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WO2018135408A1 - Composition d'alcool isopropylique et procédé de production d'alcool isopropylique - Google Patents

Composition d'alcool isopropylique et procédé de production d'alcool isopropylique Download PDF

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Publication number
WO2018135408A1
WO2018135408A1 PCT/JP2018/000645 JP2018000645W WO2018135408A1 WO 2018135408 A1 WO2018135408 A1 WO 2018135408A1 JP 2018000645 W JP2018000645 W JP 2018000645W WO 2018135408 A1 WO2018135408 A1 WO 2018135408A1
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Prior art keywords
isopropyl alcohol
distillation
concentration
dissolved oxygen
water
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PCT/JP2018/000645
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English (en)
Japanese (ja)
Inventor
信幸 山本
学 鎌本
俊輔 保坂
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株式会社トクヤマ
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Priority to JP2018563300A priority Critical patent/JP7118898B2/ja
Publication of WO2018135408A1 publication Critical patent/WO2018135408A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C07C29/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds with formation of absorption products in mineral acids and their hydrolysis
    • C07C29/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds with formation of absorption products in mineral acids and their hydrolysis the acid being phosphoric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/10—Monohydroxylic acyclic alcohols containing three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to an isopropyl alcohol composition and a method for producing isopropyl alcohol.
  • a semiconductor device is generally manufactured by a method of forming elements and wiring by repeating a film forming process, an etching process, and the like.
  • miniaturization and high integration of elements and wirings have been increasingly progressed while higher performance of semiconductor devices is required.
  • the influence of the quality of chemicals used for film formation, etching, etc. on the yield of semiconductor devices cannot be ignored, and there is a strong demand for improving the quality of chemicals.
  • isopropyl alcohol also referred to as 2-propanol
  • isopropyl alcohol used as a cleaning liquid or a drying liquid in a semiconductor device manufacturing process is strongly demanded to improve the quality as in the case of ultrapure water.
  • Isopropyl alcohol is subjected to advanced purification in the production process, filled in a canister can, and further shipped and delivered with nitrogen gas sealed.
  • This invention is made
  • the present inventors have determined that when the dissolved oxygen concentration in isopropyl alcohol and the concentration of organic acid contained as impurities exceed a certain range, isopropyl alcohol is nitrogenated. Even when encapsulated with gas, the inventors have found that the concentration of organic acid increases during storage or transportation.
  • an isopropyl alcohol composition comprising isopropyl alcohol and impurities, wherein a dissolved oxygen concentration is 0.1% or less with respect to an oxygen saturation solubility at 25 ° C. in the atmosphere, and An isopropyl alcohol composition in which the concentration of the organic acid as an impurity is 20 ppb or less on a mass basis is provided.
  • the isopropyl alcohol composition has a boiling point higher than that of isopropyl alcohol, and the concentration of the high boiling point compound as an impurity having 4 or more carbon atoms excluding the organic acid is 20 ppb on a mass basis. The following is preferable.
  • the isopropyl alcohol composition preferably has a concentration of moisture as an impurity of 20 ppm or less on a mass basis.
  • a method for producing isopropyl alcohol wherein isopropyl alcohol is produced by directly hydrating water with propylene, A raw material supply step of supplying propylene and water having an acid catalyst dissolved therein and a pH adjusted to 2.5 to 4.5 to the reactor; A reaction step of reacting propylene and water in the reactor; A recovery step of separating unreacted propylene from the reaction mixture obtained in the reaction step and recovering a reaction mixture containing isopropyl alcohol; A first distillation step of distilling the reaction mixture recovered in the recovery step in a distillation column to remove a low-boiling compound having a boiling point lower than that of isopropyl alcohol; A second distillation step of distilling the reaction mixture from which the low-boiling compounds have been removed in the first distillation step in a distillation column to remove water to obtain isopropyl alcohol, In the first distillation step, a method for producing isopropyl alcohol is provided in which the oxygen partial pressure in the gas phase at
  • the top of the distillation column has a condensing part that condenses the gas and returns a part thereof to the distilling column, and the gas present in the gas phase of the condensing part is
  • a distillation column having a structure with a vent pipe for discharging, and supplying an inert gas to the vent pipe so that the linear velocity in the discharge direction is 0.01 to 3.0 m / sec. Is a preferred embodiment for further suppressing the production of organic acid.
  • the isopropyl alcohol composition of the present invention exhibits extremely good storage stability that there is almost no change (increase) in the organic acid concentration over time even during long-term storage for 30 days or longer. It can be suitably used as a drying liquid.
  • the present inventors set the organic acid concentration within a specific range corresponding to the dissolved oxygen of isopropyl alcohol. Therefore, it is presumed that the reaction in which an organic acid is generated from dissolved oxygen and unavoidable impurities can be prevented, and the generation of a new organic acid is prevented.
  • FIG. 3 is a graph showing the change over time in the concentration of organic acid for isopropyl alcohol in Examples 1 to 3 and Comparative Example 1.
  • the isopropyl alcohol composition of the present disclosure is a high-purity isopropyl alcohol composition composed of isopropyl alcohol and impurities (unavoidable impurities, trace impurities), and the dissolved oxygen concentration is an oxygen saturation solubility at 25 ° C. in the atmosphere. And the concentration of the organic acid as an impurity is 20 ppb or less on a mass basis.
  • the dissolved oxygen concentration (%) of the isopropyl alcohol composition was measured by measuring the oxygen partial pressure corresponding to the dissolved oxygen present in the solution at 25 ° C. of the isopropyl alcohol composition to be measured. The value obtained by dividing the oxygen partial pressure by the oxygen partial pressure at 25 ° C. in the atmosphere is expressed in%.
  • the oxygen partial pressure at 25 ° C. in the atmosphere means the oxygen partial pressure in air at 25 ° C. and 1 atm, and is 21 kPa.
  • the oxygen saturation solubility at 25 ° C. in the atmosphere is the oxygen concentration when the dissolved oxygen is in an equilibrium state in an atmosphere of 1 atm and an oxygen partial pressure of 21 kPa.
  • the oxygen partial pressure corresponding to the dissolved oxygen concentration of the isopropyl alcohol composition can be measured by using an oxygen concentration meter (manufactured by Supervisor Ultra, Inc., ORBISPHERE 510 gas analyzer (trade name)) described later.
  • the dissolved oxygen concentration of the isopropyl alcohol composition is not displayed as an absolute value, but as described above, the dissolved oxygen concentration is displayed as a relative value when the oxygen saturation solubility is 100%. Can be displayed accurately.
  • various different values are shown by literature. From this, it is understood that when the dissolved oxygen concentration is displayed as an absolute value, the dissolved oxygen concentration cannot be accurately displayed.
  • the isopropyl alcohol composition of the present disclosure has a dissolved oxygen concentration of 0.1% or less with respect to oxygen saturation solubility at 25 ° C. in the atmosphere.
  • the dissolved oxygen concentration is preferably 0.075% or less with respect to the oxygen saturation solubility at 25 ° C. in the air, and more preferably 0.05% with respect to the oxygen saturation solubility at 25 ° C. in the air. It is as follows.
  • the concentration of the organic acid in the isopropyl alcohol composition is the concentration of the total amount of the organic acid identified by the ion chromatography method shown in the examples.
  • formic acid, acetic acid, and propionic acid are identified as organic acids, and the concentration of the organic acid is indicated by the total amount of the identified organic acids.
  • the concentration of the organic acid as an impurity is 20 ppb or less, preferably 5 ppb or less, on a mass basis.
  • the lower limit is not particularly limited, and may be, for example, 0.1 ppb or more.
  • the mechanism by which the change with time of the organic acid is suppressed is not clear, but the reaction of generating the organic acid from dissolved oxygen and inevitable impurities can be prevented, and the generation of a new organic acid is effective. It is estimated that the That is, this is an effect exhibited by adjusting not only the dissolved oxygen but also the organic acid to a specific range, and there has been no isopropyl alcohol composition that exhibits such an effect.
  • the isopropyl alcohol composition of the present disclosure includes a high-boiling compound as an impurity having a boiling point higher than that of isopropyl alcohol and having the carbon number of 4 or more excluding the organic acid in the production process ( Hereinafter, it is simply referred to as “high boiling point compound”).
  • a high-boiling compound as an impurity having a boiling point higher than that of isopropyl alcohol and having the carbon number of 4 or more excluding the organic acid in the production process
  • the high boiling point compound is contained in a large amount, when used as a cleaning liquid or a drying liquid for a semiconductor device, the high boiling point compound may remain or adhere to the surface of the semiconductor device, thereby reducing the yield of the semiconductor device. Therefore, it is preferable that the concentration of such a high boiling point compound is 20 ppb or less on a mass basis.
  • the concentration of the high boiling point compound is a value measured using a gas chromatography method as shown in Examples, and the detection lower limit of each high
  • High boiling compounds that may be present in the isopropyl alcohol composition of the present disclosure include 2-methyl-3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-hexanone, 3 , 3-dimethyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 2-methyl-3-pentanol, 3-hexanol, 4-methyl-2-pentanol, 3-methyl-2-pentanol, 2,2-dimethyl-1-butanol, 2-hexanol, 2-ethyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 1-hexanol, 4-methyl-1-pentanol, 1,2-propanediol, 2-methyl-2,4-pentanedi Lumpur, and the like.
  • the concentration of moisture as an impurity is preferably 20 ppm or less on a mass basis. Since the moisture contained in the isopropyl alcohol composition as well as the high boiling point compound may reduce the yield of the semiconductor device, the moisture concentration is preferably 20 ppm or less on a mass basis.
  • the isopropyl alcohol composition of the present disclosure has excellent storage stability because the dissolved oxygen concentration and the organic acid concentration are reduced. If the isopropyl alcohol composition of the present disclosure is filled in an airtight container and sealed with an inert gas (generally nitrogen gas), for example, even if it is left for 30 days, dissolved oxygen and organic acid change with time is extremely small.
  • an inert gas generally nitrogen gas
  • the isopropyl alcohol composition of the present disclosure is excellent in transportability and storage properties, and can be suitably used as a cleaning liquid or a drying liquid for semiconductor devices.
  • the method for producing isopropyl alcohol of the present disclosure is a method for producing isopropyl alcohol by directly hydrating water to propylene. As shown in FIG. It comprises a supply step, a reaction step, a recovery step, a first distillation step, and a second distillation step. Hereinafter, each step will be described in detail.
  • the raw materials used in the production method of the present disclosure are propylene and water.
  • propylene as a raw material is received in a recovery tank, mixed with propylene separated in the recovery process, and supplied to the reactor.
  • the raw material water is received in the recovery tank, and the water recovered in the second distillation step is mixed in the recovery tank and supplied to the reactor.
  • propylene having a purity of 95% by mass or more that is generally available as an industrial product can be used as propylene as a raw material.
  • unsaturated hydrocarbon compounds such as ethylene, butene, pentene, hexene and the like are contained in propylene, they undergo hydration reaction in the reaction step and become impurities. Therefore, it is preferable that the purity of propylene as a raw material is high.
  • the concentration of dissolved oxygen contained in the raw material propylene and water is not particularly limited. Even if dissolved oxygen was contained in the raw material propylene and water up to the saturated dissolved oxygen concentration at each temperature and pressure, as described later, it was provided below the supply stage of the distillation column in the first distillation step. This is because by supplying the inert gas from the inert gas supply nozzle, the dissolved oxygen is discharged out of the system, and the dissolved oxygen contained in the reaction product isopropyl alcohol is controlled to a low concentration.
  • an acid catalyst required in the reaction step is added in advance to the raw material water and supplied to the reactor.
  • the acid catalyst include acid catalysts of various polyanions such as a molybdenum-based inorganic ion exchanger and a tungsten-based inorganic ion exchanger.
  • An acid catalyst may be used individually by 1 type, and may use 2 or more types together.
  • these acid catalysts at least one selected from the group consisting of phosphotungstic acid, silicotungstic acid, and silicomolybdic acid is preferable from the viewpoint of reaction activity.
  • the amount of the acid catalyst added is adjusted so that the pH of the raw material water is 2.5 to 4.5 by checking the pH of the raw water with a pH meter.
  • the pH can be easily adjusted by adding an alkali such as sodium hydroxide.
  • pH can be easily adjusted by adding an acid catalyst.
  • an acid catalyst is added so that the pH of the raw material water is in the range of 2.5 to 4.5, it is optimal for obtaining a high selectivity to isopropyl alcohol while maintaining a high propylene conversion. It becomes possible to set it as reaction conditions, and it becomes reaction conditions with few production
  • reaction process The direct hydration reaction of propylene in the reaction step can be represented by the following formula.
  • the following reaction is performed in the reactor to obtain a reaction mixture.
  • the reaction pressure is preferably 150 to 250 atm and the reaction temperature is preferably 200 to 300 ° C.
  • the reaction conditions satisfy this range, the yield of industrial production and the durability of the acid catalyst tend to be compatible while suppressing the production of by-products.
  • water is preferably 1300 to 2100 parts by mass with respect to 100 parts by mass of propylene.
  • the amount of water relative to 100 parts by mass of propylene is more preferably 1500 to 2000 parts by mass.
  • the residence time of water in the reactor is more than 20 minutes and 50 minutes or less. It is preferable.
  • the staying time of water is more preferably 25 to 40 minutes, and further preferably 30 to 40 minutes.
  • the residence time of water in the present disclosure is a time defined by the following formula, and can be appropriately changed by changing the supply amount of water as a raw material and the volume of the reactor.
  • Water residence time (min) reactor volume (m 3 ) ⁇ water supply (m 3 / min)
  • the supply amount of water is calculated on the basis of the flow rate of water (110 ° C. in the examples described later) supplied into the reactor.
  • First distillation step In the first distillation step, distillation is performed for the purpose of removing low-boiling compounds having a boiling point lower than that of isopropyl alcohol from the reaction mixture containing isopropyl alcohol obtained in the recovery step and reducing dissolved oxygen. Perform the operation.
  • the manufacturing method according to the present disclosure is characterized in that, in the first distillation step, the oxygen partial pressure in the bottom gas phase part of the distillation column is controlled to 50 to 500 Pa.
  • the column bottom gas phase portion is a gas phase portion in equilibrium with the column bottom liquid of the distillation column, and refers to a gas phase portion from the column bottom liquid to the first stage shelf.
  • the bottom liquid of the distillation column in the first distillation step is a bottom liquid from which a low boiling point compound of 50 ° C. or less has been removed by distillation operation.
  • the oxygen partial pressure in the bottom gas phase exceeds 500 Pa, oxygen is taken into the bottom liquid, and dissolved oxygen is brought into the steps after the second distillation step. It tends to be difficult to reduce.
  • the oxygen partial pressure in the gas phase at the bottom of the column is less than 50 Pa, it is possible to reduce the oxygen taken into the bottom liquid, but it is inactive to reduce the oxygen partial pressure in the distillation column. A large amount of gas must be supplied. When a large amount of inert gas is supplied, the gas load of the distillation column in the first distillation step increases.
  • An increase in gas load leads to a decrease in the stable operation area of the distillation column and a decrease in the processing capacity of the condenser with the accumulation of inert gas in the condenser that cools the top gas. Since the capacity is reduced, it is not preferable from the viewpoint of economic efficiency.
  • the oxygen partial pressure in the bottom gas phase part of the distillation column is controlled to 50 to 500 Pa, dissolved oxygen in isopropyl alcohol can be reduced, but the oxygen partial pressure in the bottom gas phase part of the distillation column is set to 50. By controlling to ⁇ 200 Pa, dissolved oxygen can be further reduced.
  • an inert gas supply nozzle is provided below the supply stage of the distillation column, preferably at the bottom of the column.
  • An inert gas may be supplied to control the oxygen partial pressure in the tower bottom gas phase.
  • the inert gas is supplied from an inert gas supply nozzle provided at the bottom of the distillation column to 0.05 to 5 Nm 3 -inert gas / m 3 -liquid load, preferably 3 to 5 Nm 3-.
  • the partial pressure of oxygen in the bottom gas phase of the distillation column can be controlled to 50 to 500 Pa, preferably 50 to 200 Pa.
  • the inert gas is a gas other than oxygen that does not react with isopropyl alcohol and does not liquefy at the refrigerant temperature used in the condensing unit, and examples thereof include hydrogen, nitrogen, helium, and argon.
  • nitrogen, helium, and argon having low reactivity are preferable from the viewpoint of safety, and nitrogen is more preferable from the viewpoint of economy.
  • the liquid load in the distillation tower is the sum of the liquid volume (m 3 / hour) supplied to the distillation tower and the reflux liquid volume (m 3 / hour) refluxed to the top of the tower.
  • the amount of the supplied liquid and the amount of the reflux liquid vary depending on the production amount and the set reflux ratio of the distillation tower.
  • By controlling to be 3 -inert gas / m 3 -liquid load it becomes possible to control the oxygen partial pressure in the bottom gas phase of the distillation column to 50 to 500 Pa.
  • the oxygen partial pressure in the gas phase at the bottom of the column is calculated from the dissolved oxygen concentration by measuring the dissolved oxygen concentration in the column bottom liquid of the distillation column.
  • the dissolved oxygen concentration in the bottom liquid is proportional to the partial pressure in the gas phase, so as described above, the dissolved oxygen is converted to the partial pressure of oxygen in the gas phase in equilibrium with the liquid phase. it can.
  • the oxygen partial pressure measured by converting dissolved oxygen in the tower bottom liquid is the oxygen partial pressure in the tower bottom gas phase part.
  • the measurement result obtained by converting the dissolved oxygen concentration of the column bottom liquid into an oxygen partial pressure is 21 Pa
  • the oxygen partial pressure in the column bottom gas phase is 21 Pa.
  • the top of the distillation column has a condensing part that condenses gas and returns a part thereof to the distilling column, and a vent pipe is provided in the gas phase of the condensing part Is preferably used so that the linear velocity in the discharge direction of the vent pipe is 0.01 to 3.0 m / sec.
  • the vent pipe provided in the condensing part of the distillation tower. May be supplied with an inert gas so as to be 0.04 to 2.5 m / sec.
  • the condensing unit becomes negative pressure due to a disturbance such as a rapid temperature change of the refrigerant used in the condensing unit and a rapid increase in the amount of liquid supplied to the distillation column. Even when it becomes, it becomes possible to prevent the outside air containing oxygen from flowing back through the vent pipe. Thereby, oxygen contained in the outside air is not dissolved in the reaction mixture containing isopropyl alcohol, and an increase in the dissolved oxygen concentration of isopropyl alcohol can be prevented.
  • the condensing unit has a condenser provided at the top of the distillation tower for condensing the top gas and a reflux tank for receiving the condensed liquid.
  • Known condensation conditions can be used in the condensing section. Generally, if the condensation temperature in the condenser is about 5 ° C. lower than the top temperature of the distillation tower, It can be judged that it is fully condensed. For example, if the tower top temperature is 35 ° C., the condensation temperature may be set to 30 ° C. Since the reflux ratio hardly affects the dissolved oxygen concentration of isopropyl alcohol, the liquid composition of the reaction mixture containing isopropyl alcohol obtained in the distillation column may be set based on the target purity.
  • vent pipe is a degassing pipe for preventing a pressure rise inside the distillation tower provided at the top of the distillation tower, and is a pipe provided in the gas phase of the condensation section of the distillation tower.
  • the vent pipe connects the inside of the distillation tower and the outside air outside the distillation tower, and through the vent pipe, gases such as inert gas and low-boiling-point compounds staying at the top of the distillation tower are discharged out of the system.
  • the present inventors assume the following mechanism as the reason for controlling the oxygen partial pressure in the bottom gas phase of the distillation column.
  • the reaction mixture is extracted from the bottom of the column and supplied to the second distillation step.
  • the reaction mixture containing isopropyl alcohol is further purified. Therefore, in order to reduce the dissolved oxygen concentration in the reaction mixture obtained from the bottom of the distillation column in the first distillation step, the oxygen partial pressure in the bottom gas phase in equilibrium with the bottom liquid in the bottom is reduced. What is necessary is just to control to a specific range.
  • the oxygen partial pressure in the gas phase at the bottom of the column to a specific range, there is an operation of supplying an inert gas below the supply stage of the distillation column, preferably from the column bottom.
  • the supply of the inert gas is considered to replace the oxygen in the bottom gas phase with the supplied inert gas.
  • all of them can be achieved without substantially reducing the yield of the reaction mixture, reducing the capacity of the condensing unit, and increasing the gas load in the distillation column. Is considered possible.
  • the oxygen partial pressure in the gas phase at the bottom of the first distillation step in order to control the oxygen partial pressure in the gas phase at the bottom of the first distillation step to 50 to 500 Pa, it is inactive to parts other than those below the supply stage of the distillation tower, such as the top of the distillation tower and the condensation section.
  • it is possible to adjust the partial pressure of oxygen in the gas phase at the bottom of the column by supplying gas it is not preferable because it is separated from the bottom of the column and the efficiency of substitution with an inert gas is low.
  • the water recovered in the second distillation step has a low-boiling point compound having a lower boiling point than isopropyl alcohol removed in the first distillation step in the previous step, and can be suitably used as a raw material for isopropyl alcohol.
  • the recovered water is reintroduced into the water recovery tank in the raw material supply step and reacted with propylene, whereby isopropyl alcohol with reduced impurities can be produced.
  • the second distillation step it is preferable to control the oxygen partial pressure in the gas phase at the bottom of the distillation column, since the dissolved oxygen introduced into the product can be further reduced. Also in the second distillation step, dissolved oxygen can be reduced similarly to the first distillation step by controlling the oxygen partial pressure in the bottom gas phase part of the distillation column.
  • an inert gas may be supplied to the vent pipe as in the first distillation step. Also in the second distillation step, it is possible to suppress an increase in dissolved oxygen in the manufacturing process by adopting the same conditions as in the first distillation step.
  • the isopropyl alcohol with reduced impurities obtained in the second distillation step can be made into isopropyl alcohol with further reduced impurities as well as dissolved oxygen through a dehydration step and a purification step.
  • metals and inorganic particles may be removed by a filter process, or metal ions may be removed by an ion exchange resin tower.
  • a closed container such as a canister can
  • it can be stored more stably by carrying it out in an inert gas atmosphere such as nitrogen gas. Can be increased.
  • an inert gas such as nitrogen gas.
  • dissolved oxygen and organic acid are reduced in the production process.
  • Isopropyl alcohol can be stored in a state where the acid is reduced and the change with time is small.
  • the dissolved oxygen concentration of isopropyl alcohol and the partial pressure of oxygen in the gas phase at the bottom of the column are measured by ORBISPHERE 510 gas analyzer O 2 meter (trade name: sensor model 2952A DO2 measurement range 2ppb to 80 ppm, manufactured byhack Ultra, Inc. , PO2 measurement range 5 Pa to 200 kPa).
  • the measured value is displayed as an oxygen partial pressure converted from dissolved oxygen in the solution, as described above, the measured value of the column bottom liquid is the same as the measured value of the column bottom liquid.
  • the oxygen partial pressure of the part was adopted.
  • the dissolved oxygen concentration (%) of isopropyl alcohol was measured for the sampled isopropyl alcohol by measuring the partial pressure of oxygen corresponding to dissolved oxygen at 25 ° C. using the above apparatus, and the measurement result was 1 atm and 25 ° C.
  • ⁇ Measurement method of organic acid the organic acid contained in isopropyl alcohol was measured by the ion chromatography method under the following measurement conditions.
  • a compound used as the measuring object of organic acid a compound other than the compound corresponding to the retention time of formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid was not detected in both Examples and Comparative Examples. Therefore, formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid were quantified from the chart obtained by measurement.
  • acetone contained in isopropyl alcohol was measured by the gas chromatography method under the following measurement conditions.
  • Detector Mass spectrometer transfer line Temperature: 240 ° C
  • the high boiling point compound contained in isopropyl alcohol was measured by the gas chromatography method under the following measurement conditions.
  • concentration condition of the high-boiling compounds for example, distillation is performed for 24 hours with a precision distillation apparatus at a column top temperature of about 82 ° C.
  • the number of theoretical plates in the precision distillation apparatus is 2 to 30. If the number of plates is within this range, distillation and concentration can be performed.
  • Example 1 [Production of isopropyl alcohol]
  • propylene As a raw material propylene, what contained 39972 ppm propane, 20 ppm ethane, 8 ppm butene, 0.1 ppm or less pentene, and 0.1 ppm or less hexene as impurities was prepared.
  • water As raw material water, water whose pH was adjusted to 3.0 by adding phosphotungstic acid as an acid catalyst was prepared.
  • a reactor having an internal volume of 10 L is supplied with water heated to 110 ° C. at a supply amount of 18.4 kg / hour (20 L / hour because the density is 920 kg / m 3 ).
  • propylene was added at a supply rate of 1.2 kg / hour (raw material supply step).
  • the residence time of water in the reactor at this time is 30 minutes, and 1500 parts by mass of water is supplied to 100 parts by mass of propylene.
  • the reaction temperature in the reactor was 280 ° C.
  • the reaction pressure was 250 atm
  • propylene and water were reacted to obtain isopropyl alcohol (reaction step).
  • reaction product containing isopropyl alcohol generated in the reaction step is cooled to 140 ° C., and the pressure is reduced to 18 atm, whereby propylene dissolved in water contained in the reaction product is recovered as a gas (recovery). Process).
  • the recovered propylene was put into a propylene recovery tank for reuse as a raw material.
  • the conversion rate of the supplied propylene was 84.0%
  • the selectivity of propylene to isopropyl alcohol was 99.2%
  • the isopropyl alcohol concentration in the obtained reaction mixture was 7.8%.
  • the low boiling point compound which has a boiling point lower than the boiling point of isopropyl alcohol was removed from the reaction mixture after propylene collection
  • nitrogen was supplied from an inert gas supply nozzle provided at the bottom of the distillation column so that 4.0 Nm 3 -inert gas / m 3 -liquid load.
  • the dissolved oxygen concentration in the bottom liquid of the distillation tower was measured, and the partial pressure of oxygen in the gas phase at the bottom was calculated to be 56 Pa.
  • nitrogen, which is an inert gas was further supplied at a rate of 2.5 m / sec from a vent pipe provided in the condensing part of the distillation column.
  • the reaction mixture was extracted from the bottom of the distillation column and separated into water and isopropyl alcohol using the distillation column (second distillation step).
  • the water extracted from the bottom of the column and recovered was placed in a water recovery tank for reuse as a raw material under conditions of a temperature of 110 ° C. and a pressure of 1.5 atm. Further, phosphotungstic acid was added and adjusted so that the pH of the recovered water was maintained at 3.0.
  • isopropyl alcohol extracted from the top of the column contains about 12% of water, a distillation step for dehydration and a distillation step for purifying isopropyl alcohol were performed to obtain isopropyl alcohol.
  • the dissolved oxygen of the obtained isopropyl alcohol was measured according to the method described above. That is, the dissolved oxygen was measured at regular intervals using a dissolved oxygen meter, and the dissolved oxygen contained in the obtained isopropyl alcohol was quantified. The results are shown in Table 1. As shown in Table 1, the dissolved oxygen concentration of the obtained isopropyl alcohol was 0.02% with respect to the saturated solubility of dissolved oxygen.
  • Acetone contained in the obtained isopropyl alcohol was measured according to the method described above. The results are shown in Table 2. As shown in Table 2, acetone contained in isopropyl alcohol was 0.3 ppm.
  • Other high boiling point compounds include 3-methyl-2-pentanone, 2-hexanone, 3,3-dimethyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 2-methyl-3-pentanol, 3-hexanol, 3-methyl-2-pentanol, 2,2-dimethyl-1-butanol, 2-hexanol, 2-ethyl-1- Pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 1-hexanol, 4-methyl-1-pentanol, 1,2-propanediol, and 2-methyl-2,4- As a result of analyzing pentanediol, it was 20 ppb or less, which is the lower limit of detection.
  • the isopropyl alcohol of Example 1 obtained by the production method of the present disclosure, not only dissolved oxygen but also organic acids were reduced. Furthermore, the isopropyl alcohol of Example 1 was allowed to stand for 30 days in a nitrogen atmosphere that is an inert gas, and then the organic acid, acetone, and moisture were measured. The results are shown in Table 3 and FIG. As shown in Table 3 and FIG. 2, the isopropyl alcohol of Example 1 did not change the concentration of organic acid, acetone, and moisture even after being left for 30 days.
  • Example 2 In the first distillation step, nitrogen is supplied at a load of 0.1 Nm 3 -inert gas / m 3 -liquid from an inert gas supply nozzle provided at the bottom of the distillation column, and is supplied to the condensing part of the distillation column.
  • Isopropyl alcohol was produced in the same manner as in Example 1 except that nitrogen, which was an inert gas, was supplied at a rate of 0.04 m / sec from the provided air pipe.
  • the dissolved oxygen concentration of the column bottom liquid of the distillation column was measured, and the oxygen partial pressure of the column bottom gas phase was calculated, and was 300 Pa.
  • the dissolved oxygen of the obtained isopropyl alcohol was measured according to the method described above. That is, the dissolved oxygen was measured at regular intervals using a dissolved oxygen meter, and the dissolved oxygen contained in the obtained isopropyl alcohol was quantified. The results are shown in Table 1. As shown in Table 1, the dissolved oxygen concentration of the obtained isopropyl alcohol was 0.07% with respect to the saturated solubility of dissolved oxygen.
  • Acetone contained in the obtained isopropyl alcohol was measured according to the method described above. The results are shown in Table 2. As shown in Table 2, acetone contained in isopropyl alcohol was 0.2 ppm.
  • High boiling point compounds include 3-methyl-2-pentanone, 2-hexanone, 3,3-dimethyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3- Methyl-3-pentanol, 2-methyl-3-pentanol, 3-hexanol, 3-methyl-2-pentanol, 2,2-dimethyl-1-butanol, 2-hexanol, 2-ethyl-1-pentanol 2-methyl-1-pentanol, 3-methyl-1-pentanol, 1-hexanol, 4-methyl-1-pentanol, 1,2-propanediol, and 2-methyl-2,4-pentanediol As a result of the analysis, all were 20 ppb or less, which is the lower limit of detection.
  • the isopropyl alcohol of Example 2 obtained by the production method of the present disclosure, not only dissolved oxygen but also organic acids were reduced. Furthermore, the isopropyl alcohol of Example 2 was allowed to stand for 30 days in a nitrogen atmosphere that is an inert gas, and then the organic acid, acetone, and moisture were measured. The results are shown in Table 3 and FIG. As shown in Table 3 and FIG. 2, the isopropyl alcohol of Example 2 slightly increased the organic acid and acetone concentrations, but the organic acid did not exceed the target upper limit of 20 ppb even after being left for 30 days.
  • Example 3 In the first distillation step, isopropyl alcohol was produced in the same manner as in Example 2 except that the inert gas was not supplied from the vent pipe provided in the condensing part of the distillation column.
  • the dissolved oxygen concentration of the column bottom liquid of the distillation column was measured, and the oxygen partial pressure in the column bottom gas phase portion was calculated to be 480 Pa.
  • the dissolved oxygen of the obtained isopropyl alcohol was measured according to the method described above. That is, the dissolved oxygen was measured at regular intervals using a dissolved oxygen meter, and the dissolved oxygen contained in the obtained isopropyl alcohol was quantified. The results are shown in Table 1. As shown in Table 1, the dissolved oxygen concentration of the obtained isopropyl alcohol was 0.09% with respect to the saturated solubility of dissolved oxygen.
  • Acetone contained in the obtained isopropyl alcohol was measured according to the method described above. The results are shown in Table 2. As shown in Table 2, acetone contained in isopropyl alcohol was 0.3 ppm.
  • High boiling point compounds include 3-methyl-2-pentanone, 2-hexanone, 3,3-dimethyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3- Methyl-3-pentanol, 2-methyl-3-pentanol, 3-hexanol, 3-methyl-2-pentanol, 2,2-dimethyl-1-butanol, 2-hexanol, 2-ethyl-1-pentanol 2-methyl-1-pentanol, 3-methyl-1-pentanol, 1-hexanol, 4-methyl-1-pentanol, 1,2-propanediol, and 2-methyl-2,4-pentanediol As a result of the analysis, all were 20 ppb or less, which is the lower limit of detection.
  • the isopropyl alcohol of Example 2 obtained by the production method of the present disclosure, not only dissolved oxygen but also organic acids were reduced. Further, the isopropyl alcohol of Example 3 was allowed to stand for 30 days in a nitrogen atmosphere that is an inert gas, and then the organic acid, acetone, and moisture were measured. The results are shown in Table 3 and FIG. As shown in Table 3 and FIG. 2, the concentration of the organic acid and acetone of the isopropyl alcohol of Example 3 slightly increased, but the organic acid did not exceed the target upper limit of 20 ppb even after being left for 30 days.
  • Example 1 in the first distillation step, except that the inert gas nitrogen was not supplied from the inert gas supply nozzle provided at the bottom of the distillation column and the vent pipe provided at the condensing part of the distillation column. In the same manner, isopropyl alcohol was produced.
  • the dissolved oxygen concentration in the bottom liquid of the distillation tower was measured, and the oxygen partial pressure in the gas phase at the bottom was calculated.
  • the dissolved oxygen of the obtained isopropyl alcohol was measured according to the method described above. That is, the dissolved oxygen was measured at regular intervals using a dissolved oxygen meter, and the dissolved oxygen contained in the obtained isopropyl alcohol was quantified. The results are shown in Table 1. As shown in Table 1, the dissolved oxygen concentration of the obtained isopropyl alcohol was 0.13% with respect to the saturated solubility of dissolved oxygen.
  • Acetone contained in the obtained isopropyl alcohol was measured according to the method described above. The results are shown in Table 2. As shown in Table 2, acetone contained in isopropyl alcohol was 0.3 ppm.
  • High boiling point compounds include 3-methyl-2-pentanone, 2-hexanone, 3,3-dimethyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3- Methyl-3-pentanol, 2-methyl-3-pentanol, 3-hexanol, 3-methyl-2-pentanol, 2,2-dimethyl-1-butanol, 2-hexanol, 2-ethyl-1-pentanol 2-methyl-1-pentanol, 3-methyl-1-pentanol, 1-hexanol, 4-methyl-1-pentanol, 1,2-propanediol, and 2-methyl-2,4-pentanediol As a result of the analysis, all were 20 ppb or less, which is the lower limit of detection.

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Abstract

L'invention concerne une composition d'alcool isopropylique qui comprend de l'alcool isopropylique et une impureté, la composition ayant une concentration en oxygène dissous de 0,1 % ou moins par rapport à la solubilité de saturation de l'oxygène mesurée dans l'air à 25 °C et contenant un acide organique en tant qu'impureté dans une concentration de 20 ppb ou moins. L'invention concerne également un procédé de production d'alcool isopropylique dans lequel une telle composition d'alcool isopropylique peut être obtenue.
PCT/JP2018/000645 2017-01-23 2018-01-12 Composition d'alcool isopropylique et procédé de production d'alcool isopropylique WO2018135408A1 (fr)

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WO2020071481A1 (fr) * 2018-10-05 2020-04-09 株式会社トクヤマ Procédé de production d'alcool isopropylique
WO2021200936A1 (fr) * 2020-04-02 2021-10-07 株式会社トクヤマ Liquide de traitement de semi-conducteur et son procédé de fabrication
JP2023089921A (ja) * 2021-12-16 2023-06-28 サムス カンパニー リミテッド 薬液供給ユニットとこれを適用した基板処理システム及び薬液供給方法
WO2023176192A1 (fr) * 2022-03-16 2023-09-21 株式会社トクヤマ Liquide de nettoyage de semi-conducteur et procédé de production de liquide de nettoyage de semi-conducteur
KR20230142145A (ko) * 2022-04-01 2023-10-11 덕산약품공업주식회사 고순도 알코올의 제조방법
WO2024039022A1 (fr) * 2022-08-18 2024-02-22 주식회사 엘지화학 Procédé de préparation d'alcool isopropylique
JP7477730B1 (ja) 2022-06-03 2024-05-01 株式会社トクヤマ イソプロピルアルコール収容体及び該収容体の製造方法、並びにイソプロピルアルコール収容体の品質管理方法

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JPWO2020071307A1 (ja) * 2018-10-03 2021-02-15 株式会社トクヤマ 洗浄液及び高純度イソプロピルアルコールの製造方法
US11905499B2 (en) 2018-10-03 2024-02-20 Tokuyama Corporation High-purity isopropyl alcohol and method for manufacturing same
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JPWO2020071481A1 (ja) * 2018-10-05 2021-09-02 株式会社トクヤマ イソプロピルアルコールの製造方法
US11560346B2 (en) 2018-10-05 2023-01-24 Tokuyama Corporation Method for producing isopropyl alcohol
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KR102722548B1 (ko) * 2018-10-05 2024-10-29 가부시키가이샤 도쿠야마 이소프로필 알코올의 제조 방법
CN112771015A (zh) * 2018-10-05 2021-05-07 株式会社德山 异丙醇的制造方法
WO2020071481A1 (fr) * 2018-10-05 2020-04-09 株式会社トクヤマ Procédé de production d'alcool isopropylique
CN112771015B (zh) * 2018-10-05 2023-07-04 株式会社德山 异丙醇的制造方法
WO2021200936A1 (fr) * 2020-04-02 2021-10-07 株式会社トクヤマ Liquide de traitement de semi-conducteur et son procédé de fabrication
KR20220139401A (ko) * 2020-04-02 2022-10-14 가부시키가이샤 도쿠야마 반도체 처리액 및 그 제조 방법
KR102471394B1 (ko) 2020-04-02 2022-11-28 가부시키가이샤 도쿠야마 반도체 처리액 및 그 제조 방법
CN115335966B (zh) * 2020-04-02 2023-07-18 株式会社德山 半导体处理液及其制造方法
JP6980952B1 (ja) * 2020-04-02 2021-12-15 株式会社トクヤマ 半導体処理液及びその製造方法
CN115335966A (zh) * 2020-04-02 2022-11-11 株式会社德山 半导体处理液及其制造方法
JP7500672B2 (ja) 2021-12-16 2024-06-17 サムス カンパニー リミテッド 薬液供給ユニットとこれを適用した基板処理システム及び薬液供給方法
JP2023089921A (ja) * 2021-12-16 2023-06-28 サムス カンパニー リミテッド 薬液供給ユニットとこれを適用した基板処理システム及び薬液供給方法
JP7402385B1 (ja) * 2022-03-16 2023-12-20 株式会社トクヤマ 半導体洗浄液および半導体洗浄液の製造方法
WO2023176192A1 (fr) * 2022-03-16 2023-09-21 株式会社トクヤマ Liquide de nettoyage de semi-conducteur et procédé de production de liquide de nettoyage de semi-conducteur
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