化合物(以下、「無機塩基溶液」とも称する)を用いて、気液接触により反応を進めることが好ましい。気液接触を採用する場合、気固接触の場合と比べて、接触効率がよく、生産性を向上させることができる。
次に、脂肪族ヨウ化物を製造する場合について説明する。本明細書等における脂肪族ヨウ化物とは、ヨウ化アルキルを意味している。すなわち、目的とする脂肪族ヨウ化物は、ヨウ化水素ガスと、アルコール類含有溶液とを接触させることにより得ることができる。脂肪族ヨウ化物の製造は、上述した無機ヨウ化物の製造とほぼ同様である。
したがって、脂肪族ヨウ化物の製造について、無機ヨウ化物の製造において説明した内容は省略し、無機ヨウ化物の製造と異なる点についてのみ以下に説明する。
次に、芳香族ヨウ化物を製造する場合について説明する。目的とする芳香族ヨウ化物は、ヨウ化水素ガスと、芳香族ジアゾニウム溶液とを接触させることにより得ることができる。すなわち、芳香環に結合しているジアゾニウム基がヨウ素に置換され、芳香族ヨウ化物として得られる。芳香族ヨウ化物の製造は、上述した無機ヨウ化物の製造とほぼ同様である。したがって、芳香族ヨウ化物の製造について、無機ヨウ化物の製造において説明した内容は省略し、無機ヨウ化物の製造と異なる点についてのみ以下に説明する。
本発明に係るヨウ素化合物製造システムについて、実施形態2として図1を参照して以下に説明する。図1は、本発明に係るヨウ素化合物製造システムの概略を示すブロック図である。したがって、図1は、ヨウ素化合物製造システムにおける各ユニットを繋ぐラインの形状、各ユニット寸法などを正確に示すものではない。これらは、装置を製造する際に適宜変更することができる。なお、本実施形態において実施形態1と同一の用語は、特に断りのない限り同一の意味として用いている。
原料調整ユニット1は、ヨウ素化合物の製造に用いるヨウ化水素を生成するための原料を調整するためのユニットである。より具体的には、ガス状ヨウ素および水素を所定のモル比および温度となるように調整するためのユニットである。
ヨウ素溶融釜4では、固体のヨウ素を融点~150℃程度に加熱して得られる液体ヨウ素5に対して水素含有ガス供給器2からライン3を経て供給される水素含有ガスを接触させることにより、ガス状ヨウ素が生成される。生成されたガス状ヨウ素は、ライン6を経てミキサー部8へと送られる。
ミキサー部8は、ヨウ素溶融釜4において生成されたガス状ヨウ素に水素を混合した混合ガスにおいて、ヨウ素と水素との組成が均一となるように混合するガス混合器、および混合ガスを120~350℃程度にまで加熱する加熱器を備えている。ミキサー部8において加熱された混合ガスは、ライン14を経てヨウ化水素生成ユニット10へと送られる。
ヨウ化水素生成ユニット10は、水素とガス状ヨウ素とを反応させるヨウ化水素生成塔12を備えている。ヨウ化水素生成塔12は、その内部に触媒層(触媒部)12aを備えている。水素ガスおよびガス状のヨウ素は、ライン14を経てヨウ化水素生成塔12の下部から供給される。そして、粗ヨウ化水素ガスが、ヨウ化水素生成塔12の上部から得られる。生成された粗ヨウ化水素ガスはライン16を経てヨウ化水素精製ユニット20へと送られる。触媒層12aには、実施形態1において説明した触媒が充填されている。また、ヨウ化水素生成塔12の外面には、触媒層加熱器(触媒部加熱器)13(例えば、電気炉、オイルバスなど)が備えられている。
ヨウ化水素精製ユニット20は、充填物が充填された充填塔22と、精製溶液が貯留されたタンク24とを備えている。充填塔22は、ヨウ化水素生成ユニット10で生成され、ライン16を経て供給された粗ヨウ化水素ガスと、精製溶液とを気液接触させるものである。精製溶液については、実施形態1において説明したため、ここではその説明を省略する。
ヨウ素化合物生成ユニット30は、ライン26を経て供給されたヨウ化水素ガスとライン38を経て供給された反応原料溶液とを接触させるヨウ素化合物生成塔32と、反応により得られた生成物を回収する回収槽34とを備えている。なお、本実施形態における「反応原料溶液」とは、実施形態1において説明した、無機塩基化合物水溶液、アルコール類含有溶液、および芳香族ジアゾニウム溶液を総称する用語である。また、実施形態1において説明したように、脂肪族ヨウ化物および芳香族ヨウ化物の製造は、ヨウ化水素溶液を用いてもよいが、本実施形態では、ヨウ化水素ガスを用いる場合を例に挙げて説明する。
ヨウ化水素精製ユニット20およびヨウ素化合物生成ユニットにおいて、ヨウ素、ヨウ化水素、およびヨウ化水素溶液に接触する部材は、ヨウ素、ヨウ化水素およびヨウ化水素酸により腐食されないか、または腐食されにくい材質からなることが好ましい。
以上のように、本発明に係るヨウ素化合物の製造システムおよび製造方法は、ガス状ヨウ素と水素とを用いた気相接触還元反応において粗ヨウ化水素ガスを生成している。これによって、粗ヨウ化水素ガスからヨウ化水素を精製する際に、副生成物の除去などの煩雑な処理工程を不要とすることができる。これによって、高純度のヨウ化水素を簡便、かつ効率よく得ることができるとともに、製造に要するコストを削減することができる。また、このように得られたヨウ化水素ガスを用いてヨウ素化合物を製造すれば、多様なヨウ素化合物を容易に、かつ効率よく得ることができるとともに、製造したヨウ素化合物を廉価で提供することができる。
(固体ヨウ素の溶融)
本実施例では、ヨウ素溶融釜4として、ジャケット付きガラスライニングされた内容積2Lの容器を用いた。容器には、溶融ヨウ素液へ水素含有ガスを吹き込むための吹き込み管と、水素含有ガスおよびガス状ヨウ素の排出管とを設けた。
得られた水素およびガス状ヨウ素の混合ガスを粒径3mmのガラス玉を充填した内径20mm、長さ50mmのハステロイ製円筒(ミキサー部8)に導入し、均一な混合ガスに調整した。
ミキサー部8において調整した水素流量450ml/分、ガス状ヨウ素流量75ml/分の均一混合ガスをヨウ化水素生成部10において気相接触還元反応させ、ヨウ化水素を生成した。このとき用いた触媒は、粒径3mmの球状アルミナに白金を1g/L(担体1リットル当たりの担持量が1gであることを示す)を担持させた白金族触媒である。また、触媒は外部加熱型ハステロイ製円筒に充填して用いた。さらに、触媒の温度は350℃とした。なお、触媒層12aの入口部には、粒径5mmのガラス球を充填し、均一混合ガスの予熱を行った。
20mlの充填管にリング状の磁性充填物を充填した縦型ガラス吸収管を用意し、ポンプを用いて飽和ヨウ化水素水溶液をガラス吸収管の上部から下部へと流下するように循環させた。なお、飽和ヨウ化水素水溶液の流速度は、50ml/分とした。次いで、接触還元反応により得られた粗ヨウ化水素ガスをガラス吸収管の上部から導入し、並流気液接触させて、未反応ヨウ素を飽和ヨウ化水素水溶液に吸収させた。ガラス吸収管からの排出ガスの一部を水に吸収させ、化学分析を用いてヨウ素とヨウ化水素の量を定量した。
本実施例では、バッチ式の装置を用いてヨウ化カリウムの製造を実施した。200mlの四つ口フラスコに、純度96重量%の水酸化カリウムを用いて調整した48重量%の水酸化カリウム水溶液20.1g、およびイオン交換水100gを用意した。そして、この四つ口フラスコに精製したヨウ化水素ガスを吹き込み、ヨウ化水素と水酸化カリウムとを中和反応させた。ヨウ化水素ガスの吹き込みは、反応液のpH値をpHメーター計を用いて追跡しながら行い、反応水溶液のpH値が5.72になったところで終了し、高純度のヨウ化カリウム水溶液を製造した。
1Lフラスコにヨウ素200gを取り、47.6%の水酸化カリウム水溶液92.9g、イオン交換水20.5gを加え、ヨウ素を溶解した。これに87.1%ギ酸水溶液43.7gを少量ずつ添加した。2時間かけて全てのギ酸水溶液を添加し、反応液が発泡しなくなった後、加熱しつつ1時間攪拌し、反応を行った。反応後、活性炭の層に溶液を通し、未反応のギ酸を吸着させてヨウ化カリウムの水溶液を得た。
(ヨウ化水素含有ガスの生成方法)
水素流量450ml/分、ガス状ヨウ素流量75ml/分の混合ガスを、350℃に加熱した、粒径3mmの球状アルミナに担体1Lあたり1gの白金を担持させた白金族触媒に接触させ、ヨウ化水素含有ガス(粗ヨウ化水素ガス)を生成した。なお、ヨウ化水素含有ガスにおける未反応ヨウ素と生成したヨウ化水素との重量比は、2/98であった(残りは水素ガスであった)。
20mlの充填管にリング状の磁性充填物を充填した縦型ガラス吸収管(以下、単に吸収管とも称する)を用意し、ポンプを用いて飽和ヨウ化水素水溶液を吸収管の上部から下部へと流下するように循環させた。なお、飽和ヨウ化水素水溶液の流速度は、50ml/分とした。次いで、生成したヨウ化水素含有ガスを吸収管の下部から導入し、未反応ヨウ素を飽和ヨウ化水素水溶液に吸収させた。
吸収管を通過した後のヨウ化水素含有ガス(すなわち、ヨウ化水素)は、水に吸収させ、水溶液として回収した。回収したヨウ化水素の水溶液中のヨウ素量およびヨウ化水素量は、それぞれチオ硫酸ナトリウムおよび水酸化ナトリウム水溶液による滴定分析によって測定した。
(ヨウ化水素含有ガスの生成方法)
300mlの四つ口フラスコに水(100g;5.556mol)、赤リン(9g;0.290mol)を入れ、撹拌しながら0℃に冷却した。そこに、ヨウ素(200g;0.788mol)を4回に分けて加え、2時間反応させてヨウ化水素を合成した。次に、常圧下において、四つ口フラスコ内に窒素ガスを30ml/分で流しながら加熱し、常圧下におけるヨウ化水素と水との共沸組成(重量比)である57.6%に対して過剰なヨウ化水素をヨウ化水素含有ガスとして発生させた。
20mlの充填管にリング状の磁性充填物を充填した縦型ガラス吸収管(以下、単に吸収管とも称する)を用意し、ポンプを用いて飽和ヨウ化水素水溶液を吸収管の上部から下部へと流下するように循環させた。なお、飽和ヨウ化水素水溶液の流速度は、50ml/分とした。次いで、生成したヨウ化水素含有ガスを吸収管の下部から導入し、未反応ヨウ素を飽和ヨウ化水素水溶液に吸収させた。
吸収管を通過した後のヨウ化水素含有ガス(すなわち、ヨウ化水素)は、水に吸収させ、水溶液として回収した。回収したヨウ化水素の水溶液中のヨウ素量およびヨウ化水素量は、それぞれチオ硫酸ナトリウムおよび水酸化ナトリウム水溶液による滴定分析によって測定した。
飽和ヨウ化水素溶液の溶媒を、水からアセトンに変更した以外は、実施例2と同様の方法を用いてヨウ化水素を製造し、製造したヨウ化水素を水に溶解して得ることができるヨウ化水素水溶液に含有されているヨウ素の量を測定した。
飽和ヨウ化水素溶液の溶媒を、水から10重量%のヨウ化カリウムを含有した飽和ヨウ化水素水溶液に変更した以外は、実施例2と同様の方法を用いてヨウ化水素を製造し、製造したヨウ化水素を水に溶解して得ることができるヨウ化水素水溶液に含有されているヨウ素の量を測定した。
飽和ヨウ化水素溶液の溶媒を、水からテトラヒドロフランに変更した以外は、実施例2と同様の方法を用いてヨウ化水素を製造し、製造したヨウ化水素を水に溶解して得ることができるヨウ化水素水溶液に含有されているヨウ素の量を測定した。
飽和ヨウ化水素溶液の溶媒を、水からトルエンに変更した以外は、実施例2と同様の方法を用いてヨウ化水素を製造し、製造したヨウ化水素を水に溶解して得ることができるヨウ化水素水溶液に含有されているヨウ素の量を測定した。
飽和ヨウ化水素溶液を、イオン交換水に変更した以外は、実施例2と同様の方法を用いてヨウ化水素を製造した。ヨウ化水素に含有されるヨウ素とヨウ化水素との比は、ヨウ化水素含有ガスを吸収管に導入してから1時間後のイオン交換水中に含まれるヨウ素量と、ヨウ化水素量とを実施例2と同様の方法によって測定し、算出した。
Claims (30)
- ヨウ化水素ガスを用いてヨウ素化合物を製造するヨウ素化合物製造システムであって、
水素ガスとガス状ヨウ素とを触媒の存在下で接触させることにより生成される粗ヨウ化水素ガスに対して、当該粗ヨウ化水素ガスに含有されるヨウ化水素以外の物質を溶解し、かつ、ヨウ化水素を溶解しない精製溶液を接触させることにより、ヨウ化水素ガスを得る精製器を備えたヨウ化水素精製ユニットを備えていることを特徴とするヨウ素化合物製造システム。 - 固体ヨウ素を溶融し、液化させた液状ヨウ素を貯留するヨウ素貯留槽、および、水素を含む水素含有ガスを供給する水素供給器を備えた原料調整ユニットであって、上記ヨウ素貯留槽に貯留されている液状ヨウ素および当該液状ヨウ素を気化させることにより得られるガス状ヨウ素の少なくともいずれかに対して、上記水素供給器から供給される水素含有ガスを供給することにより、ガス状ヨウ素および水素を含む混合ガスを得る原料調整ユニットと、
上記原料調整ユニットにおいて得られた混合ガスを粗ヨウ化水素ガスとする触媒からなる触媒部を有するヨウ化水素生成器を備えたヨウ化水素生成ユニットと、
上記ヨウ化水素精製ユニットにおいて得られたヨウ化水素ガスと、当該ヨウ化水素ガスに対して反応性を有する反応原料とを接触させることにより、ヨウ素化合物を生成するヨウ素化合物生成器備えたヨウ素化合物生成ユニットと、
をさらに備えていることを特徴とする請求の範囲第1項に記載のヨウ素化合物製造システム。 - 上記ヨウ素貯留槽は、当該ヨウ素貯留槽を加熱するヨウ素貯留槽加熱器を備えていることを特徴とする請求の範囲第2項に記載のヨウ素化合物製造システム。
- 上記ヨウ化水素生成ユニットは、上記触媒部を加熱する触媒部加熱器を備えていることを特徴とする請求の範囲第2項または第3項に記載のヨウ素化合物製造システム。
- 上記ヨウ化水素精製ユニットは、上記粗ヨウ化水素ガスから未反応のヨウ素を除去する精製溶液を循環させる循環機構を備えており、
上記循環機構は、上記精製器に戻される上記精製溶液を冷却する冷却器を備えていることを特徴とする請求の範囲第1項から第4項のいずれか1項に記載のヨウ素化合物製造システム。 - 上記ヨウ素化合物生成器には、上記反応原料溶液を流す流路が設けられているとともに、上記流路に上記ヨウ化水素ガスを導入するガスノズルが接続されていることを特徴とする請求の範囲第2項から第5項のいずれか1項に記載のヨウ素化合物製造システム。
- 上記原料調整ユニットは、上記混合ガスにおける上記ガス状ヨウ素と上記水素との組成を均一とするガス混合器をさらに備えていることを特徴とする請求の範囲第2項から第6項のいずれか1項に記載のヨウ素化合物製造システム。
- 上記原料調整ユニットは、上記混合ガスを加熱する混合ガス加熱器をさらに備えていることを特徴とする請求の範囲第2項から第7項のいずれか1項に記載のヨウ素化合物製造システム。
- 上記混合ガス加熱器は、上記ガス混合器に備えられていることを特徴とする請求の範囲第8項に記載のヨウ素化合物製造システム。
- 上記混合ガス加熱器および上記ガス混合器は、上記ヨウ化水素生成器に備えられていることを特徴とする請求の範囲第9項に記載のヨウ素化合物製造システム。
- 上記原料調整ユニットの少なくともヨウ素との接触面の材質は、ハステロイ、ガラス、セラミック、メタルタンタル、白金、およびポリテトラフルオロエチレンから選択される少なくとも1種からなることを特徴とする請求の範囲第2項から第10項のいずれか1項に記載のヨウ素化合物製造システム。
- 上記ヨウ化水素生成ユニットのヨウ化水素およびヨウ素との接触面の材質は、ハステロイ、耐熱ガラス、セラミック、および白金から選択される少なくとも1種からなることを特徴とする請求の範囲第2項から第10項のいずれか1項に記載のヨウ素化合物製造システム。
- 本発明に係るヨウ素化合物製造システムでは、さらに、上記ヨウ化水素精製ユニットおよび上記ヨウ素化合物生成ユニットの材質は、ハステロイ、ガラス、セラミック、メタルタンタル、白金、ポリ塩化ビニル、およびポリテトラフルオロエチレンから選択される少なくとも1種からなることを特徴とする請求の範囲第2項から第10項のいずれか1項に記載のヨウ素化合物製造システム。
- 上記ヨウ化水素精製ユニットにおける精製器は、充填物を充填した充填塔を備えており、当該充填塔には、上記粗ヨウ化水素ガスおよび当該粗ヨウ化水素ガスから未反応のヨウ素を除去する精製溶液を導入する導入口が設けられていることを特徴とする請求の範囲第1項に記載のヨウ素化合物製造システム。
- 上記ヨウ化水素精製ユニットにおける精製器は、上記粗ヨウ化水素ガスから未反応のヨウ素を除去する精製溶液を貯留する精製槽と、当該精製槽に上記粗ヨウ化水素ガスを供給する供給器と、を備えていることを特徴とする請求項の範囲第1項に記載のヨウ素化合物製造システム。
- ヨウ化水素ガスを用いてヨウ素化合物を製造するヨウ素化合物製造方法であって、
水素ガスとガス状ヨウ素とを触媒の存在下で接触させることにより生成される粗ヨウ化水素ガスに対して、当該粗ヨウ化水素ガスに含有されるヨウ化水素以外の物質を溶解し、かつ、ヨウ化水素を溶解しない精製溶液を接触させることにより、ヨウ化水素ガスを得るヨウ化水素精製工程を含むことを特徴とするヨウ素化合物製造方法。 - 上記ヨウ化水素精製工程における精製溶液は、飽和ヨウ化水素溶液であることを特徴とする請求の範囲第16項に記載のヨウ素化合物製造方法。
- 上記飽和ヨウ化水素溶液の溶媒は、水、ケトン類、エーテル類、アルコール類、および芳香族化合物の少なくともいずれか1種であることを特徴とする請求の範囲第17項に記載のヨウ素化合物製造方法。
- 上記ヨウ化水素精製工程では、充填物を充填した充填塔内において、上記粗ヨウ化水素ガスと上記精製溶液とを気液接触させることを特徴とする請求の範囲第16項から第18項のいずれか1項に記載のヨウ素化合物製造方法。
- 上記ヨウ化水素精製工程では、上記粗ヨウ化水素ガスを上記精製溶液中に吹き込むことにより気液接触させることを特徴とする請求の範囲第16項から第18項のいずれか1項に記載のヨウ素化合物製造方法。
- 上記触媒は、少なくとも1種類以上の白金族元素を酸化物および活性炭の少なくともいずれか一方に分散担持させたものであることを特徴とする請求の範囲第16から第20項に記載のヨウ素化合物製造方法。
- 固体のヨウ素を加熱して得られる液状ヨウ素に、当該液状ヨウ素に対して不活性なガスおよび水素の少なくともいずれかを含むガスを接触させ、ガス状ヨウ素を得るガス状ヨウ素生成工程と、
上記ガス状ヨウ素および水素を含む混合ガスを上記触媒存在下で接触還元させ、粗ヨウ化水素ガスを生成するヨウ化水素生成工程と、
上記ヨウ化水素精製工程において得られたヨウ化水素ガスを用いて、ヨウ素化合物を製造するヨウ素化合物生成工程と、をさらに含むことを特徴とする請求の範囲第16項に記載のヨウ素化合物製造方法。 - 上記混合ガス中のガス状ヨウ素に対する水素のモル比を、上記ヨウ化水素生成工程の前までに、0.5~10の範囲内とすることを特徴とする請求の範囲第22項に記載のヨウ素化合物製造方法。
- 上記ヨウ素化合物生成工程では、無機塩基化合物溶液に対して、上記ヨウ化水素ガスを接触させることを特徴とする請求の範囲第22項または第23項に記載のヨウ素化合物製造方法。
- 上記ヨウ素化合物生成工程において得られる無機ヨウ化物溶液を乾燥する乾燥工程をさらに含むことを特徴とする請求の範囲第24項に記載のヨウ素化合物製造方法。
- 上記ヨウ素化合物生成工程では、アルコール類含有溶液または芳香族ジアゾニウム溶液に対して、上記ヨウ化水素ガスまたは上記ヨウ化水素ガスを溶質とする溶液を接触させることを特徴とする請求の範囲第22項から第25項のいずれか1項に記載のヨウ素化合物製造方法。
- 上記ヨウ素化合物生成工程において得られる有機ヨウ化物溶液を精製する有機ヨウ化物精製工程をさらに含むことを特徴とする請求の範囲第26項に記載のヨウ素化合物製造方法。
- 請求の範囲第16から第21項に記載のヨウ素化合物製造方法におけるヨウ化水素生成工程において得られたヨウ化水素。
- 上記ヨウ化水素に含有されるヨウ素の含有量は、上記ヨウ化水素に含有される全成分の重量を100重量%としたとき、少なくとも2重量%以下であることを特徴とする請求の範囲第28項に記載のヨウ化水素。
- 請求の範囲第29項に記載のヨウ化水素を水に溶解して得られたヨウ化水素酸。
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JP2015061524A (ja) * | 2013-08-21 | 2015-04-02 | 三菱化学株式会社 | 糖液の精製方法、活性炭処理糖液、有機化合物の製造方法および微生物の培養方法 |
JP6330064B1 (ja) * | 2017-01-10 | 2018-05-23 | 伊勢化学工業株式会社 | ヨウ化水素酸の製造方法及びヨウ化金属水溶液の製造方法 |
JP2018111618A (ja) * | 2017-01-10 | 2018-07-19 | 伊勢化学工業株式会社 | ヨウ化水素酸の製造方法及びヨウ化金属水溶液の製造方法 |
JP2019163180A (ja) * | 2018-03-19 | 2019-09-26 | 国立研究開発法人日本原子力研究開発機構 | ブンゼン反応器 |
JP7141612B2 (ja) | 2018-03-19 | 2022-09-26 | 国立研究開発法人日本原子力研究開発機構 | ブンゼン反応器 |
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KR20100123704A (ko) | 2010-11-24 |
US8268284B2 (en) | 2012-09-18 |
KR101531734B1 (ko) | 2015-06-25 |
US20100308261A1 (en) | 2010-12-09 |
JP5437082B2 (ja) | 2014-03-12 |
JPWO2009096446A1 (ja) | 2011-05-26 |
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