WO2011052065A1 - テトラヒドロフランの精製方法及び精製システム - Google Patents
テトラヒドロフランの精製方法及び精製システム Download PDFInfo
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- WO2011052065A1 WO2011052065A1 PCT/JP2009/068663 JP2009068663W WO2011052065A1 WO 2011052065 A1 WO2011052065 A1 WO 2011052065A1 JP 2009068663 W JP2009068663 W JP 2009068663W WO 2011052065 A1 WO2011052065 A1 WO 2011052065A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
Definitions
- the present invention relates to a technique for purifying tetrahydrofuran from tetrahydrofuran and a liquid containing at least water, dihydrofuran and butanol as impurities.
- PBT polybutylene terephthalate
- 1,4-BDO 1,4-butanediol
- TA terephthalic acid
- the esterification reaction is a condensation reaction between the carboxyl group of dibasic acid and the OH group of glycol that occurs under an inert gas atmosphere such as normal pressure or weak negative pressure and nitrogen, and water is produced as a by-product. (Formula 1). Therefore, the reaction is promoted by devolatilizing and removing water. The reaction can also be accelerated by adding a polymerization catalyst such as titanium tetrabutoxide as necessary.
- the terminal glycol of one oligomer is eliminated between the oligomers produced by the esterification reaction in a reduced pressure environment and in the presence of a polymerization catalyst, and the carboxyl group of the oligomer is condensed with the terminal glycol of the other oligomer.
- This is an ester bond reaction (Formula 2).
- the reaction is promoted by removing it by devolatilization, and the degree of polymerization increases.
- a dibasic acid acid which is another raw material, acts as a catalyst with respect to the raw material glycol, and a dehydration reaction may occur to deteriorate the glycol.
- the glycol is ethylene glycol
- diethylene glycol is generated (formula 3)
- 1,4-BDO is formed
- THF tetrahydrofuran
- Non-Patent Document 1 describes a method for suppressing the production of THF in an esterification step with respect to the production of PBT.
- the formation of THF in the esterification process is promoted by the acid catalyst of TA, and the activation energy (32.1 kcal) for the side reaction is the same as that of the main reaction, that is, esterification reaction (30.5 kcal).
- esterification reaction 30.5 kcal
- it is effective to add a polymerization catalyst that promotes only the main reaction as a countermeasure it is described that the production of THF itself, that is, the reduction of the raw material yield is unavoidable.
- THF is produced as a by-product in the production of PBT.
- THF is polytetramethylene glycol (hereinafter referred to as a raw material for spandex and urethane elastomer) It is useful as a monomer raw material for PTMG), and if it can be recovered, it can be used as a valuable resource.
- a raw material for spandex and urethane elastomer polytetramethylene glycol
- 1,4-BDO 1,4-BDO
- Patent Document 1 describes a method for purifying THF in which a hydration reaction tower, a first distillation tower, a hydrogenation tower, a second distillation tower, and a third distillation tower are installed in series.
- a part of dihydrofuran hereinafter referred to as DHF
- DHF dihydrofuran
- the resin is converted to hydroxyfuran by a hydration reaction as a catalyst, and the vapor pressure is reduced (formulas 5 and 6).
- the aqueous solution passed through the hydration reaction tower is supplied to the first distillation tower and separated into a tower bottom liquid and a tower top liquid.
- hydrogen is added to DHF remaining in the presence of the catalyst supporting the noble metal in the hydrogenation tower and converted to THF (Equation 7).
- the liquid circulated through the hydrogenation tower is supplied to the second distillation tower.
- THF containing a large amount of water becomes the column top liquid
- the column bottom liquid containing THF and the water removed is supplied to the third distillation column.
- the THF recovery rate is improved by refluxing the top liquid of the second distillation column to the first distillation column.
- high-purity THF is recovered as a column top liquid, and waste liquid containing butanol is discharged from the column bottom liquid.
- the concentration of water difficult to separate from THF is reduced and the loss of THF is reduced by refluxing the top liquid of the second distillation column to the first distillation column.
- DHF in THF is reduced.
- an object of the present invention is to provide a method and a system for purifying THF from a liquid containing THF and impurities such as DHF, which has a small number of steps and does not require additional raw materials and / or equipment.
- the present inventors have intensively studied to solve the above problems.
- a part of the top liquid of the second distillation column is obtained.
- the high-purity THF with few impurities such as DHF can be purified at a high recovery rate without adding a hydration reaction or hydrogenation step
- the headline and the present invention were completed.
- the gist of the present invention is as follows.
- a method for purifying tetrahydrofuran from a liquid containing tetrahydrofuran and at least water, dihydrofuran and butanol as impurities A first distillation step of separating the liquid into a first tower bottom liquid containing water as a main component and a first tower top liquid containing tetrahydrofuran, dihydrofuran and butanol as main components by subjecting the liquid to a distillation treatment.
- Second distillation in which the first column top liquid is distilled by a distillation column and separated into a second column bottom liquid containing tetrahydrofuran and butanol as main components and a second column top liquid containing dihydrofuran as main components.
- a first distillation column having a raw material supply port, a column bottom liquid discharge port and a column top liquid discharge port, comprising a tetrahydrofuran supplied from the material supply port and a liquid containing at least water, dihydrofuran and butanol as impurities.
- the first column bottom liquid containing water as a main component and the first column top liquid containing tetrahydrofuran, dihydrofuran and butanol as main components are distilled, and the first column bottom liquid is The first distillation column discharged from the liquid outlet, and the first tower top liquid discharged from the top liquid outlet;
- a second distillation column having a raw material supply port, a column bottom liquid discharge port, and a column top liquid discharge port, wherein the first column top liquid supplied from the material supply port is subjected to distillation treatment to mainly produce tetrahydrofuran and butanol.
- the second tower bottom liquid containing as a component and the second tower top liquid containing dihydrofuran as a main component are separated, and the second tower bottom liquid is discharged from the outlet of the tower bottom liquid.
- the second distillation column for discharging the liquid from the outlet of the column top liquid;
- a third distillation column having a raw material supply port, a column bottom liquid discharge port, and a column top liquid discharge port, wherein the second column bottom liquid supplied from the material supply port is subjected to distillation treatment, and butanol as a main component
- the third column bottom liquid and the third column top liquid containing tetrahydrofuran as a main component are separated, and the third column bottom liquid is discharged from the column bottom liquid discharge port.
- the third distillation column discharged from the top liquid outlet; A flow path connecting the outlet of the top liquid of the first distillation column and the raw material supply port of the second distillation column; A flow path connecting the outlet of the bottom liquid of the second distillation column and the raw material supply port of the third distillation column; A reflux path that connects the outlet of the top liquid of the second distillation column and the upstream side of the first distillation column, and refluxs a part of the top liquid of the second distillation column to the first distillation column; A discharge path for discharging the remainder of the top liquid of the second distillation column out of the system from the outlet of the top liquid of the second distillation column; A system for purifying tetrahydrofuran.
- Tetrahydrofuran purification method the invention, a tetrahydrofuran (THF), least of water, from a liquid containing dihydrofuran (DHF) and butanol as impurities, to a method for purifying THF in high purity.
- DHF dihydrofuran
- THF tetrahydrofuran
- THF tetrahydrofuran
- THF is preferably in a concentration of 10 to 98%.
- concentration of water is preferably 1 to 90%
- DHF is preferably 10 to 5000 ppm
- butanol is preferably 0.1 to 2%.
- the purification method of the present invention is similarly applied to a liquid containing acetic acid, isopropanol, propanol, methyl ethyl ketone (MEK), 1-butyraldehyde (NBD) and the like as other impurities.
- MEK methyl ethyl ketone
- NBD 1-butyraldehyde
- acetic acid is preferably at a concentration of 0.01 to 0.5%
- isopropanol is preferably at a concentration of 1 to 100 ppm
- propanol is preferably at a concentration of 1 to 100 ppm
- MEK is 1 to 50 ppm.
- the concentration is preferably ppm
- NBD is preferably 1 to 30 ppm.
- the purification method of the present invention can purify THF with high purity from a liquid containing DHF or the like as an impurity. Therefore, it is discharged from the condensate or polycondensation process of by-products discharged from the esterification process of a polymerization plant using 1,4-butanediol as a raw material, such as a PBT or PBS (polybutylene succinate) polymerization plant.
- the purification method of the present invention can be applied to the by-product condensate. By applying the purification method of the present invention to the liquid as described above, it is possible to obtain high-purity THF as a valuable material from the effluent of the polymerization plant.
- the first distillation step is intended to roughly separate and remove water, which is a major impurity, by subjecting the above-described THF-containing liquid to a distillation treatment using a distillation column.
- the liquid containing THF described above is separated into a first tower bottom liquid containing water as a main component and a first tower top liquid containing tetrahydrofuran, dihydrofuran and butanol as main components. I can do it.
- This step includes a raw material supply port for supplying the above liquid, a column bottom liquid discharge port for discharging the first column bottom liquid, and a first column top liquid containing THF, DHF and butanol as main components.
- This can be carried out by using a distillation column equipped with a column top liquid outlet for discharging water.
- the distillation column used in this step preferably has 8 to 15 theoretical plates, and preferably has an operating pressure of 1 atm.
- the heating temperature at the bottom of the column is preferably 70 to 120 ° C.
- the first tower bottom liquid obtained in this step is supplied from the outlet of the distillation tower to the reboiler, reheated and then discharged out of the system.
- the first tower bottom liquid discharged out of the system contains impurities such as water and acetic acid as main components.
- the reheating temperature by the reboiler is preferably 80 to 120 ° C.
- the recovery rate of THF can be further improved by returning the steam obtained by reheating to the distillation column.
- the distilled steam is introduced into a condenser, and the steam is condensed to obtain the first tower top liquid.
- the total amount of the first top liquid obtained in this step may be used in the second distillation step described below, but in order to further improve the purity of THF, a part of the first top liquid is used. It is preferable to further include a step of returning to the distillation column.
- the flow rate ratio of the liquid supplied to the second distillation step and the liquid returned to the distillation column is preferably 1: 2 to 1: 4.
- the first column top liquid supplied to the second distillation step contains THF, DHF and butanol as main components.
- the first tower top liquid described above may be used as it is in the second distillation step, but in some cases, a hydrogenation step may be performed.
- the purpose of this step is to further improve the purity and recovery rate of THF by subjecting DHF or NBD contained as the main component of the first tower top liquid to a hydrogenation reaction.
- This step uses a hydrogen addition tower provided with a raw material supply port for supplying the first tower top liquid, a hydrogen gas supply port for supplying hydrogen gas, and a discharge port for discharging the liquid after the reaction.
- a hydrogen addition tower provided with a raw material supply port for supplying the first tower top liquid, a hydrogen gas supply port for supplying hydrogen gas, and a discharge port for discharging the liquid after the reaction.
- Examples of the hydrogenation tower used in this step include a packed tower in which a noble metal such as ruthenium, palladium, or platinum is supported on graphite.
- NBD is contained as an impurity
- at least a part thereof is hydrogenated by a catalytic reduction reaction, and is converted into butanol that can be easily separated in a third distillation step described below.
- the concentration of NBD contained in the condensate is usually not high. Therefore, sufficient THF purity can be achieved without carrying out this step.
- the internal temperature of the hydrogenation tower used in this step is preferably 80 to 120 ° C., and the hydrogen gas partial pressure is preferably 1 atm.
- the residence time of the first column top liquid in the column is preferably 0.25 to 1 hour.
- the second distillation step is intended to separate and remove DHF by distilling the first column top liquid or the liquid after the hydrogenation reaction with a distillation column.
- the first tower top liquid or the liquid after the hydrogenation reaction is separated into a second tower bottom liquid containing THF and butanol as main components and a second tower top liquid containing DHF as main components. I can do it.
- This step consists of a raw material supply port for supplying the first tower top liquid, a tower bottom liquid outlet for discharging the second tower bottom liquid containing THF and butanol as main components, and DHF as the main component. It can implement by using the distillation column provided with the discharge port of the tower top liquid for discharging
- the distillation column used in this step preferably has 12 to 16 theoretical plates, and preferably has an operating pressure of 8 to 9 atmospheres.
- the heating temperature at the bottom of the column is preferably 120 to 180 ° C.
- the second column bottom liquid obtained in this step is supplied from the outlet of the distillation column to the reboiler, reheated, and then supplied to the third distillation step as the second column bottom liquid.
- the second column bottom liquid supplied to the third distillation step contains THF and butanol as main components.
- the reheating temperature by the reboiler is preferably 120 to 180 ° C.
- the distilled steam is introduced into a condenser, and the steam is condensed to obtain a second tower top liquid.
- the total amount of the second top liquid obtained in this step may be used in the reflux step described below, but in order to further improve the recovery of THF, a part of the second top liquid is distilled. It is preferable to further include a step of returning to the tower.
- the flow ratio of the liquid supplied to the reflux process and the liquid returned to the distillation column is preferably 1: 0.1 to 1: 0.6.
- the second tower top liquid supplied to the reflux step contains DHF as a main component, and further contains water azeotroped with DHF.
- the refluxing step a part of the second column top liquid separated in the second distillation step is refluxed to the first distillation step as a refluxing solution, and the remainder is discharged out of the system.
- the purpose is to further improve the separation and removal efficiency of DHF and water, which are impurities contained in.
- Patent Document 1 discloses a hydration reaction column, a first distillation column, a hydrogenation column, a second distillation column, and a third distillation column in series. Describes the purification method of THF installed in According to this document, by performing distillation at a pressure higher than atmospheric pressure in the second distillation column, the water content in the column bottom liquid can be reduced, and the column top liquid is refluxed to the first distillation column. By doing so, water can be further separated and removed.
- Patent Document 1 it is planned to remove DHF by a hydrogenation reaction in a hydrogenation tower, and it is assumed that DHF is contained in the liquid supplied to the second distillation tower. Absent. Therefore, Patent Document 1 does not describe separation and removal of DHF.
- the present inventors have completely removed DHF from the second column bottom liquid by carrying out the refluxing step described in this section without performing the hydrogenation step as an essential step. It was found that it can be transferred to the top liquid. That is, by refluxing a part of the second tower top liquid as a reflux liquid to the first distillation step, water contained in the tower top liquid is removed as a component of the first tower bottom liquid after reflux, DHF is again fed to the second distillation step as a component of the first top liquid after reflux. Therefore, DHF is concentrated in the second column top liquid by carrying out the reflux step.
- the present inventors do not reflux the entire amount of the second column top liquid to the first distillation step, but partially use it as the reflux liquid for the first distillation step. It was found that DHF can be separated and removed by refluxing and discharging the remainder as a discharge liquid.
- the second column top liquid contains THF to be separated as a main component of the second column bottom liquid. For this reason, if the flow rate of the effluent discharged outside the system is increased in the reflux step, the separation efficiency of DHF is improved, but the THF discharged at the same time also increases. As a result, the recovery rate of THF decreases and the economic efficiency of the purification method of the present invention deteriorates.
- the flow rate ratio of the reflux liquid to the first distillation step and the discharged liquid to the outside of the system is an important factor that defines the recovery rate and purity of THF in the purification method of the present invention. Therefore, in this step, the flow rate ratio of the reflux liquid to the first distillation step and the discharged liquid to the outside of the system is preferably in the range of 5: 1 to 20: 1.
- the above flow ratio is the flow rate of the reflux liquid to the first distillation step and the discharge liquid to the outside of the system by combining a flow rate measuring means such as a flow meter or an anemometer and a flow rate adjusting means such as a flow rate control valve. Can be adjusted by appropriately setting.
- Third distillation step is intended to separate the second column bottom liquid with a distillation column to separate the target THF.
- the second tower bottom liquid is mainly composed of a third tower bottom liquid mainly containing impurities such as butanol, acetic acid, isopropanol, propanol, methyl ethyl ketone (MEK), 1-butyraldehyde (NBD), and THF. It can isolate
- This step is a raw material supply port for supplying the second column bottom liquid, a column bottom solution discharge port for discharging the third column bottom liquid containing impurities such as butanol as main components, and a target product. It can be carried out by using a distillation column having a column top liquid outlet for discharging a third column top liquid containing THF as a main component.
- the distillation column used in this step preferably has a theoretical plate number of 15 to 25 plates, and preferably has an operating pressure of 1 atm.
- the heating temperature at the bottom of the column is preferably 60 to 90 ° C.
- the third tower bottom liquid obtained in this step is supplied to the reboiler from the outlet of the distillation tower, reheated and then discharged out of the system as the third tower bottom liquid.
- the third column bottom liquid discharged out of the system contains impurities such as butanol, acetic acid, isopropanol, propanol, MEK, and NBD as main components.
- the reheating temperature by the reboiler is preferably 60 to 75 ° C.
- the distilled steam is introduced into a condenser, and the steam is condensed to obtain a third tower top liquid.
- the total amount of the third tower top liquid obtained in this step may be discharged out of the system as it is as high-purity THF.However, in order to further improve the purity of THF, a part of the third tower top liquid is added to the third tower top liquid. It is preferable to further include a step of returning to the distillation column.
- the flow ratio of the liquid discharged out of the system and the liquid returned to the distillation column is preferably 1: 0.3 to 1: 1.
- the liquid discharged out of the system is the target high-purity THF.
- the purification method of the present invention can obtain the target THF from a liquid containing at least water, DHF and butanol as impurities without reducing the recovery rate and purity of THF. Therefore, the purification method of the present invention makes it possible to obtain high-purity THF with a small number of steps.
- Tetrahydrofuran purification system The present invention further relates to a purification system for purifying THF in high purity from THF and liquids containing at least water, DHF and butanol as impurities.
- the THF purification system of the present invention will be described below with reference to the accompanying drawings, but the purification system of the present invention is not limited thereto.
- the basic embodiment of the THF purification system of the present invention shown in FIG. 1 is a first distillation column 107 having a raw material supply port 135, a column bottom liquid discharge port 136, and a column top liquid discharge port 137.
- the THF supplied from the raw material supply port 135 and the liquid containing at least water, DHF and butanol as impurities are subjected to distillation treatment, and the first tower bottom liquid containing water as the main component, and THF, DHF and butanol are mainly used.
- the first column top liquid is separated from the first column top liquid contained as a component, the first column bottom liquid is discharged from the column bottom liquid discharge port 136, and the first column top liquid is discharged from the column top liquid discharge port 137.
- a distillation column 107 having a raw material supply port 138, a column bottom liquid discharge port 139 and a column top liquid discharge port 140, wherein the first column top liquid supplied from the raw material supply port 138 is subjected to distillation treatment, Separated into a second tower bottom liquid containing THF and butanol as main components and a second tower top liquid containing DHF as main components, and the second tower bottom liquid was discharged from the bottom liquid outlet 139.
- the second distillation column 108 for discharging the second column top liquid from the column top liquid discharge port 140;
- a third distillation column 109 having a raw material supply port 141, a column bottom liquid discharge port 142, and a column top liquid discharge port 143, wherein the second column bottom liquid supplied from the raw material supply port 141 is subjected to distillation treatment,
- the third tower bottom liquid containing butanol as a main component and the third tower top liquid containing THF as a main ingredient are separated, and the third tower bottom liquid is discharged from the bottom liquid outlet 142,
- the third distillation column 109 for discharging the three-column top liquid from the column-top liquid outlet 143;
- a flow path 116 connecting the outlet 137 of the top liquid of the first distillation column 107 and the raw material supply port 138 of the second distillation column 108;
- a flow path 121 connecting the outlet 139 of the bottom liquid of the second distillation column 108 and the raw material supply port 141 of the third distillation column
- each flow path and the discharge path are not necessarily formed by a single flow path member, and a plurality of flow path members may be arranged in series or in parallel to form a flow path, Further, other devices such as a liquid feed pump, a reboiler, a condenser, a hydrogenation tower, etc., described below, may be interposed in the flow path.
- Arbitrary members, such as piping, are used as said channel member.
- the liquid supplied from the raw material supply port 135 of the first distillation column 107 preferably has the same composition as the liquid described in 1-1.
- Such liquid is usually discharged as a by-product condensate from the esterification process or the condensation polymerization process of the PBT polymerization plant. Therefore, it is preferable that the purification system of the present invention is disposed on the downstream side of a polyester plant 101 using 1,4-butanediol as a raw material, such as a PBT or PBS polymerization plant.
- the storage tank 104 is disposed on the downstream side of the plant 101, and the liquid discharged from the plant 101 is supplied to the storage tank 104 via the flow path.
- a transport mechanism such as a liquid feed pump 103 may be disposed in the channel 102 as necessary.
- the liquid containing THF and at least water, DHF and butanol as impurities is supplied from the storage tank 104 to the raw material supply port 135 of the first distillation column 107 through the flow path 105.
- a transport mechanism such as a liquid feed pump 106 may be disposed in the channel 105 as necessary.
- the first column bottom liquid containing water as a main component and the first column top liquid containing THF, DHF and butanol as main components are separated.
- the first distillation column 107 preferably has 8 to 15 theoretical plates, and preferably has an operating pressure of 1 atm.
- the heating temperature at the bottom of the column is preferably 90 to 120 ° C.
- the first column bottom liquid discharged from the discharge port 136 of the first distillation column 107 is supplied to the reboiler 110.
- the steam generated by reheating the first column bottom liquid is returned to the first distillation column 107 via the flow path 111, and the reheated first column bottom liquid is returned via the discharge path 112.
- Discharge out of the system includes a flow path member extending from the discharge port 136 to the reboiler 110, a reboiler 110, and a flow path member extending from the reboiler 110 to the outside of the system.
- a transport mechanism such as a liquid feed pump 113 may be disposed in the discharge path 112 as necessary.
- the reheating temperature by the reboiler 110 is preferably 80 to 120 ° C.
- the discharged first tower bottom liquid contains water as a main component.
- the vapor distilled from the discharge port 137 is introduced into the condenser 114, and the vapor is condensed to obtain the first column top liquid.
- the total amount of the first tower top liquid obtained in this step may be supplied to the second distillation tower 108 via the flow path 116, but in order to further improve the purity of the THF, the flow through the flow path 115.
- a part of the first column top liquid is preferably returned to the first distillation column 107.
- the flow rate ratio of the liquid supplied to the second distillation column 108 via the flow path 116 and the liquid returned to the distillation tower via the flow path 115 is 1: 2 to 1: 4. Preferably there is.
- the flow path 116 includes a flow path member extending from the discharge port 137 to the condenser 114, a condenser 114, and a flow path member extending from the condenser 114 to the raw material supply port 138 of the second distillation column 108.
- a transport mechanism such as a liquid feed pump 117 may be disposed in the flow path 116 as necessary.
- the first column top liquid supplied to the second distillation column 108 via the flow path 116 contains THF, DHF and butanol as main components.
- the first column top liquid is supplied to the raw material supply port 138 of the second distillation column 108 via the flow path 116.
- the second distillation column 108 separates into a second column bottom liquid containing THF and butanol as main components and a second column top liquid containing DHF as main components.
- the second distillation column 108 preferably has 12 to 16 theoretical plates, and preferably has an operating pressure of 8 to 9 atmospheres.
- the heating temperature at the bottom of the column is preferably 130 to 170 ° C.
- the second column bottom liquid discharged from the discharge port 139 of the second distillation column 108 is supplied to the reboiler 119.
- the steam generated by reheating the second column bottom liquid is returned to the second distillation column 108 via the flow path 120, and the reheated second column bottom liquid is returned via the flow path 121.
- the flow path 121 includes a flow path member extending from the discharge port 139 to the reboiler 119, a reboiler 119, and a flow path member extending from the reboiler 119 to the raw material supply port 141 of the third distillation column 109.
- a transport mechanism such as a liquid feed pump 122 may be disposed in the flow path 121 as necessary.
- the reheating temperature by the reboiler 119 is preferably 120 to 180 ° C.
- the second column bottom liquid supplied to the third distillation column 109 via the channel 121 contains THF and butanol as main components.
- the vapor distilled from the discharge port 140 is introduced into the condenser 123, and the vapor is condensed to obtain the second column top liquid.
- the total amount of the second column top liquid obtained in this step may be supplied to the reflux channel 151 and the discharge channel 153, but in order to further improve the recovery rate of THF, the second column is passed through the channel 124. It is preferable to return a part of the top liquid to the second distillation column 108.
- the flow ratio of the liquid supplied to the reflux path 151 and the discharge path 153 and the liquid returned to the distillation column via the flow path 124 is preferably 1: ⁇ ⁇ 0.1 to 1: 0.6. .
- the second column top liquid supplied to the reflux path 151 and the discharge path 153 contains DHF as a main component.
- the second column top liquid may be directly supplied to the reflux path and the discharge path from the second column top liquid discharge port, and is connected to the second column top liquid discharge port 140 at one end as shown in FIG.
- the other end may be supplied to the reflux path 151 and the discharge path 153 from the second tower top liquid discharge port 140 via the flow path 125 branched to the reflux path 151 and the discharge path 153.
- the flow path 125 includes a flow path member extending from the discharge port 140 to the condenser 123, a condenser 123, and a flow path member extending from the condenser 123 to the reflux path 151 and the discharge path 153. Is done.
- a transport mechanism such as a liquid feed pump 126 may be arranged in the flow path 125 as necessary.
- the second tower top liquid contains DHF as a main component, and also contains water azeotroped with DHF.
- a part of the second column top liquid is supplied to the raw material supply port 135 of the first distillation column 107 via the reflux path 151.
- the liquid supplied via the reflux path 151 and the liquid supplied via the flow path 105 are mixed by a mixing means such as a static mixer 152 as necessary, and then mixed into the raw material supply port 135 of the first distillation column 107. You may supply.
- the second column top liquid containing DHF as a main component supplied via the reflux path 151 is again distilled in the first distillation column 107.
- the first top liquid after reflux containing DHF as the main component is supplied again to the raw material supply port 138 of the second distillation column 108 via the flow path 116, and after reflux containing water as the main component.
- the first tower bottom liquid is discharged out of the system via the discharge path 112.
- the remainder of the second column top liquid is discharged out of the system via the discharge path 153.
- the amount of DHF contained in the liquid supplied via the reflux path 151 can be reduced, and as a result, the amount of DHF contained in the bottom liquid of the second distillation column 108 can be reduced. Therefore, it is possible to improve the purity of THF obtained in the third distillation column 109 described below.
- a means for adjusting the flow rate ratio of the reflux path 151 and the discharge path 153 is disposed on the downstream side of the second distillation column 108.
- Examples of such means include a combination of flow rate measuring means such as flow meters 155 and 157 and flow rate adjusting means such as flow rate control valves 154 and 156.
- the flow rate measuring means and the flow rate adjusting means may be arranged as separate parts as shown in FIG. 1, or may be arranged as a single part having both functions.
- the flow rate measuring means and the flow rate adjusting means may be arranged on the downstream side of the second distillation column 108, and may be arranged in each of the reflux path 151 and the discharge path 153 as shown in FIG. It may be arranged in one of the path 151 and the discharge path 153.
- the second column bottom liquid is supplied to the raw material supply port 141 of the third distillation column 109 via the channel 121.
- the second bottom liquid is separated into a third bottom liquid containing butanol as a main component and a third top liquid containing THF as a main component.
- the third distillation column 109 preferably has 15 to 25 theoretical plates, and preferably has an operating pressure of 1 atm.
- the heating temperature at the bottom of the column is preferably 60 to 90 ° C.
- the third column bottom liquid discharged from the discharge port 142 of the third distillation column 109 is supplied to the reboiler 127.
- the steam generated by reheating the third column bottom liquid is returned to the third distillation column 109 via the flow path 128, and the reheated third column bottom liquid is returned via the discharge path 129.
- the discharge path 129 includes a flow path member from the discharge port 142 to the reboiler 127, a reboiler 127, and a flow path member from the reboiler 127 to the outside of the system.
- a transport mechanism such as a liquid feed pump 130 may be disposed in the discharge path 129 as necessary.
- the reheating temperature by the reboiler 127 is preferably 60 to 75 ° C.
- the column bottom liquid discharged out of the system through the discharge path 129 contains butanol as a main component.
- the steam distilled from the discharge port 143 is introduced into the condenser 131, and the steam is condensed to obtain the third tower top liquid.
- the total amount of the third tower top liquid obtained in this step may be supplied to the discharge path 133, but in order to further improve the purity of THF, a part of the third tower top liquid is passed through the channel 132. Is preferably returned to the third distillation column 109.
- the flow rate ratio between the flow rate of the liquid supplied to the discharge path 133 and the liquid returned to the distillation column via the flow path 132 is preferably 1: 0.3 to 1: 1.
- the discharge path 133 includes a flow path member extending from the discharge port 143 to the condenser 131, a condenser 131, and a flow path member extending from the condenser 131 to the outside of the system.
- a transport mechanism such as a liquid feed pump 134 may be disposed in the discharge path 133 as necessary.
- the third column top liquid discharged from the discharge path 133 is high-purity THF which is a target product.
- the purification system of the embodiment shown in FIG. 1 can obtain the target THF from a liquid containing at least water, DHF and butanol as impurities without reducing the recovery rate and purity of THF. Since the purification system has a small number of steps and does not require additional raw materials and equipment, high-purity THF can be obtained without increasing manufacturing costs and equipment costs.
- FIG. 2 is the same as the purification system shown in FIG. 1 except that a hydrogenation column 261 is further disposed between the top liquid outlet of the first distillation column and the raw material supply port of the second distillation column. It has the composition of.
- a raw material supply port and a hydrogen gas supply port for supplying hydrogen gas are provided in the middle of the flow path connecting the outlet of the top liquid of the first distillation column and the raw material supply port of the second distillation column.
- a hydrogenation tower 261 having a discharge port for discharging the liquid after the reaction.
- the first column top liquid containing THF, DHF and butanol as main components is a flow path member extending from the outlet 137 to the condenser 114, the condenser 114, and the raw material of the hydrogenation tower 261 from the condenser 114. It is supplied to the raw material supply port of the hydrogenation tower 261 via a flow path member that reaches the supply port.
- the hydrogenation tower 261 is preferably a packed tower in which a noble metal such as ruthenium, palladium, or platinum is supported on graphite.
- a hydrogen gas supply port of the hydrogenation tower 261 is connected to a tank 263 filled with hydrogen gas via a pipe 262, and hydrogen gas is supplied from the tank 263 to the hydrogenation tower 261.
- the supplied hydrogen gas partial pressure is adjusted to a suitable partial pressure by a flow rate adjusting means such as a regulator 264 disposed between the hydrogen addition tower 261 and the tank 263. Further, the hydrogenation tower 261 is provided with a heater, and the inside of the hydrogenation tower is maintained at a suitable temperature. Thereby, inside the hydrogenation tower 261, at least a part of DHF contained in the top liquid of the first distillation tower 107 is hydrogenated by a catalytic reduction reaction and converted to THF. Further, when NBD is contained as an impurity, at least a part thereof is hydrogenated by a catalytic reduction reaction and converted into butanol that can be easily separated in the third distillation column 109.
- a flow rate adjusting means such as a regulator 264 disposed between the hydrogen addition tower 261 and the tank 263.
- the hydrogenation tower 261 is provided with a heater, and the inside of the hydrogenation tower is maintained at a suitable temperature.
- NBD is contained as an impurity
- at least a part thereof is
- the internal temperature of the hydrogenation tower 261 is preferably 80 to 120 ° C., and the hydrogen gas partial pressure is preferably 1 atm. Further, the residence time of the top liquid of the first distillation column 107 in the column is preferably 0.25 to 1 hour.
- the purification system of the embodiment shown in FIG. 2 can increase the total amount of THF by converting DHF contained as impurities into THF, and as a result, the recovery rate of THF can be improved. Moreover, when applying with respect to the liquid which contains NBD as an impurity, it becomes possible to improve the purity of THF by converting difficult NBD into butanol which is easy to separate.
- the THF purification system used in this example is a first distillation column having a raw material supply port, a column bottom liquid discharge port, and a column top liquid discharge port. And a condensate of a by-product of a PBT polymerization plant containing butanol, and a first tower bottom liquid containing water as a main component and a first tower top containing THF, DHF and butanol as main components.
- the first distillation column the first column bottom liquid is discharged from the column bottom liquid discharge port, the first column top liquid is discharged from the column top liquid discharge port, the raw material supply port, the column A second distillation column having a bottom liquid discharge port and a column top liquid discharge port, wherein the first column top liquid supplied from the raw material supply port is subjected to distillation treatment, and contains THF and butanol as main components.
- the second tower bottom liquid is discharged from the bottom liquid outlet.
- a second distillation column provided with the second distillation column for discharging the second column top liquid from the column top liquid discharge port, a raw material supply port, a column bottom liquid discharge port, and a column top liquid discharge port.
- the second column bottom liquid supplied from the raw material supply port is subjected to distillation treatment to be separated into a third column bottom liquid containing butanol as a main component and a third column top liquid containing THF as a main component.
- the third distillation column for discharging the third column bottom liquid from the column bottom liquid discharge port and discharging the third column top liquid from the column top liquid discharge port is arranged in series, and further the second distillation A reflux path for connecting a column top liquid outlet and an upstream side of the first distillation column to reflux a part of the top liquid of the second distillation column to the first distillation column; and a column of the second distillation column And a discharge path for discharging the remainder of the top liquid of the second distillation column from the top liquid discharge port to the outside of the system.
- the by-product condensate was supplied from the PBT polymerization plant 101 to the by-product condensate tank 104 by the liquid feed pump 103 via the flow path 102.
- the condensate contained 68% water, 30.83% THF, 0.82% butanol, 0.22% acetic acid, 1200 ppm DHF, 35 ppm isopropanol, 10 ppm NBD, 10 ppm MEK.
- the temperature was maintained at a temperature equal to or higher than the melting point of 1,4-BDO (20 to 25 ° C.) as necessary.
- the by-product condensate 1995 part was supplied to the first distillation column 107 by the feed pump 106 via the flow path 105. Further, 298 parts of the top liquid of the second distillation column 108 was refluxed to the first distillation column 107 via the reflux path 151 from the second distillation column 108 described below. After the reflux liquid and the by-product condensate were mixed using a static mixer 152, the mixed liquid was supplied to the first distillation column 107.
- the first distillation column 107 had 15 theoretical plates, a column bottom temperature of 100 ° C., an operating pressure of 1 atm, and a column top liquid reflux ratio of 2.9.
- the bottom liquid of the first distillation column 107 contains 99.06% water, 0.56% butanol, 0.38% acetic acid, and 0.01% THF as high boiling components. 1368 parts were discharged out of the system by the pump 113.
- the top liquid of the first distillation column 107 contains 94.5% THF, 2.32% DHF, 0.92% butanol, 0.01% isopropanol, 20 ⁇ ppm NBD, and 20 ppm MEK.
- a liquid feed pump 117 by a liquid feed pump 117 via a flow path member consisting of a flow path member extending from 137 to the condenser 114, a condenser 114, and a flow path member extending from the condenser 114 to the raw material supply port of the hydrogenation tower 261. The portion was discharged and supplied to the hydrogenation tower 261.
- the hydrogenation tower 261 is a packed tower of a pellet-shaped catalyst in which 2% of metal ruthenium is supported on graphite, the tower bottom temperature is 100 ° C., the operation pressure is 9.5 atm, and the residence time is 0.5 hours. Hydrogen gas was adjusted to the above operating pressure from the tank 263 by the regulator 264 and supplied to the hydrogenation tower 261 via the pipe 262. The solution supplied to the hydrogenation tower 261 was brought into contact with hydrogen gas in the tower. Thereby, a part of DHF was reduced to THF.
- the hydrogenation tower 261 can be omitted if necessary. Hereinafter, a case where the hydrogenation tower 261 is omitted will be described.
- the second distillation column 108 had 14 theoretical plates, a column bottom temperature of 150 ° C., an operating pressure of 8.4 atm, and a reflux ratio of the column top liquid of 0.3.
- the bottom liquid of the second distillation column 108 is 98.54% THF, 1.41% butanol, 0.04% DHF, 0.01% isopropanol, 0.01% acetic acid, 50 ⁇ ppm water, 10 ppm MEK, It contains 10 ppm, and passes through a flow path member 121 from the discharge port 139 to the reboiler 119, a reboiler 119, and a flow path member from the reboiler 119 to the raw material supply port 141 of the third distillation column 108.
- the flow path 125 includes a flow path member extending from the discharge port 140 to the condenser 123, a condenser 123, and a flow path member extending from the condenser 123 to the branch points of the reflux path 151 and the discharge path 153.
- the discharged top liquid was allowed to flow into the reflux path 151 and the discharge path 153 via the flow path 125.
- Flow control valves 154 and 156 and flow meters 155 and 157 are installed in the reflux path 151 and the discharge path 153. By operating the flow control valves 154 and 156, 298 parts of the return path 151 and the discharge path 153 The flow rate ratio was adjusted so that 26 parts flowed.
- the liquid flowing through the reflux path 151 was refluxed to the first distillation column 107. Further, the liquid flowing through the discharge path 153 was discharged out of the system as a discharged liquid. Accordingly, the flow rate ratio between the reflux liquid and the discharged liquid to the outside at this time was 11.46.
- the third distillation column 109 had 19 theoretical plates, a column bottom temperature of 67 ° C., an operating pressure of 1 atm, and a reflux ratio of the column top liquid of 0.6.
- the bottom liquid of the third distillation column 109 contains 97.85% butanol, 0.8% THF, 0.64% isopropanol, 0.36% acetic acid, 0.02% water, 0.11% MEK, 0.11% NBD as high boiling components.
- the top liquid of the third distillation column 109 contains 99.96% THF and 0.04% DHF, a flow path member extending from the outlet 143 to the condenser 131, the condenser 131, and the condenser 131. 593 parts were discharged by the liquid feed pump 134 via a discharge path 133 consisting of a flow path member extending from to the outside of the system.
- the top liquid of the third distillation column 109 is the high-purity THF of the final product in this example.
- the purity of THF recovered in this example was 99.96%, and the recovery rate was 96.4%. This was the result of achieving a target purity of 99.9% or higher and a target recovery rate of 90% or higher.
- the THF purification system of the present invention from the condensate of the by-product containing THF, which is generated in the polymerization plant of PBT, from a condensate of high purity with few processes and reasonable equipment. It becomes possible to purify THF with a high recovery rate.
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Abstract
Description
該液体を蒸留塔によって蒸留処理し、水を主成分として含有する第一塔底液と、テトラヒドロフラン、ジヒドロフラン及びブタノールを主成分として含有する第一塔頂液とに分離する第一の蒸留工程と、
第一塔頂液を蒸留塔によって蒸留処理し、テトラヒドロフラン及びブタノールを主成分として含有する第二塔底液と、ジヒドロフランを主成分として含有する第二塔頂液とに分離する第二の蒸留工程と、
第二塔底液を蒸留塔によって蒸留処理し、ブタノールを主成分として含有する第三塔底液と、テトラヒドロフランを主成分として含有する第三塔頂液とに分離する第三の蒸留工程とを含み、
第二塔頂液の一部を還流液として第一の蒸留工程に還流させ、残部を系外に排出する還流工程をさらに含むことを特徴とする、テトラヒドロフランの精製方法。
第一塔頂液に含有されるジヒドロフランを水素添加してテトラヒドロフランに変換する水素添加工程をさらに含む、前記(1)又は(2)の精製方法。
原料供給口、塔底液の排出口及び塔頂液の排出口を備える第一蒸留塔であって、原料供給口から供給されるテトラヒドロフラン並びに不純物として少なくとも水、ジヒドロフラン及びブタノールを含有する液体を蒸留処理して、水を主成分として含有する第一塔底液と、テトラヒドロフラン、ジヒドロフラン及びブタノールを主成分として含有する第一塔頂液とに分離して、第一塔底液を塔底液の排出口から排出し、第一塔頂液を塔頂液の排出口から排出する前記第一蒸留塔と、
原料供給口、塔底液の排出口及び塔頂液の排出口を備える第二蒸留塔であって、原料供給口から供給される第一塔頂液を蒸留処理して、テトラヒドロフラン及びブタノールを主成分として含有する第二塔底液と、ジヒドロフランを主成分として含有する第二塔頂液とに分離して、第二塔底液を塔底液の排出口から排出し、第二塔頂液を塔頂液の排出口から排出する前記第二蒸留塔と、
原料供給口、塔底液の排出口及び塔頂液の排出口を備える第三蒸留塔であって、原料供給口から供給される第二塔底液を蒸留処理して、ブタノールを主成分として含有する第三塔底液と、テトラヒドロフランを主成分として含有する第三塔頂液とに分離して、第三塔底液を塔底液の排出口から排出し、第三塔頂液を塔頂液の排出口から排出する前記第三蒸留塔と、
第一蒸留塔の塔頂液の排出口と第二蒸留塔の原料供給口とを接続する流路と、
第二蒸留塔の塔底液の排出口と第三蒸留塔の原料供給口とを接続する流路と、
第二蒸留塔の塔頂液の排出口と第一蒸留塔の上流側とを接続し、第二蒸留塔の塔頂液の一部を第一蒸留塔に還流させる還流路と、
第二蒸留塔の塔頂液の排出口から第二蒸留塔の塔頂液の残部を系外に排出する排出路と、
を備える、テトラヒドロフランの精製システム。
本発明は、テトラヒドロフラン(THF)と、不純物として少なくとも水、ジヒドロフラン(DHF)及びブタノールを含有する液体から、THFを高純度で精製する方法に関する。本発明のTHFの精製方法に含まれる各工程について、以下に説明する。
本発明のTHFの精製方法は、THF並びに不純物として少なくとも水、DHF及びブタノールを含有する液体に適用することが出来る。上記の液体において、THFは10~98%の濃度であることが好ましい。また、水は1~90%の濃度であることが好ましく、DHFは10~5000 ppmの濃度であることが好ましく、ブタノールは0.1~2%の濃度であることが好ましい。また、上記の成分に加えて、他の不純物として、酢酸、イソプロパノール、プロパノール、メチルエチルケトン(MEK)、1-ブチルアルデヒド(NBD)等を含有する液体に対しても、本発明の精製方法を同様に適用することが出来る。この場合、酢酸は0.01~0.5%の濃度であることが好ましく、イソプロパノールは1~100 ppmの濃度であることが好ましく、プロパノールは1~100 ppmの濃度であることが好ましく、MEKは1~50 ppmの濃度であることが好ましく、NBDは1~30 ppmの濃度であることが好ましい。
第一の蒸留工程は、上記で説明したTHFを含有する液体を蒸留塔によって蒸留処理し、主要な不純物である水を粗く分離除去することを目的とする。本工程において、上記で説明したTHFを含有する液体を、水を主成分として含有する第一塔底液と、テトラヒドロフラン、ジヒドロフラン及びブタノールを主成分として含有する第一塔頂液とに分離することが出来る。
上記で説明した第一塔頂液をそのまま第二の蒸留工程に用いても良いが、場合により水素添加工程を実施しても良い。本工程は、第一塔頂液の主成分として含有されるDHFやNBDを水素添加反応に供することにより、THFの純度及び回収率をさらに向上させることを目的とする。
第二の蒸留工程は、第一塔頂液又は水素添加反応後の液体を蒸留塔によって蒸留処理し、DHFを分離除去することを目的とする。本工程において、第一塔頂液又は水素添加反応後の液体を、THF及びブタノールを主成分として含有する第二塔底液と、DHFを主成分として含有する第二塔頂液とに分離することが出来る。
還流工程は、第二の蒸留工程で分離された第二塔頂液の一部を還流液として第一の蒸留工程に還流させ、残部を系外に排出することにより、該塔頂液に含有される不純物であるDHF及び水の分離除去効率をさらに向上させることを目的とする。
第三の蒸留工程は、第二塔底液を蒸留塔によって蒸留処理し、目的物であるTHFを分離することを目的とする。本工程において、第二塔底液を、ブタノール、酢酸、イソプロパノール、プロパノール、メチルエチルケトン(MEK)、1-ブチルアルデヒド(NBD)等の不純物を主成分として含有する第三塔底液と、THFを主成分として含有する第三塔頂液とに分離することが出来る。
さらに本発明は、THF並びに不純物として少なくとも水、DHF及びブタノールを含有する液体からTHFを高純度で精製するための精製システムに関する。本発明のTHFの精製システムについて、添付図面に基づき以下に説明するが、本発明の精製システムはこれらに限定されるものではない。
原料供給口138、塔底液の排出口139及び塔頂液の排出口140を備える第二蒸留塔108であって、原料供給口138から供給される第一塔頂液を蒸留処理して、THF及びブタノールを主成分として含有する第二塔底液と、DHFを主成分として含有する第二塔頂液とに分離して、第二塔底液を塔底液の排出口139から排出し、第二塔頂液を塔頂液の排出口140から排出する前記第二蒸留塔108と、
原料供給口141、塔底液の排出口142及び塔頂液の排出口143を備える第三蒸留塔109であって、原料供給口141から供給される第二塔底液を蒸留処理して、ブタノールを主成分として含有する第三塔底液と、THFを主成分として含有する第三塔頂液とに分離して、第三塔底液を塔底液の排出口142から排出し、第三塔頂液を塔頂液の排出口143から排出する前記第三蒸留塔109と、
第一蒸留塔107の塔頂液の排出口137と第二蒸留塔108の原料供給口138とを接続する流路116と、
第二蒸留塔108の塔底液の排出口139と第三蒸留塔109の原料供給口141とを接続する流路121と、
第二蒸留塔108の塔頂液の排出口140と第一蒸留塔107の上流側とを接続し、第二蒸留塔108の塔頂液の一部を第一蒸留塔107に還流させる還流路151と、
第二蒸留塔108の塔頂液の排出口140から第二蒸留塔108の塔頂液の残部を系外に排出する排出路153とを主な構成要素とする。
本実施例で使用されたTHFの精製システムは、原料供給口、塔底液の排出口及び塔頂液の排出口を備える第一蒸留塔であって、原料供給口から供給されるTHF、DHF及びブタノールを含有するPBT重合プラントの副生成物の凝縮液を蒸留処理して、水を主成分として含有する第一塔底液と、THF、DHF及びブタノールを主成分として含有する第一塔頂液とに分離して、第一塔底液を塔底液の排出口から排出し、第一塔頂液を塔頂液の排出口から排出する前記第一蒸留塔と、原料供給口、塔底液の排出口及び塔頂液の排出口を備える第二蒸留塔であって、原料供給口から供給される第一塔頂液を蒸留処理して、THF及びブタノールを主成分として含有する第二塔底液と、DHFを主成分として含有する第二塔頂液とに分離して、第二塔底液を塔底液の排出口から排出し、第二塔頂液を塔頂液の排出口から排出する前記第二蒸留塔と、原料供給口、塔底液の排出口及び塔頂液の排出口を備える第三蒸留塔であって、原料供給口から供給される第二塔底液を蒸留処理して、ブタノールを主成分として含有する第三塔底液と、THFを主成分として含有する第三塔頂液とに分離して、第三塔底液を塔底液の排出口から排出し、第三塔頂液を塔頂液の排出口から排出する前記第三蒸留塔とが直列に配置されており、さらに第二蒸留塔の塔頂液の排出口と第一蒸留塔の上流側とを接続し、第二蒸留塔の塔頂液の一部を第一蒸留塔に還流させる還流路と、第二蒸留塔の塔頂液の排出口から第二蒸留塔の塔頂液の残部を系外に排出する排出路とを含む構成からなる。以下では図2に基づき、本発明の実施例を説明する。
上記の実施例で説明した本発明のTHF精製システムを適用せず、従来どおり、第二蒸留塔の塔頂液について、その一部を系外排出せずに精製システムを運転した。その結果、最終製品のTHF溶液はDHFを7%含有しており、著しい純度の低下が発生することが確認された。
108・・・第二蒸留塔
109・・・第三蒸留塔
135・・・第一蒸留塔の原料供給口
136・・・第一蒸留塔の塔底液の排出口
137・・・第一蒸留塔の塔頂液の排出口
138・・・第二蒸留塔の原料供給口
139・・・第二蒸留塔の塔底液の排出口
140・・・第二蒸留塔の塔頂液の排出口
141・・・第三蒸留塔の原料供給口
142・・・第三蒸留塔の塔底液の排出口
143・・・第三蒸留塔の塔頂液の排出口
151・・・還流路
116, 121, 125・・・流路
112, 129, 133, 153・・・排出路
154, 156,・・・流量調節弁
155, 157・・・流量計
261・・・水素添加塔
262・・・配管
263・・・タンク
264・・・レギュレータ
1000・・・テトラヒドロフランの精製システム
2000・・・テトラヒドロフランの精製システム
Claims (6)
- テトラヒドロフラン並びに不純物として少なくとも水、ジヒドロフラン及びブタノールを含有する液体からのテトラヒドロフランの精製方法であって、
該液体を蒸留塔によって蒸留処理し、水を主成分として含有する第一塔底液と、テトラヒドロフラン、ジヒドロフラン及びブタノールを主成分として含有する第一塔頂液とに分離する第一の蒸留工程と、
第一塔頂液を蒸留塔によって蒸留処理し、テトラヒドロフラン及びブタノールを主成分として含有する第二塔底液と、ジヒドロフランを主成分として含有する第二塔頂液とに分離する第二の蒸留工程と、
第二塔底液を蒸留塔によって蒸留処理し、ブタノールを主成分として含有する第三塔底液と、テトラヒドロフランを主成分として含有する第三塔頂液とに分離する第三の蒸留工程とを含み、
第二塔頂液の一部を還流液として第一の蒸留工程に還流させ、残部を系外に排出する還流工程をさらに含むことを特徴とする、テトラヒドロフランの精製方法。 - 還流工程において、第一の蒸留工程への還流液と系外への排出液との流量比が5:1~20:1の範囲である、請求項1のテトラヒドロフランの精製方法。
- 第一の蒸留工程と第二の蒸留工程の間に、
第一塔頂液に含有されるジヒドロフランを水素添加してテトラヒドロフランに変換する水素添加工程をさらに含む、請求項1又は2の精製方法。 - テトラヒドロフランの精製システムであって、
原料供給口、塔底液の排出口及び塔頂液の排出口を備える第一蒸留塔であって、原料供給口から供給されるテトラヒドロフラン並びに不純物として少なくとも水、ジヒドロフラン及びブタノールを含有する液体を蒸留処理して、水を主成分として含有する第一塔底液と、テトラヒドロフラン、ジヒドロフラン及びブタノールを主成分として含有する第一塔頂液とに分離して、第一塔底液を塔底液の排出口から排出し、第一塔頂液を塔頂液の排出口から排出する前記第一蒸留塔と、
原料供給口、塔底液の排出口及び塔頂液の排出口を備える第二蒸留塔であって、原料供給口から供給される第一塔頂液を蒸留処理して、テトラヒドロフラン及びブタノールを主成分として含有する第二塔底液と、ジヒドロフランを主成分として含有する第二塔頂液とに分離して、第二塔底液を塔底液の排出口から排出し、第二塔頂液を塔頂液の排出口から排出する前記第二蒸留塔と、
原料供給口、塔底液の排出口及び塔頂液の排出口を備える第三蒸留塔であって、原料供給口から供給される第二塔底液を蒸留処理して、ブタノールを主成分として含有する第三塔底液と、テトラヒドロフランを主成分として含有する第三塔頂液とに分離して、第三塔底液を塔底液の排出口から排出し、第三塔頂液を塔頂液の排出口から排出する前記第三蒸留塔と、
第一蒸留塔の塔頂液の排出口と第二蒸留塔の原料供給口とを接続する流路と、
第二蒸留塔の塔底液の排出口と第三蒸留塔の原料供給口とを接続する流路と、
第二蒸留塔の塔頂液の排出口と第一蒸留塔の上流側とを接続し、第二蒸留塔の塔頂液の一部を第一蒸留塔に還流させる還流路と、
第二蒸留塔の塔頂液の排出口から第二蒸留塔の塔頂液の残部を系外に排出する排出路と、
を備える、テトラヒドロフランの精製システム。 - 前記還流路と前記排出路との流量比を5:1~20:1の範囲に調整する手段をさらに備える、請求項4の精製システム。
- 第一蒸留塔の塔頂液の排出口と第二蒸留塔の原料供給口とを接続する流路の途中に水素添加塔をさらに備える、請求項4又は5の精製システム。
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US13/505,022 US20120215012A1 (en) | 2009-10-30 | 2009-10-30 | Process and system for purification of tetrahydrofuran |
JP2011538164A JP5536090B2 (ja) | 2009-10-30 | 2009-10-30 | テトラヒドロフランの精製方法及び精製システム |
CN2009801621764A CN102596926A (zh) | 2009-10-30 | 2009-10-30 | 四氢呋喃的精制方法以及精制系统 |
KR1020127009824A KR101398614B1 (ko) | 2009-10-30 | 2009-10-30 | 테트라히드로푸란의 정제 방법 및 정제 시스템 |
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WO2015194568A1 (ja) * | 2014-06-17 | 2015-12-23 | 三菱化学株式会社 | テトラヒドロフラン化合物の精製方法 |
JP2016088867A (ja) * | 2014-10-31 | 2016-05-23 | 三菱化学株式会社 | テトラヒドロフランの精製方法 |
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CN102816139A (zh) * | 2012-07-30 | 2012-12-12 | 南通星辰合成材料有限公司 | 四氢呋喃的提纯工艺 |
CN103833497B (zh) * | 2012-11-27 | 2016-01-20 | 上海富诺林精细化工有限公司 | 用乙醇胺处理粗环醚的方法和由其制得的精环醚 |
CN103601705B (zh) * | 2013-11-08 | 2015-05-20 | 盐城科菲特生化技术有限公司 | 四氢呋喃精馏方法 |
WO2018039848A1 (zh) * | 2016-08-29 | 2018-03-08 | 沈建美 | 四氢呋喃的回收工艺 |
CN107746394A (zh) * | 2017-12-06 | 2018-03-02 | 成都化润药业有限公司 | 含水四氢呋喃的精制纯化方法 |
CN116041285A (zh) * | 2022-12-08 | 2023-05-02 | 杰特(宁夏)科技有限公司 | 一种四氢呋喃脱水新工艺 |
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