WO2015030156A1

WO2015030156A1 - Method for separating, concentrating and/or collecting phenol, and system for achieving said method

Info

Publication number: WO2015030156A1
Application number: PCT/JP2014/072683
Authority: WO
Inventors: 宮内啓行; 橋本龍馬; 松尾洋志
Original assignee: 住友ベークライト株式会社; 木村化工機株式会社
Priority date: 2013-08-30
Filing date: 2014-08-29
Publication date: 2015-03-05
Also published as: JP2016188176A

Abstract

In one or multiple embodiments, a method for separating, concentrating and/or collecting a phenol from a dilute aqueous solution of the phenol which contains an inorganic ionic substance is provided. According to the method, the phenol can be concentrated while separating the inorganic ionic substance and the phenol from each other by the distillation not using an additive such as an extracting agent, and the energy saving performance can be improved. In one or multiple embodiments, the present invention relates to a method as mentioned above, which involves a separation step of separating the phenol and the inorganic ionic substance from each other, wherein the separation step comprises: producing, as a distillate, a phenol-containing solution having the inorganic ionic substance removed therefrom through a column top of a distillation column, to which the aqueous solution has been supplied, by employing an autovapor compression method; and obtaining a bottom solution containing the inorganic ionic substance from the column bottom of the distillation column.

Description

Method, system for separating, concentrating and / or recovering phenol

The present disclosure relates to a method for separating, concentrating and / or recovering phenol, and a system thereof.

A solvent extraction method is known as a method for recovering phenol from an aqueous solution containing phenol. Patent Document 1 discloses a method for recovering phenol by azeotropic distillation using xylene, toluene, benzene, cyclohexane, cumene, ethylbenzene and the like as azeotropic agents.

On the other hand, as a method not using an extractant or an azeotropic agent, there is a method using a pervaporation membrane. Patent Document 2 discloses a pervaporation membrane that can separate and recover phenol from a permeate on the decompression side.

JP 2007-196171 A JP H6-29631 A1

When recovering phenol from a dilute aqueous phenol solution by a solvent extraction method, an organic solvent as an extractant is mixed in the waste water after extraction, which causes a heavy load on waste water treatment. Further, for example, when the recovered phenol is reused in the phenol resin production process, mixing of the extractant becomes a problem in product quality. Further, rectifying the extractant from the recovered phenol requires a process that consumes significant energy. Even when phenol is recovered by an ordinary distillation method without using an extractant, if the phenol concentration in the aqueous solution is low, very large energy is required for the distillation operation.

Further, the aqueous phenol solution is an azeotropic mixture, and there is a problem that the concentration operation of dilute phenol is limited to about 10% by mass which is an azeotropic composition.

On the other hand, in the method using a pervaporation membrane, when the dilute phenol aqueous solution contains an inorganic ionic substance, this inorganic ionic substance causes the filterability of the pervaporation membrane to be extremely deteriorated. Therefore, when the dilute phenol aqueous solution contains an inorganic ionic substance, it is difficult to apply the phenol concentration operation using a membrane.

In one or a plurality of embodiments, the present disclosure is a method for separating, concentrating, and / or recovering phenol from a dilute aqueous phenol solution containing an inorganic ionic substance by distillation without using an additive such as an extractant. Provided is a method capable of concentrating phenol while separating inorganic ionic substances and phenol and improving energy saving.

In one or a plurality of embodiments of the present disclosure, the phenol is contained at a concentration of 0.05% by mass or more and 10% by mass or less, and the phenol is separated, concentrated, and / or recovered from an aqueous solution containing an inorganic ionic substance. A method,
The inorganic ionic substance is sulfate ion, phosphate ion, potassium ion, and magnesium ion,
A separation step of separating the phenol and the inorganic ionic substance,
The separation step includes obtaining, as a distillate, a phenol-containing liquid from which the inorganic ionic substances have been removed from the top of the distillation column supplied with the aqueous solution using a self-vapor compression method, and The present invention relates to a method including obtaining a bottom liquid containing the inorganic ionic substance from the bottom of the tower.

In one or a plurality of embodiments, the present disclosure includes a self-vapor compression distillation for separating phenol from an aqueous solution containing phenol at a concentration of 0.05% by mass or more and 10% by mass or less and containing an inorganic ionic substance. A system,
The inorganic ionic substance is sulfate ion, phosphate ion, potassium ion, and magnesium ion,
Equipped with a distillation tower, compressor and heat exchange type distillation tower reboiler,
Piping and / or configured so that the compressor compresses the steam discharged from the top of the distillation column to which the aqueous solution is supplied, and the compressed steam can be supplied as a heating source for the heat exchange distillation column reboiler. Relates to a self-vapor compression distillation system.

In one or a plurality of embodiments of the present disclosure, the phenol is contained at a concentration of 0.05% by mass or more and 10% by mass or less, and the phenol is separated, concentrated, and / or recovered from an aqueous solution containing an inorganic ionic substance. A system,
The inorganic ionic substance is sulfate ion, phosphate ion, potassium ion, and magnesium ion,
A self-vapor compression distillation system according to the present disclosure, a dehydration apparatus by an osmotic vaporization method, a two-phase separation tank, and a phenol fractionator
The phenol-containing liquid obtained by the self-vapor compression distillation system is supplied to the dehydrator and concentrated, the concentrated phenol concentrate is supplied to the two-phase separation tank, and the heavy liquid in the two-phase separation tank is The present invention relates to a system configured to be supplied with piping and / or configured to be supplied to a phenol rectification column.

According to the present disclosure, in one or a plurality of embodiments, an inorganic ionic substance and phenol are separated from a dilute phenol aqueous solution containing an inorganic ionic substance by distillation without using an additive and having high energy conservation. Phenol can be concentrated.

FIG. 1 is a diagram illustrating an example of a self-vapor compression distillation system according to an embodiment. FIG. 2 is a flowchart illustrating an example of a method for separating, concentrating and / or recovering phenol including a self-vapor compression (MVR) method and a pervaporation (PV) method according to an embodiment. FIG. 3 is a flowchart illustrating an example of a method for separating, concentrating and / or recovering phenol including a self-vapor compression (MVR) method, a pervaporation (PV) method, and a two-phase separation method according to an embodiment. . FIG. 4 shows an example of a method for separating, concentrating and / or recovering phenol including self-vapor compression (MVR), pervaporation (PV), two-phase separation, and rectification (distillation) according to one embodiment. It is a flowchart to explain. FIG. 5 shows a method for separating, concentrating and / or recovering phenol including self-vapor compression (MVR), pervaporation (PV), two-phase separation, rectification (distillation) and ammonia removal according to one embodiment. It is a flowchart explaining an example. FIG. 6 is a flowchart illustrating an example of phenol separation and concentration according to an embodiment. FIG. 7 is a flowchart illustrating an example of phenol separation and concentration according to an embodiment. FIG. 8 is a diagram illustrating an example of a phenol separation, concentration, and / or recovery system according to an embodiment.

In the present disclosure, when phenol is recovered from dilute phenol water containing an inorganic ionic substance for the purpose of using phenol, separation of the inorganic ionic substance and phenol to some extent is achieved by adopting a self-vapor compression type distillation system. Is based on the finding that high energy efficiency is possible without the use of additives. The present disclosure can also concentrate phenol by avoiding an azeotropic point by dehydrating phenol water separated by a self-vapor compression distillation system by an osmotic vaporization method, and further combining two-phase separation and rectification processes. Thus, it is based on the knowledge that recovery of high concentration phenol from dilute phenol water containing inorganic ionic substances is possible with high energy efficiency without using additives.

In one or more embodiments that are not limited, according to the present disclosure, the phenol can be concentrated and recovered in the flow diagram shown in FIG. That is, dilute phenol water containing inorganic ionic substances (1 mass% or more and 2 mass% or less phenol + inorganic ionic substance-containing water) is treated with inorganic ionic properties in the separation step (10) by the self-vapor compression (MVR) method. The substance is separated and removed, and concentrated to 5% by mass or more and 10% by mass or less of phenol water. Next, the phenol water of 5% by mass or more and 10% by mass or less is supplied to a concentration step (20) by a pervaporation (PV) method, and dehydrated by a pervaporation membrane, whereby an azeotropic composition (phenol about 10% by mass). ) Over about 30% by weight. And about 30 mass% phenol water is provided to the concentration process (30) by a two-phase separation method. Generally, phenol water is divided into two phases, a water-rich phase (about 8% by mass phenol: light liquid) and a phenol-rich phase (about 70% by mass phenol: heavy liquid) in the concentration range of 8% by mass to 70% by mass. To separate. Therefore, when about 30% by mass phenol water is separated in a two-phase separation tank and the heavy liquid is recovered, about 70% by mass phenol water is obtained. By subjecting this about 70% by mass phenol water to the purification step (40) and rectification, 80% by mass or more and 98% by mass or less of concentrated phenol can be obtained. In this series of processes, energy saving can be improved by performing the first separation step having the largest processing volume by the self-vapor compression (MVR) method. In addition, since this series of processes does not require the use of an additive (in one non-limiting example, an extractant or the like), the convenience of using the recovered phenol can be improved. Furthermore, by not using an additive (in one non-limiting example, an extractant or the like), the load on the treatment of wastewater generated in large quantities can be reduced. That is, it is possible to concentrate and recover industrial-level phenol in that a series of processes can be performed with energy saving and contamination-free.

[Diluted phenol water as raw material]
In the present disclosure, dilute phenol water (hereinafter also referred to as “diluted phenol stock solution”) that is a target (raw material or stock solution) to be subjected to the separation, concentration, and / or recovery of phenol is phenol and inorganic ionic substances. contains.
In one or more embodiments that are not limited, the phenol concentration in the diluted phenol stock solution is 0.05% by mass or more, 0.1% by mass or more, 0.5% by mass or more, from the viewpoint of concentration and recovery of phenol at an industrial level. Or 10% by weight or less, less than 10% by weight, 8% by weight or less, 5% by weight or less, 3% by weight or less, or 2% by weight or less, or 0.05% by weight to 10% by weight. Or less, 0.1 to 8 mass%, 0.5 to 5 mass%, 1 to 3 mass%, or 1 to 2 mass%.

The diluted phenol stock solution contains at least sulfate ions, phosphate ions, potassium ions, and magnesium ions as inorganic ionic substances. The concentration of each of these ions is 10% by mass or less, 5% by mass or less, or 1% by mass or less in one or more embodiments. In addition, in each or a plurality of embodiments, each of these ion concentrations exceeds 0, is detection sensitivity or higher, 0.0001% by mass or higher, 0.001% by mass or higher, 0.005% by mass or higher, or 0.0. 01 mass% or more is mentioned.

In one or more embodiments that are not limited, the concentration of each ion of sulfate ion, phosphate ion, and potassium ion is 0.005% by mass to 10% by mass, 0.01% by mass to 5% by mass, or 0 It is 0.01 mass% or more and 1 mass% or less. In one or a plurality of non-limiting embodiments, the magnesium ion concentration is 0.00005% by mass to 1% by mass, 0.0001% by mass to 0.1% by mass, or 0.0001% by mass to 0%. 0.001% by mass or less, and 0.0001% by mass or more and 0.001% by mass or less.

The total content of inorganic ionic substances contained in the diluted phenol stock solution is 0.005% by mass or more, 0.01% by mass or more, or 0.1% by mass or more in one or more embodiments. 10 mass% or less, 5 mass% or less, or 3 mass% or less, or 0.005 mass% or more and 10 mass% or less, 0.01 mass% or more and 5 mass% or less, or 0.1 mass% or more. 3% by mass or less.
Examples of other inorganic ionic substances that can be contained in the diluted phenol stock solution include sodium ions, chloride ions, and nitrate ions in one or a plurality of embodiments, and the content thereof is one or a plurality of embodiments. 1% by mass or less.

The diluted phenol stock solution may contain ammonium ions in one or more embodiments. In the case where the diluted phenol stock solution contains ammonium ions, the concentration thereof is 1.0% by mass or less, 0.5% by mass or less, or 0.3% by mass or less, or 0 in one or more embodiments. It is 1 mass% or more and 1.0 mass% or less, 0.1 mass% or more and 0.5 mass% or less, or 0.1 mass% or more and 0.3 mass% or less.

When the diluted phenol stock solution contains ammonium ions, as shown in the flow chart of FIG. 7, ammonium ions are mixed with phenol in the heavy liquid (about 70% by mass phenol water) in the concentration step (30) by the two-phase separation method. Will remain (in one or more embodiments, ammonia concentration of several hundred ppm). However, as shown in the flowchart of FIG. 7, most of the ammonium ions can be removed in the rectification step of the purification step (40).

In one or a plurality of embodiments, the diluted phenol stock solution includes a liquid recovered in the phenol production process. The liquid recovered in the phenol production process may be a phenol resin production factory waste liquid or a green phenol recovery liquid in one or more embodiments. The diluted phenol stock solution includes, in one or more other embodiments, a recovered solution from biomass resources.

[Separation process by self-vapor compression (MVR) method]
In one aspect, the present disclosure is a method for separating, concentrating, and / or recovering phenol from a dilute phenol stock solution, wherein the phenol and the inorganic ionic substance in the dilute phenol stock solution are separated using a self-vapor compression method. The present invention relates to a method including a separation step. In one or a plurality of embodiments of the separation step, a phenol-containing liquid from which the inorganic ionic substances have been removed from the top of the distillation tower supplied with the dilute phenol stock solution is obtained as a distillate, and the tower of the distillation tower A bottom liquid containing the inorganic ionic substance is obtained from the bottom.

In one or a plurality of embodiments of the present disclosure, the self-vapor compression (MVR) method uses steam (phenol water vapor) discharged from the top of a distillation column supplied with a dilute phenol stock solution. It refers to a distillation method that includes compressing and supplying the compressed steam to the distillation column reboiler as a heating source for the autodistillation column. Steam compression is mechanically performed by a compressor in one or a plurality of embodiments, and examples of the compressor include a fan and a blower in one or a plurality of embodiments. The phenol water vapor used as a heating source is recovered as a phenol-containing liquid from which inorganic ionic substances have been removed. The energy required for the MVR method is only the work of mechanically compressing and heating the steam while maintaining the latent heat of vaporization of the phenol water discharged from the top of the tower. Can be used as a source. Therefore, the energy required for the MVR method can exhibit epoch-making energy saving in one or a plurality of embodiments.

In one or a plurality of embodiments of the present disclosure, the phenol concentration of the distillate obtained from the top of the distillation column by the MVR method is a phenol concentration of 5% by mass or more and 10% by mass or less. When the phenol content in the dilute phenol stock solution is lower, the phenol can be concentrated.

In one or more embodiments of the present disclosure, the separation step by the MVR method can be performed without adding an additive such as an extractant or an azeotropic agent.

[Self-vapor compression (MVR) distillation system]
In one or a plurality of embodiments of the present disclosure, the separation step by the MVR method includes a distillation column, a compressor, and a heat exchange type distillation column reboiler, and steam discharged from the top of the distillation column to which the aqueous solution is supplied. Can be performed by an MVR type distillation system in which the compressor compresses and the compressed steam can be supplied as a heat source for the heat exchange type distillation column reboiler.

Hereinafter, an embodiment of an MVR type distillation system according to the present disclosure will be described with reference to the drawings. FIG. 1 is a diagram illustrating an MVR distillation system 10 according to one or more non-limiting embodiments. The MVR type distillation system 10 includes a distillation column 12, a compressor 13, and a heat exchange type distillation column reboiler 14. A dilute phenol stock solution 11 is supplied to the distillation column 12. The phenol-containing water vapor discharged from the top of the tower is supplied to the compressor 13 through the pipe 100. The compressor 13 mechanically compresses and raises the temperature of the steam. The vapor of the phenol-containing water that has been compressed and heated passes through the pipe 101 and is supplied to the heat exchange distillation column reboiler 14 as a heating source. The phenol-containing liquid 15 that is used as a heating source and discharged from the heat exchange distillation column reboiler 14 is recovered through the

pipes

102 and 103 or is returned to the distillation tower 12 through the pipe 104 as a reflux liquid. The bottoms discharged from the bottom of the column is recovered as inorganic ionic substance-containing water 16 through the

pipes

105 and 108, or is supplied to the heat exchange distillation column reboiler 14 through the pipe 106 and becomes steam to form the pipe 107. And supplied to the distillation column 12.

As the distillation column 12, in one or a plurality of embodiments, a distillation column usually used for distillation can be used, and it may be a packed distillation column or a multi-tray distillation column. In one or more embodiments that are not limited as operating conditions, the pressure in the column is 20 kPa or more and 100 kPa or less, the column bottom temperature is 60 ° C. or more and 110 ° C. or less, the column top temperature is 50 ° C. or more and 100 ° C. or less, and the reflux ratio (R / D ) Is about 1 or more and 5 or less.
In one or a plurality of embodiments, the compressor 13 is a fan or a blower.
In one or a plurality of embodiments, the heat exchange distillation column reboiler 14 can be a heat exchange distillation column reboiler that is usually used for distillation. In one or a plurality of embodiments, the compressor 13 and / or the reboiler 14 is preferably operated under vacuum from the viewpoint of preventing leakage of phenol-containing steam. Further, the reboiler 14 is preferably a thin film effect type (falling film type) in one or a plurality of embodiments from the viewpoint of effectively utilizing the temperature difference between the shell side and the tube side.

[Concentration by pervaporation (PV) method]
In one or a plurality of embodiments, a method for separating, concentrating, and / or recovering phenol from a dilute phenol stock solution according to the present disclosure includes a concentration step by a pervaporation (PV) method after a separation step by an MVR method. FIG. 2 is a flowchart for explaining an example of the present embodiment. The inorganic ionic substance 16 is separated from the dilute phenol stock solution 11 by the separation step 10 by the MVR method. The obtained phenol-containing water is concentrated in the concentration step 20 by the PV method, and a phenol concentrate 22 is obtained.

In the present disclosure, the concentration step by the pervaporation (PV) method refers to, in one or a plurality of embodiments, the phenol-containing liquid obtained in the separation step by the MVR method using a pervaporation membrane (PV membrane). Including dehydration to concentrate phenol. Since the inorganic ionic substance is removed by the MVR method, a PV membrane can be used.

In one or more embodiments of the present disclosure, the concentration step by the PV method is performed to a phenol concentration exceeding the azeotropic composition (phenol about 10% by mass). In one or more embodiments, the phenol concentration in the concentrate obtained in the concentration step by the PV method is 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, or It is 40 mass% or less, or about 30 mass%.

In one or a plurality of embodiments of the present disclosure, the concentration step by the PV method can be performed by a dehydration apparatus including a PV membrane. In one or some embodiment, inorganic membranes, such as a ceramic membrane and a zeolite membrane, are mentioned as PV membrane.

In one or more embodiments of the present disclosure, the permeate on the permeate side of the PV membrane contains a trace amount of phenol (eg, about 0.2% by weight) and can therefore be used back into a dilute phenol stock or its supply line. . In one or a plurality of embodiments of the present disclosure, when the diluted phenol stock solution contains ammonium ions, the permeated water on the permeation side of the PV membrane also contains ammonium ions (for example, several hundred ppm) as in the concentrated solution. In that case, after removing ammonia by the ammonia removal process 50 mentioned later (FIG. 5), it can return to a diluted phenol stock solution or its supply line, and can be used.

[Concentration by two-phase separation method]
In one or a plurality of embodiments, the method for separating, concentrating, and / or recovering phenol from a diluted phenol stock solution according to the present disclosure may further include two-phase after the separation step by the MVR method and the concentration step by the PV method. Concentration step by separation method is included. FIG. 3 is a flowchart illustrating an example of this embodiment. The diluted phenol stock solution 11 is separated from the inorganic ionic substance 16 by the separation step 10 by the MVR method, further concentrated by the concentration step 20 by the PV method, and the obtained phenol concentrated solution is separated by the two-phase separation method 30. Rich phase (heavy liquid) 32 is recovered.

The phenol concentrate obtained in the concentration step 20 by the PV method is separated into two phases of a water-rich phase (about 8% by mass phenol: light liquid) and a phenol-rich phase (about 70% by mass phenol: heavy liquid) at room temperature. By recovering the phenol-rich phase (heavy liquid) 32, a phenol concentrate of about 70% by mass can be obtained.

In one or more embodiments of the present disclosure, the concentration step by the two-phase separation method can be performed by a two-phase separation tank. As a two-phase separation tank, in one or some embodiment, the two-phase separation tank normally used is mentioned.

In one or more embodiments of the present disclosure, the water-rich phase (about 8% by mass phenol: light liquid) can be returned to the diluted phenol stock solution or its supply line for use. In one or a plurality of embodiments of the present disclosure, when the diluted phenol stock solution contains ammonium ions, the light solution contains ammonium ions as well as the heavy solution (for example, several hundred ppm). In that case, after removing ammonia by the ammonia removal process 50 mentioned later (FIG. 5), it can return to a diluted phenol stock solution or its supply line, and can be used.

[Phenol purification process]
In one or a plurality of embodiments, a method for separating, concentrating, and / or recovering phenol from a diluted phenol stock solution according to the present disclosure includes a separation step by an MVR method, a concentration step by a PV method, and a concentration step by a two-phase separation method. Is followed by a phenol purification step. FIG. 4 is a flowchart illustrating an example of this embodiment. In the diluted phenol stock solution 11, the inorganic ionic substance 16 is removed by the separation step 10 by the MVR method, and further concentrated by the concentration step 20 by the PV method and the concentration step 30 by the two-phase separation method. Further, in the phenol purification step 40 Concentrated and concentrated phenol 44 is obtained.

In one or more embodiments of the present disclosure, the phenol purification step 40 is performed by distillation (rectification) to obtain purified concentrated phenol as a bottoms. As a distillation column (rectification column) of distillation (rectification) in the phenol purification step 40, in one or a plurality of embodiments, a distillation column usually used for distillation (rectification) can be used, and a packed distillation column is used. However, a multi-stage tray distillation column may be used. In one or more embodiments that are not limited as operating conditions, the pressure in the column is 20 kPa or more and 100 kPa or less, the column bottom temperature is 65 ° C. or more and 105 ° C. or less, the column top temperature is 45 ° C. or more and 95 ° C. or less, and the reflux ratio (R / D ) Is about 1 or more and 10 or less.

In one or more embodiments, the concentration of the purified concentrated phenol is 80% by mass or more, 85% by mass or more, or 90% by mass or more, or 80% by mass or more and 99% by mass or less, and 80% by mass or more. It is 98 mass% or less, 80 mass% or more and 95 mass% or less, or 85 mass% or more and 95 mass% or less. In one or a plurality of embodiments, even when the diluted phenol stock solution contains ammonium ions, the ammonium ions contained in the bottoms of the phenol purification step (purified concentrated phenol) are not limited to one or more. In embodiments, it can be reduced to 100 ppm to 1000 ppm, 50 ppm to 1000 ppm, or about 50 ppm.

In one or more embodiments of the present disclosure, the distillate of the phenol purification step can be used by returning to the diluted phenol stock solution or its supply line. In one or a plurality of embodiments of the present disclosure, when the diluted phenol stock solution contains ammonium ions, ammonia that is a low boiling component and phenol that is an azeotropic component are each several mass% (for example, 1 mass% or more and 5 mass%). % Or less, or 2% by mass or more and 3% by mass or less) is obtained as a distillate from the top of the column. In that case, after removing ammonia by the ammonia removal process 50 mentioned later (FIG. 5), it can return to a diluted phenol stock solution or its supply line, and can be used.

[Ammonia removal step]
The method for separating, concentrating and / or recovering phenol from a dilute phenol stock solution according to the present disclosure includes an ammonia removal step in one or more embodiments. FIG. 5 is a flowchart for explaining an example of this embodiment. As described above, when the diluted phenol stock solution 11 contains ammonium ions, the permeated water of the PV membrane in the concentration step 20 by the PV method, the light liquid in the concentration step 30 by the two-phase separation method, and the distillate in the phenol purification step 40 May contain ammonium ions with low concentrations of phenol. In one or a plurality of embodiments, ammonia can be removed from these liquids by the ammonia removal step 50 to obtain a diluted phenol liquid, which can be returned to the diluted phenol stock solution or its supply line for use.

In one or more embodiments of the present disclosure, the ammonia removal step 50 is performed by distillation to obtain a dilute phenol aqueous solution in which ammonium ions are reduced to several ppm as a bottoms. A distillate containing about 20% by mass of ammonia is obtained from the top of the column. As a distillation column for distillation in the ammonia removal step 50, in one or a plurality of embodiments, a distillation column usually used for distillation can be used, and a packed distillation column or a multi-tray distillation column may be used. In one or a plurality of embodiments that are not limited as operating conditions, the pressure in the column is 20 kPa to 100 kPa, the column bottom temperature is 60 ° C. to 100 ° C., the column top temperature is 55 ° C. to 95 ° C., and the reflux ratio (R / D ) Is about 1 or more and 10 or less.

[System for separating, concentrating and recovering phenol from dilute phenol stock solution]
In one or a plurality of embodiments, a method for separating, concentrating, and / or recovering phenol from a diluted phenol stock solution according to the present disclosure includes an MVR type distillation system according to the present disclosure, a dehydration apparatus by a PV method, a two-phase separation tank, A phenol-containing liquid provided with a phenol rectification column and supplied by the MVR type condensed distillation system is supplied to the dehydrator and concentrated, and the concentrated phenol concentrate is supplied to the two-phase separation tank, and the two-phase separation It can be carried out by a system (hereinafter also referred to as “phenol recovery system”) in which a heavy liquid is supplied to the phenol rectification column and / or configured.

Hereinafter, an embodiment of a phenol recovery system according to the present disclosure will be described with reference to the drawings. FIG. 8 is a diagram illustrating a system for recovering phenol from a dilute phenol raw material containing ammonium ions in one or more non-limiting embodiments.
The phenol recovery system shown in FIG. 1 includes an MVR distillation system 10, a concentration device 20 using a PV method, a concentration device 30 using a two-phase separation method, a phenol purification system 40, and an ammonia removal system 50.

The MVR type distillation system 10 includes the distillation column 12, the compressor 13, and the heat exchange type distillation column reboiler 14 as described above. The diluted phenol stock solution 11 is supplied to the distillation column 12 through the pipe 109. The phenol-containing water vapor discharged from the top of the tower is supplied to the compressor 13 through the pipe 100. The compressor 13 mechanically compresses and raises the temperature of the steam. The vapor of the phenol-containing water that has been compressed and heated passes through the pipe 101 and is supplied to the heat exchange distillation column reboiler 14 as a heating source. The phenol-containing liquid used as a heating source and discharged from the heat exchange distillation column reboiler 14 is sent to the concentration apparatus 20 by the PV method through the

pipes

102 and 103, or is sent to the distillation tower 12 as a reflux liquid through the pipe 104. Refluxed. The bottoms discharged from the bottom of the column is recovered as inorganic ionic substance-containing water 16 through the

pipes

The concentration device 20 by the PV method is provided with a PV membrane dewatering device 21. The phenol-containing liquid supplied through the pipe 103 is concentrated by the PV membrane dehydrator 21. The concentrated phenol water is sent to the concentration device 30 by the two-phase separation method through the pipe 201. On the other hand, the permeated water on the permeate side of the PV membrane of the PV membrane dehydrator 21 is sent to the ammonia removal system 50 through the

pipes

202 and 501.

The concentration device 30 by the two-phase separation method includes a two-phase separation tank 31. The concentrated phenol water supplied through the pipe 201 is separated into two phases in the two-phase separation tank 31. A heavy liquid that is a phenol-rich phase (about 70% by mass of phenol concentrate) is sent to the phenol purification system 40 through the pipe 301. On the other hand, the light liquid that is a water-rich phase is sent to the ammonia removal system 50 through the

pipes

302 and 501.

The phenol purification system 40 includes a rectifying column 41, a condenser 42, and a distillation column reboiler 43. About 70% by mass of the phenol concentrate is supplied to the rectification column 41 through the pipe 301. The purified concentrated phenol 44 is recovered from the bottom of the rectifying column 41 through the

pipes

401 and 402 as the bottoms, or is supplied to the reboiler 43 through the pipe 403 and becomes steam to the rectifying tower 41 through the pipe 404. Supplied. The distillate obtained from the top of the rectification column 41 through the condenser 42 is sent to the ammonia removal system 50 through the

pipes

406 and 501, or is sent to the rectification tower 41 as a reflux liquid through the pipe 407. To be supplied.

The ammonia removal system 50 includes a distillation column 51, a condenser 52, and a distillation column reboiler 53. An aqueous solution containing ammonium ions and phenol is supplied to the distillation column 51 through the pipe 501. A dilute phenol aqueous solution in which ammonium ions are reduced to several ppm as a bottoms of the distillation column 51 passes through a pipe 506 and is supplied to a pipe 109 to which the diluted phenol stock solution 11 is supplied. Alternatively, it is supplied to the reboiler 53 through the pipe 507 and is supplied to the distillation tower 51 through the pipe 508 as steam. The distillate obtained from the top of the distillation column 51 through the condenser 52 is recovered as ammonia drainage 54 through a pipe 503 or supplied to the distillation tower 51 as a reflux liquid through a pipe 504.

In the phenol recovery system according to the present disclosure, the energy saving can be improved by performing the first separation step with the largest processing volume by the self-vapor compression (MVR) method. Moreover, since the phenol recovery system according to the present disclosure does not need to use an additive (in one non-limiting example, an extractant or the like), the convenience of using the recovered phenol can be improved. Furthermore, by not using an additive (in one non-limiting example, an extractant or the like), the load on the treatment of wastewater generated in large quantities can be reduced. That is, according to the phenol recovery system according to the present disclosure, in one or a plurality of embodiments, industrial level phenol recovery from a dilute phenol stock solution is possible in that it can be performed in an energy saving and contamination-free manner.

The present invention further relates to one or a plurality of embodiments below.

<A1> A method of separating, concentrating, and / or recovering phenol from an aqueous solution containing phenol at a concentration of 0.05% by mass or more and 10% by mass or less and containing an inorganic ionic substance,
The inorganic ionic substance is sulfate ion, phosphate ion, potassium ion, and magnesium ion,
A separation step of separating the phenol and the inorganic ionic substance,
The separation step includes obtaining, as a distillate, a phenol-containing liquid from which the inorganic ionic substances have been removed from the top of the distillation column supplied with the aqueous solution using a self-vapor compression method, and Obtaining a bottoms containing the inorganic ionic substance from the bottom of the tower.
<A2> In the self-vapor compression method, the vapor discharged from the top of the distillation column is compressed, the compressed vapor is supplied to the distillation column reboiler as a heating source for the distillation column, and the distillation The method according to <A1>, comprising obtaining a phenol-containing liquid by exchanging heat as a heating source of the distillation tower in a tower reboiler.
<A3> The method according to <A1> or <A2>, wherein the total content of sulfate ion, phosphate ion, potassium ion, and magnesium ion in the aqueous solution is 0.005 mass% or more and 10 mass% or less.
<A4> The method according to any one of <A1> to <A3>, wherein the aqueous solution further contains ammonium ions.
<A5> The method according to any one of <A1> to <A4>, further including a concentration step of concentrating the phenol-containing liquid obtained in the separation step by a pervaporation method.
<A6> The method according to <A5>, comprising two-phase separation of the phenol concentrate obtained in the concentration step.
<A7> The method according to <A6>, comprising supplying the heavy liquid from the two-phase separation to a rectification column to obtain purified concentrated phenol.
<A8> A self-vapor compression distillation system for separating phenol from an aqueous solution containing phenol at a concentration of 0.05% by mass to 10% by mass and containing an inorganic ionic substance,
The inorganic ionic substance is sulfate ion, phosphate ion, potassium ion, and magnesium ion,
Equipped with a distillation tower, compressor and heat exchange type distillation tower reboiler,
Piping and / or configured so that the compressor compresses the steam discharged from the top of the distillation column to which the aqueous solution is supplied, and the compressed steam can be supplied as a heating source for the heat exchange distillation column reboiler. A self-vapor compression distillation system.
<A9> A system for separating, concentrating and / or recovering phenol from an aqueous solution containing phenol at a concentration of 0.05% by mass or more and 10% by mass or less and containing an inorganic ionic substance,
The inorganic ionic substance is sulfate ion, phosphate ion, potassium ion, and magnesium ion,
A self-vapor compression distillation system according to <A8>, a dehydration apparatus by permeation vaporization, a two-phase separation tank, and a phenol rectification column,
The phenol-containing liquid obtained by the self-vapor compression distillation system is supplied to the dehydrator and concentrated, the concentrated phenol concentrate is supplied to the two-phase separation tank, and the heavy liquid of the two-phase separation is the phenol. A system that is piped and / or configured to be supplied to a rectification column.

10: Separation process by self-vapor compression (MVR) method or its system 20 ... Concentration process by pervaporation (PV) method or apparatus 30 ... Concentration process by two-phase separation method or apparatus 40 ...・ Phenol purification step or its system 50 ... Ammonia removal step or its system 11 ... Diluted phenol water 12 ... Distillation tower (MVR type distillation tower)
DESCRIPTION OF SYMBOLS 13 ... Compressor 14 ... MVR type distillation column reboiler 15 ... Separated phenol water 16 ... Inorganic ionic substance containing water 21 ... PV membrane dehydrator 22 ... Concentrated phenol Water 31 ... two-phase separation tank 32 ... concentrated phenol water 41 ... rectification tower (phenol purification tower)
42 ... Condenser 43 ... Distillation tower reboiler 44 ... Concentrated phenol water 51 ... Distillation tower (ammonia removal tower)
52 ... Condenser 53 ... Distillation tower reboiler 54 ... Ammonia waste water 100-109 ... Piping 201-202 ... Piping 301-302 ... Piping 401-407 ... Piping 501-508 ... Piping

Claims

A method for separating, concentrating and / or recovering phenol from an aqueous solution containing phenol at a concentration of 0.05% by mass or more and 10% by mass or less and containing an inorganic ionic substance and ammonium ion,
The inorganic ionic substance is sulfate ion, phosphate ion, potassium ion, and magnesium ion,
A separation step of separating the phenol and the inorganic ionic substance,
The separation step includes obtaining, as a distillate, a phenol-containing liquid from which the inorganic ionic substances have been removed from the top of the distillation column supplied with the aqueous solution using a self-vapor compression method, and Obtaining a bottoms containing the inorganic ionic substance from the bottom of the tower.
In the self-vapor compression method, the vapor discharged from the top of the distillation column is compressed, the compressed vapor is supplied to the distillation column reboiler as a heating source for the distillation column, and the distillation column reboiler The method according to claim 1, comprising obtaining a phenol-containing liquid by heat exchange as a heating source of the distillation column.
The method according to claim 1 or 2, wherein the total content of sulfate ion, phosphate ion, potassium ion, and magnesium ion in the aqueous solution is 0.005 mass% or more and 10 mass% or less.
The method according to any one of claims 1 to 3, wherein the content of ammonium ions in the aqueous solution is 1.0 mass% or less.
The method according to any one of claims 1 to 4, further comprising a concentration step of concentrating the phenol-containing liquid obtained in the separation step by a pervaporation method.
The method according to claim 5, comprising two-phase separation of the phenol concentrate obtained in the concentration step.
The method according to claim 6, comprising supplying the heavy liquid of the two-phase separation to a rectification column to obtain purified concentrated phenol.
A self-vapor compression distillation system for separating phenol from an aqueous solution containing phenol at a concentration of 0.05% by mass to 10% by mass and containing an inorganic ionic substance and ammonium ions,
The inorganic ionic substance is sulfate ion, phosphate ion, potassium ion, and magnesium ion,
Equipped with a distillation tower, compressor and heat exchange type distillation tower reboiler,
Piping and / or configured so that the compressor compresses the steam discharged from the top of the distillation column to which the aqueous solution is supplied, and the compressed steam can be supplied as a heating source for the heat exchange distillation column reboiler. A self-vapor compression distillation system.
A system for separating, concentrating and / or recovering phenol from an aqueous solution containing phenol at a concentration of 0.05% by mass or more and 10% by mass or less and containing an inorganic ionic substance and ammonium ion,
The inorganic ionic substance is sulfate ion, phosphate ion, potassium ion, and magnesium ion,
A self-vapor compression distillation system according to claim 8, a dewatering device by pervaporation, a two-phase separation tank, and a phenol rectification column,
The phenol-containing liquid obtained by the self-vapor compression distillation system is supplied to the dehydrator and concentrated, the concentrated phenol concentrate is supplied to the two-phase separation tank, and the heavy liquid in the two-phase separation tank is A system that is piped and / or configured to be fed to a phenol rectification column.