JP6514426B1 - Solution processing apparatus and solution processing method - Google Patents

Abstract

An object of the present invention is to provide a solution processing apparatus and a solution processing method which can exhibit excellent processing efficiency even if non-volatile components of the liquid to be treated are deposited. The solution processing apparatus (1A) according to the present invention heats the liquid to be treated (L1), distills off the vapor, and the first gas-liquid separation means (10) which can partially release the liquid concentrate to be held A second gas-liquid separation means (20) for heating the concentrated solution discharged from the first gas-liquid separation means (10) to distill a vapor and for partially releasing the retained concentrate; Control means (30) for controlling the first gas-liquid separation means (10) such that non-volatile components contained in the liquid to be treated (L1) are not precipitated in the first gas-liquid separation means (10) It is characterized in that it is a place where the concentrate of the second gas-liquid separation means (20) is heated and a wetted part in contact with the concentrate exhibits adhesion resistance to non-volatile components.

Description

  The present invention relates to a solution processing apparatus and a solution processing method for separating an organic solvent from a liquid to be treated in which a nonvolatile component is mixed with an organic solvent.

The organic solvent is used as a solubilizer for dissolving an object such as a resin or a dispersing agent for dispersing it. In addition, organic solvents are also used as release agents for photosensitive resins, called photoresists, also in the manufacturing process of liquid crystal substrates and semiconductor integrated circuits.
And although the organic solvent used for such a use removes an impurity and is recycled in many cases, about the recycle of an organic solvent, the isolation | separation method of the impurity called distillation is usually applied.

  Various techniques have been proposed for recycling organic solvents by distillation. For example, Patent Document 1 discloses a process of recovering a liquid mixture of a resist and an organic solvent discharged from a resist coating apparatus, and the organic solvent And volatilizing to concentrate the mixture, liquefying the volatilized organic solvent, and adjusting the viscosity of the mixture to a desired value by adding the organic solvent to the concentrated mixture. A resist regeneration method is disclosed, characterized in that:

Japanese Patent Application Laid-Open No. 09-082602

However, in the conventional method as disclosed in Patent Document 1, the non-volatile components such as the resin dissolved in the organic solvent are deposited, and the wetted part of the evaporator for evaporating the organic solvent is obtained. There is a possibility that the deposited non-volatile component may adhere (stick, adhere, etc.). As a result, in the conventional method, the heating performance of the evaporator decreases with time, and the expected effects of improving the recovery rate of the solvent, preventing the adiabatic loss in the pipe, and saving energy can not be exhibited.
As a countermeasure against this problem, there is a method in which the separation operation of the organic solvent is performed under the condition that the non-volatile component does not precipitate, but with this countermeasure, the processing efficiency (distillation rate) of the organic solvent is deteriorated. Since the amount of waste increases, it is not economically and environmentally preferable.

  Then, this invention makes it a subject to provide the solution processing apparatus and the solution processing method which can exhibit the outstanding processing efficiency, even if the non-volatile component of a to-be-processed liquid precipitates.

  As means for solving the above problems, a solution processing apparatus according to the present invention is a solution processing apparatus for separating an organic solvent as distillate vapor from a liquid to be treated containing an organic solvent and a non-volatile component. The process liquid is heated to distill a vapor, and the first gas-liquid separation means for making a part of the concentrated liquid to be held down and the concentrate from the first gas-liquid separation means are heated, the steam being The second gas-liquid separation means for distilling a portion of the concentrate to be distilled while distilling out the non-volatile components contained in the liquid to be treated in the first gas-liquid separation means 1) Control means for controlling the gas-liquid separation means, wherein the liquid-wetted place in the second gas-liquid separation means which heats the liquid concentrate and in contact with the liquid concentrate is resistant to adhesion to non-volatile components It is characterized by showing.

  The solution processing method according to the present invention is a solution processing method for separating an organic solvent as distillate vapor from a liquid to be treated containing an organic solvent and a non-volatile component, wherein the liquid to be treated is heated to A first gas-liquid separation step of distilling and partially releasing the retained concentrate, and heating the concentrated solution released in the first gas-liquid separation step to distill a vapor and holding the same And a second gas-liquid separation step of partially draining the concentrated liquid, wherein in the first gas-liquid separation step, control is performed such that non-volatile components contained in the liquid to be treated are not precipitated; It is characterized in that it is a place where the concentrate is heated in the gas-liquid separation step and the wetted part in contact with the concentrate exhibits adhesion resistance to non-volatile components.

  ADVANTAGE OF THE INVENTION According to this invention, even if the non-volatile component of to-be-processed liquid precipitates, the solution processing apparatus and solution processing method which can exhibit the outstanding processing efficiency can be provided.

It is a schematic diagram of the solution processing apparatus which concerns on this embodiment. It is a schematic diagram of the solution processing apparatus which concerns on a modification. 3 is a table showing the results obtained in the preliminary test in Example 1. 7 is a graph of the concentrate temperature and the non-volatile component concentration obtained in the preliminary test in Example 1. FIG. It is a graph of the concentrate temperature and the distillation rate which were obtained by the preliminary test in Example 1. 7 is a table showing the results obtained in the preliminary test in Example 3. 15 is a graph of the concentrate temperature and the non-volatile component concentration obtained in the preliminary test in Example 3. FIG. 15 is a graph of the concentrate temperature and the distillation rate obtained in the preliminary test in Example 3.

  Hereinafter, a solution processing apparatus according to the present invention and an embodiment (embodiment) for carrying out a solution processing method according to the present invention will be described with reference to the drawings as appropriate.

First, an outline of a solution processing apparatus according to the present embodiment will be described with reference to FIG.
<< Outline of Solution Processing Device According to the Present Embodiment >>
The solution processing apparatus 1A according to the present embodiment is an apparatus for separating an organic solvent as a distillate vapor G4 from a liquid to be treated L1 containing an organic solvent and a non-volatile component.
Then, as shown in FIG. 1, the solution processing apparatus 1A includes a first gas-liquid separation unit 10 (a first gas-liquid separation container 11 and a first evaporator 12) and a second gas-liquid separation unit 20 (a second gas-liquid separation unit). The separation container 21, the second evaporator 22), and the control means 30.
In addition, the solution processing apparatus 1A connects the respective members (and the outside) by the pipes t1 to t11, and adjusts the flow of the solution (liquid to be treated, concentrate) inside the pipes and the respective members. , Pumps P1 and P2 and valves V1 to 5 are provided.
Further, the solution processing apparatus 1A includes solid removing means 40, and also includes instruments such as flow meters F1 to F4, liquid level meters S1 and S2, and thermometers T1 and T2.
Next, each member of the solution processing apparatus 1A according to the present embodiment will be described with reference to FIG.

<First gas-liquid separation means>
The first gas-liquid separation unit 10 is a unit that heats the liquid to be treated L1 to distill a vapor, and also allows a part of the concentrated liquid to be retained.
The first gas-liquid separation unit 10 is configured to include the first gas-liquid separation container 11 and the first evaporator 12.
In the first gas-liquid separation means 10, control is carried out so that non-volatile components contained in the liquid to be treated are not deposited, but a detailed control method will be described in detail later.

(First gas-liquid separation container)
In the first gas-liquid separation container 11, the liquid to be treated L1 supplied through the pipe t1 and the vapors G1 and G3 supplied through the pipes t4 and t9 are condensed and flowed down by a gas-liquid separator 13 described later. The liquid and the concentrated liquid supplied through the pipe t4 are held at the bottom of the container in a predetermined amount, and caned out at the predetermined flow rate from the bottom.
Further, the first gas-liquid separation container 11 causes the vapor which is separated by the gas-liquid separator 13 among the vapors G1 and G3 supplied through the pipes t4 and t9 to be distilled from the top of the container. , And is delivered to the outside as distillate vapor G4 via the pipe t10.
The first gas-liquid separation container 11 is provided with the gas-liquid separator 13 inside the container and above the connection points of the pipes t1, t4, and t9, and is held at the bottom of the container. A liquid level gauge S1 that measures the height of the liquid surface of the concentrate (including the liquid to be treated L1) and a thermometer T1 that measures the temperature of the concentrate are provided.

The first gas-liquid separation container 11 has a tower-like shape in FIG. 1, but the shape is not particularly limited, and the size may be appropriately set according to the processing amount of the liquid L1 to be treated, etc. .
Further, the gas-liquid separator 13 is not particularly limited as long as it is a device capable of separating a liquid from gas, and for example, known devices such as a mist eliminator and a cyclone-type gas-liquid separator can be applied.

(1st evaporator)
The first evaporator 12 is cooled down from the first gas-liquid separation container 11 and heats and evaporates the concentrate supplied through the pipes t2 and t3. Then, the first evaporator 12 supplies the generated vapor G1 and the heated concentrate to the first gas-liquid separation container 11 through the pipe t4.

  The first evaporator 12 is not particularly limited as long as it is an apparatus capable of heating and evaporating the concentrate, and various types such as multi-tube type, plate type, jacket type, coil type, double tube type A heat exchanger etc. can be applied. Then, it is preferable to provide a strainer on the upstream side or downstream side of the first evaporator 12 in order to prevent clogging and the like.

<Second gas-liquid separation means>
The second gas-liquid separation unit 20 is a unit that heats the concentrated solution discharged from the first gas-liquid separation unit 10 to distill a vapor and allows a part of the retained concentrated solution to be released.
The second gas-liquid separation unit 20 is configured to include the second gas-liquid separation container 21 and the second evaporator 22.

(Second gas-liquid separation container)
The second gas-liquid separation container 21 holds a predetermined amount of the concentrate supplied from the first gas-liquid separation container 11 via the pipe t5 at the bottom of the container and allows the bottom to flow out at a predetermined flow rate.
The second gas-liquid separation container 21 distills the vapor G2 supplied through the pipe t8 from the top of the container and supplies the vapor G2 as the vapor G3 to the first gas-liquid separation container 11 through the pipe t9.
Then, the second gas-liquid separation container 21 is provided with a liquid level meter S2 that measures the height of the liquid level of the concentrate held at the bottom of the container, and a thermometer T2 that measures the temperature of the concentrate. ing.

In addition, the 2nd gas-liquid separation container 21 is not limited to the structure of FIG. 1 like the 1st gas-liquid separation container 11. FIG.
Although not shown in FIG. 1, the second gas-liquid separation container 21 includes a gas-liquid separator 13 such as that provided in the first gas-liquid separation container 11 inside the container, and the pipe t8. It may be provided above the connection point of

(2nd evaporator)
The second evaporator 22 heats and evaporates the concentrate which is extracted from the second gas-liquid separation container 21 and supplied via the pipes t6 and t7. Then, the second evaporator 22 supplies the generated vapor G2 to the second gas-liquid separation container 21 through the pipe t8.
In addition, the thing of various structures can be applied to the 2nd evaporator 22 similarly to the 1st evaporator 12. FIG.

(Waste liquid location: place)
A wetted part, which is a place to heat the concentrate of the second evaporator 22 (the second gas-liquid separation means 20) and in contact with the concentrate, exhibits adhesion resistance to non-volatile components.
This “wetted portion” is, for example, a portion where the transfer of thermal energy from the heat medium H to the concentrate occurs in the second evaporator 22, and a member (pipe) that divides the heat medium H and the concentrate , And the like) of the wall surface of the plate (the side in contact with the concentrate).

(Wearing point: Status)
This "showing the adhesion resistance to the non-volatile component" indicates that the treatment is performed such that the deposited non-volatile component hardly adheres, specifically, It is in the "coated state" or "flat state" with the adhesive material.

  The "state coated with the adhesion resistant material" is a state in which the adhesion resistant material is coated at a thickness of 1 to 100 μm, preferably 5 to 50 μm with respect to the wetted portion. By setting the thickness of the adhesion resistant material to a predetermined value or more, the adhesion resistance can be made reliable, and by setting the thickness of the adhesion resistant material to a predetermined value or less, the heat transfer efficiency decreases. Can be suppressed.

And as the adhesion resistant material, for example, as an organic material, (meth) acrylic resin, epoxy resin, urethane resin, silicone resin, fluorine resin, polyimide resin, polyetheretherketone resin, polyolefin resin, etc. may be mentioned. Examples of the inorganic material include, but are not limited to, metal oxide-containing paints exhibiting adhesion resistance, carbon-containing paints and the like.
In particular, in the case of a liquid to be treated containing a photoresist (resin) to be described later, the adhesion resistant material is at least one of a fluorocarbon resin, a polyetheretherketone resin, a metal oxide containing paint, and a carbon containing paint. One is preferred.
Specific examples of the fluorocarbon resin include polytetrafluoroethylene, perfluoroalkoxyalkane, tetrafluoroethylene-ethylene copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer and the like.

The “flat state” is a state in which the surface roughness is 1 μm or less. And the method of making it a "flat state" is a method of making surface roughness into a predetermined value or less by performing polishing processing, such as electrolytic polishing and buffing, to the wetted part of the 2nd evaporator 22. Alternatively, a material (plate material or the like) having a surface roughness equal to or less than a predetermined value may be selected and applied to the wetted part of the second evaporator 22.
In addition, this surface roughness is arithmetic mean roughness (Ra) in detail.

(Solid removal means)
The solid removal means 40 is a means for removing a solid (such as precipitated non-volatile components) contained in the concentrate from the concentrate. The solid removing means 40 plays the role of preventing the inflow of solid into a pump described later.
The solid removing means 40 is not particularly limited as long as it is an apparatus capable of separating a solid from a liquid, and, for example, a bucket strainer, a filtration filter, a hydrocyclone, a centrifugal settling device, a static settling device or the like can be applied.
In addition, although the solid removal means 40 is provided between the 2nd gas-liquid separation container 21 and the 2nd evaporator 22 with high possibility that a non volatile matter precipitates in FIG. 1, it is a 1st gas-liquid separation container It may be provided between 11 and the first evaporator 12.

<Pump>
The pump P1 transfers the concentrated liquid from the first gas-liquid separation container 11 to the first evaporator 12 through the pipes t2 and t3 and a pipe from the first gas-liquid separation container 11 to the second gas-liquid separation container 21. Send the concentrate through t2 and t5.
The pump P2 sends the concentrated solution from the second gas-liquid separation container 21 to the second evaporator 22 through the pipes t6 and t7, and the outside from the second gas-liquid separation container 21 through the pipes t6 and t11. Send the concentrate.
In addition, a pump will not be specifically limited if it is a thing of the structure which can send a liquid, A well-known pump can be applied. Further, the installation site of the pump is not limited to the installation site of FIG. 1 as long as the concentrate can be fed appropriately between the members, and the number of installed pumps may be increased or decreased appropriately.

<Valve>
The valve V1 adjusts the flow rate of the liquid to be treated L1 supplied from the outside to the first gas-liquid separation container 11 via the pipe t1.
The valve V2 adjusts the flow rate of the concentrate supplied from the first gas-liquid separation container 11 to the first evaporator 12 through the pipes t2 and t3.
The valve V3 adjusts the flow rate of the concentrate supplied from the first gas-liquid separation container 11 to the second gas-liquid separation container 21 through the pipes t2 and t5.
The valve V4 adjusts the flow rate of the concentrate supplied from the second gas-liquid separation container 21 to the second evaporator 22 through the pipes t6 and t7.
The valve V5 adjusts the flow rate of the concentrate discharged from the second gas-liquid separation container 21 to the outside through the pipes t6 and t11.
The valve is not particularly limited as long as the flow rate of the liquid can be adjusted by adjusting the open / close level (the degree to which the flow path is open / closed) or the like, and a known valve is applied. be able to. Further, the installation site of the valve is not limited to the installation site of FIG. 1 as long as the flow rate of the concentrate can be appropriately adjusted between the respective members, and the number of installed valves may be increased or decreased appropriately.

<Instrument>
The solution processing apparatus 1A is a flow meter F1, F2, F3, F4 that measures the flow rate of the solution (liquid to be treated, concentrate) in each pipe, in addition to the liquid level gauges S1 and S2 and the thermometers T1 and T2. Equipped with
These instruments are not particularly limited as long as desired information can be obtained, and known instruments can be applied.

<Control means>
The control unit 30 is a unit that reads data from each meter and controls a valve or the like based on the data. The control unit 30 is provided with a storage unit (not shown) that stores data serving as a reference of control.
The control method by the control means 30 will be described in detail later.

  The control unit 30 is realized by an execution process of a program by a CPU (Central Processing Unit), a dedicated circuit, or the like. The storage unit provided in the control unit 30 can be configured by a general storage device such as a random access memory (RAM), a read only memory (ROM), a hard disk drive (HDD), or a flash memory.

Next, the to-be-processed liquid used as the object of a process of the solution processing apparatus which concerns on this embodiment is demonstrated.
<< liquid to be treated >>
The liquid to be treated L1 is a solution containing an organic solvent and a non-volatile component.
The liquid to be treated L1 is, for example, a peeling liquid containing a resin (nonvolatile component) called a photoresist which is generated in a photolithography process in manufacturing a liquid crystal substrate or a semiconductor integrated circuit.

Examples of the organic solvent of the liquid L1 to be treated include, but are not limited to, monoethanolamine, dimethyl sulfoxide, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Absent.
Examples of the non-volatile component of the liquid L1 to be treated include resins (photosensitive resin materials) such as the photoresist described above, and specifically, novolak resin is assumed, but it is limited to these. Absent.
In addition, as for content of the non-volatile component (resin) contained in the to-be-processed liquid L1, it is preferable that it is 0.1-5.0 mass% from a viewpoint of implementing isolation | separation processing appropriately.

The “non-volatile component” of the liquid L1 to be treated is a component that does not volatilize during operation of the solution processing apparatus, and more specifically, the evaporator (the first evaporator 12 and the second evaporator 22) of the solution processing apparatus. The boiling point at the operating pressure is a component higher than the heating temperature of the evaporator. Therefore, as the non-volatile components, in addition to the above-mentioned resins, suspended substances such as inorganic particles generated at the time of production of liquid crystal substrates and semiconductor integrated circuits, and high-boiling components (for example, And the like) components such as sorbitol contained in a corrosion inhibitor and an anticorrosive.
In addition, as for content (total amount) of all the non-volatile components contained in the to-be-processed liquid L1, it is more preferable that it is 0.1-5.0 mass% from a viewpoint of implementing isolation | separation processing appropriately.
When not only the resin but also the suspended matter is contained as the non-volatile component in the liquid L1 to be treated, the precipitated resin coagulates the suspended matter, and as a result, a substance which precipitates in the second evaporator 22 etc. Tend to increase the size and quantity of However, in such a case, according to the present invention, the deposition component is prevented from adhering to the wetted part of the second evaporator 22, and the concentrate is appropriately heated to achieve the desired effect (excellent processing efficiency). ) Can be obtained.
In addition, the to-be-processed liquid L1 may contain water other than the above-mentioned organic solvent and non-volatile component.

Next, the solution processing method according to the present embodiment will be described with reference to FIG. The operation of the solution processing apparatus according to the above-described embodiment will also be described.
«Solution processing method according to the present embodiment»
The solution processing method according to the present embodiment includes a first gas-liquid separation step and a second gas-liquid separation step.
Each step will be described below.

<First gas-liquid separation process>
The first gas-liquid separation step is a step in which the liquid to be treated L1 is heated to distill a vapor, and a part of the concentrated liquid to be held is decanted.
Specifically, in the first gas-liquid separation step, the concentrated liquid which is extracted from the first gas-liquid separation container 11 and supplied through the pipes t2 and t3 is heated and evaporated by the first evaporator 12. Then, the vapor G1 generated in the first evaporator 12 and the heated concentrate are supplied to the first gas-liquid separation container 11 through the pipe t4. Then, the vapor separated by the gas-liquid separator 13 of the first gas-liquid separation container 11 is distilled from the top of the container, and is delivered to the outside as a distilled vapor G4 through the pipe t10. On the other hand, the concentrated liquid condensed and flowing down by the gas-liquid separator 13 of the first gas-liquid separation container 11 is held at the bottom of the container by a predetermined amount, and caned out from the bottom at a predetermined flow rate. Then, the concentrated liquid which is drained is supplied to the first evaporator 12 and the second gas-liquid separation container 21.

Then, in the first gas-liquid separation step, the first gas-liquid separation means 10 is controlled so that non-volatile components contained in the liquid to be treated are not precipitated.
Although the content of the control in a specific 1st gas-liquid separation process is illustrated below, it is not limited to the following content.

First, the evaporative concentration test is carried out in advance using the liquid to be treated L1 under the conditions simulating the conditions of the actual machine, and the distillation rate at which the precipitation of the non-volatile component starts (the “first distillation Check the temperature of the concentrate (referred to as “first concentrate temperature” as appropriate), and store the obtained first distillation rate and first concentrate temperature in the storage unit of the control means 30. .
When the distillation rate at which the non-volatile component precipitates is 83% in the previous evaporation concentration test, a value slightly smaller than the value (for example, 80%) may be set as the "first distillation rate". If the temperature of the concentrate at which the non-volatile component precipitates is 97.7 ° C., a value slightly smaller than the value (eg, 97 ° C.) may be set as the “first concentrate temperature”.

In the first gas-liquid separation step, the control means 30 reads out the flow rate data of the liquid to be treated L1 of the flow meter F1 and the flow rate data of the concentrate of the flow meter F2. Then, the control means 30 calculates the distillation rate of the first gas-liquid separation means 10 based on these data, and compares it with the first distillation rate stored in the storage unit. When the distillation rate is equal to or higher than the first distillation rate, control to increase the level of the opening degree of the valve V1 (degree of opening of the flow path) and control to increase the level of the opening degree of the valve V3 The control means 30 implements at least one of the controls. On the other hand, when the calculated distillation rate is too low, the control means 30 may perform control reverse to the control described above.
Further, in the first gas-liquid separation step, the control means 30 reads out temperature data of the thermometer T1. Then, the control means 30 compares the temperature of the read-out concentrate with the temperature of the first concentrate stored in the storage unit. Control to lower the heating temperature of the first evaporator 12 (decrease the temperature of the heat medium H, reduce the flow rate of the heat medium H) when the temperature of the concentrate becomes equal to or higher than the first concentrate temperature The control means 30 carries out at least one of the control of increasing the level of the opening degree of V1 and the control of increasing the level of the opening degree of the valve V3. On the other hand, when the temperature of the concentrate is too low, the control means 30 may perform control reverse to the control described above.
Note that the timing of control (data readout, comparison, control of valves, etc.) by the control means 30 may be appropriately set to a predetermined interval or continuously, and further, after being in a steady state, the timing may be set. The setting may be to widen the timing interval (or to stop the control). The same applies to the following control in this regard.

In the first gas-liquid separation step, the following control may be performed from the viewpoint of setting the retention amount of the concentrate in the first gas-liquid separation container 11 within a predetermined range.
In the first gas-liquid separation step, the control means 30 reads out the liquid level data of the liquid level gauge S1. Then, the control means 30 calculates the amount of the concentrate held in the first gas-liquid separation container 11 based on this data, and the predetermined amount (upper limit amount, lower limit amount) stored in the storage unit Compare. When the calculated amount of the concentrate reaches the upper limit amount, at least one of the control of increasing the level of the opening of the valve V3 and the control of decreasing the level of the opening of the valve V1 is controlled by the control means 30. Will carry out. Further, when the calculated amount of the concentrate reaches the lower limit amount, control opposite to the above control may be performed.

The above-mentioned "distillation rate" in the first gas-liquid separation step means, for example, that the liquid L1 to be treated is supplied at 1000 kg / h to the first gas-liquid separation container 11, and the concentrate is 200 kg / h via the pipe t5. When it is supplied to the 2nd gas-liquid separation container 21, it can calculate with 80% (= (1000-200) / 1000 x 100). That is, the distillation rate in the first gas-liquid separation process (the first gas-liquid separation means 10) can be calculated based on the flow rate data of the flow meter F1 and the flow meter F2.
Further, the state of “deposition of non-volatile component” described above is a state in which non-volatile components deposited by heating the liquid to be treated L1 are attached to the wall surface of the evaporator, piping, and the like. In other words, the non-volatile components are deposited and deposited on the evaporator (the first evaporator 12, the evaporator used in the evaporative concentration test), whereby the overall heat transfer coefficient (non-volatile components deposited) exhibited by the original evaporator is The coefficient is reduced by 10% or more from the overall heat transfer coefficient of the evaporator in a state in which the heat transfer efficiency is not lowered at all. Note that the overall heat transfer coefficient U, which is a coefficient indicating the performance of the evaporator, is “Q (exchange heat quantity: kcal / hr) = U (overall heat transfer coefficient: kcal / m ² hr ° C.) × A (heat transfer area: It can calculate from the formula of m ² ) × ΔT (average temperature difference between the medium to be heated and the heat medium: ° C.) ”.

<Second gas-liquid separation process>
The second gas-liquid separation step is a step of heating the concentrated solution drained in the first gas-liquid separation step to distill a vapor and partially discharging the retained concentrated solution.
Specifically, in the second gas-liquid separation step, the concentrated liquid which is extracted from the second gas-liquid separation container 21 and supplied through the pipes t6 and t7 is heated and evaporated by the second evaporator 22. Then, the vapor G2 generated in the second evaporator 22 is supplied to the second gas-liquid separation container 21 through the pipe t8. Then, this vapor is distilled as vapor G3 from the top of the second gas-liquid separation container 21, and is supplied to the first gas-liquid separation container 11 through the pipe t9.

Then, in the second gas-liquid separation step, the temperature of the retained concentrate is controlled to be equal to or lower than a predetermined temperature at which the increase in the distillation rate stagnates.
Although the content of the control in a specific 2nd gas-liquid separation process is illustrated below, it is not limited to the following content.

First, the evaporative concentration test is performed in advance using the target liquid L1 to be treated under the conditions simulating the conditions of the actual machine, and the temperature at which the increase in the distillation rate stagnates (appropriately, “limit concentrate temperature” ) And store the obtained limit concentrate temperature in the storage unit of the control means 30.
If the temperature at which the increase in the distillation rate stagnates in the previous evaporative concentration test is 99.4 ° C, a value slightly smaller than the value (for example, 99 ° C) is set as the "limit concentrate temperature". It is also good.

  In the second gas-liquid separation step, the control means 30 reads out temperature data of the thermometer T2. Then, the control means 30 compares the temperature of the read-out concentrate with the limit concentrate temperature stored in the storage unit. When the temperature of the concentrate exceeds the limit concentrate temperature, the control to increase the level of the opening of the valve V5, the control to increase the level of the opening of the valve V3, the heating temperature of the second evaporator 22 is lowered. The control means 30 carries out at least one of the controls of decreasing the temperature of the heat medium H and decreasing the flow rate of the heat medium H. When the temperature of the concentrate is too low, the control means 30 may perform control reverse to the control described above.

In the second gas-liquid separation step, when the concentrate L2 is discharged from the pipe t11 to the outside, a predetermined amount may always be discharged under the control as described above, but as described below, it is performed at a predetermined timing. It may be configured to discharge.
Specifically, in the second gas-liquid separation step, the control means 30 reads out the liquid level data of the liquid level gauge S2. Then, the control means 30 calculates the amount of the concentrate held in the second gas-liquid separation container 21 based on this data, and the predetermined amount (upper limit amount, lower limit amount) stored in the storage unit Compare. The control to close the valve V5 from open to open is performed at the timing when the calculated amount of the concentrate reaches the upper limit, and the control from open to close the valve V5 is performed at the timing when the lower limit is reached. It may be
Further, in the second gas-liquid separation step, the control means 30 reads out temperature data of the thermometer T2. Then, the control means 30 compares the temperature of the read-out concentrate with the limit concentrate temperature stored in the storage unit. At the timing when the temperature of the concentrate reaches the limit concentrate temperature, control is performed to close the valve V5 and open it. The timing when the valve V5 is changed from open to closed may be timing when the amount of concentrate calculated based on the liquid level data of the liquid level gauge S2 reaches the lower limit amount as described above.

(Flow rate of concentrate in second gas-liquid separation process)
In the second gas-liquid separation step, the flow rate of the concentrate in the second evaporator 22 is such that the deposited non-volatile component is not deposited, specifically, 0.5 to 2.0 m / s, preferably 1 m / s. Control to be s or more.
By setting the velocity of the concentrate in the second evaporator 22 to a predetermined value or more, even if the non-volatile component is deposited, the deposition of the deposited component in the second evaporator 2 can be suppressed, so It is possible to suppress the adhesion of the precipitation component to the place at a very high level.
Specifically, the following control is performed.

In the second gas-liquid separation step, the control means 30 reads out the flow rate data of the flow meter F3. Then, the control unit 30 calculates the flow velocity of the concentrate in the second evaporator 22 calculated from the flow rate data read out and the predetermined flow velocity (for example, 0.5 m / s described above) stored in the storage unit. Compare. When the flow rate of the concentrate becomes less than the predetermined flow rate, the control means 30 carries out control to intensify the level of the liquid delivery of the pump P2. On the other hand, when the flow rate of the concentrate is too high, the control means 30 may perform control reverse to the control described above.
The flow rate of the concentrate in the second evaporator 22 can be calculated from the flow rate data of the flow meter F3 and the cross-sectional area of the flow passage through which the concentrate of the second evaporator 22 flows. For example, when the second evaporator 22 is a multi-tubular heat exchanger and the concentrate flows in a plurality of tubes, the total cross-sectional area is calculated by summing the cross-sectional areas inside the tubes, and the value of the flow rate data ( The flow rate (m / s) of the concentrate can be calculated by dividing m ³ / s) by the total cross-sectional area (m ² ).

(Flow rate of the concentrate in the second gas-liquid separation process: Judgment based on the formula for settling velocity)
When the fluid is laminar, the particle density 密度_p (kg / m ³ ), the fluid density _{f f} (kg / m ³ ), the typical particle diameter d _p (m), the gravitational acceleration g (m / s ² ) When the fluid viscosity η (Pa · s) is used, the sedimentation velocity V (m / s) of the particles can be represented by “V = (ρ _p −ρ _f ) d _p ² · g / (18))”.
This equation is a equation known as a equation for calculating the sedimentation velocity, and is an equation that is suitable when the Reynolds number is less than 6, but it is particularly suitable when the diameter of the target particles is 1 mm or less Do.
For example, assuming that particles larger than 1 mm in diameter are excluded with a strainer to avoid clogging problems in piping etc. and the representative diameter of the particles is defined as 1 mm, the sedimentation velocity of the particles is fluid Assuming that the density of 1000 kg / m ³ , the density of particles 2000 kg / m ³ , and the viscosity of the fluid 0.01 Pa · s, it can be calculated as about 0.05 m / s. The Reynolds number in this case is 5.45, which is less than six.
Therefore, when the sedimentation velocity of particles in the fluid (about 0.05 m / s) is taken into consideration, the second evaporator 22 is made by flowing the concentrate at a flow velocity (0.5 m / s or more) which is 10 times this velocity. It is understood that the above-mentioned judgment that deposition of precipitation components in the inside can be prevented is appropriate.

«Functional effect»
According to the solution processing apparatus and the solution processing method according to the present embodiment as described above, the following effects can be achieved.
In the solution processing apparatus and the solution processing method according to the present embodiment, a first gas-liquid separation unit (first gas-liquid separation step) that controls non-volatile components contained in the liquid to be treated not to be precipitated; The gas-liquid separation process is performed by the second gas-liquid separation means (second gas-liquid separation process) exhibiting adhesion resistance to the non-volatile components. That is, the solution processing apparatus and the solution processing method according to the present embodiment not only carry out the gas-liquid separation process in two steps, but also the liquid to be treated in the second gas-liquid separation means (second gas-liquid separation step). Even if the evaporation treatment is carried out under such a high level of conditions that the non-volatile component precipitates, it is possible to suppress the decrease in the treatment efficiency associated with the deposition of the precipitated components. Therefore, according to the solution processing apparatus and the solution processing method according to the present embodiment, excellent processing efficiency can be exhibited even if non-volatile components of the liquid to be treated are deposited.

«Modification»
As mentioned above, although the solution processing apparatus and the solution processing method which concern on this embodiment were demonstrated, this embodiment is not limited to this, For example, it can change as follows.

In the solution processing apparatus 1A of FIG. 1, the first gas-liquid separation container 11 and the first evaporator 12 are separately provided. However, as in the solution processing apparatus 1B shown in FIG. The first gas-liquid separation unit 100 may be integrated by being installed in the gas-liquid separation container 101.
The first gas-liquid separation unit 100 shown in FIG. 2 is a heat transfer pipe 102 (first heat transfer tube) in which the heat medium H flows so that the concentrate held in the bottom of the first gas-liquid separation container 101 can be heated. It comprises the evaporator 102).

  As described above, the second evaporator 22 is not particularly limited as long as it is an apparatus capable of heating and evaporating the concentrate, and the plate type heat exchanger 202 (second evaporator 202) as shown in FIG. 2 is also used. Good.

In the second gas-liquid separation means 20 shown in FIG. 1, there is a high possibility that the concentrated liquid is likely to be solidified (or the viscosity is high and the flow is difficult to flow) by increasing the concentration of the non-volatile components. Therefore, you may provide the heating means heated to the level which does not solidify the concentrate in the 2nd gas-liquid separation means 20 (or the level of the viscosity which can be sent by pump P2).
The heating means is a heat from the outside with respect to the place where the concentrate flows (specifically, the bottom part where the concentrate of the second gas-liquid separation container 21 is held, and the pipes t6, t7, t11) If it is an apparatus which adds, it will not be limited in particular, but a thermal solvent storage tank, a heater, etc. which can immerse a heating location in a heat carrier are mentioned.

Although the case where the wetted part in contact with the concentrated liquid of the second evaporator 22 shown in FIG. 1 exhibits adhesion resistance to the non-volatile component has been described, the part exhibiting adhesion resistance is limited to this wetted part. I will not.
For example, at the place where the concentrate flows in the second gas-liquid separation means 20 (specifically, the bottom part of the second gas-liquid separation container 21 where the concentrate is held, and the piping t6, t7, t11) The inner surface in contact with the concentrate may also be configured to exhibit adhesion resistance.
In addition, although it is good also as a structure which exhibits adhesion resistance also about the liquid contact location in the 1st evaporator 12, while the expense of processing generate | occur | produces, the heat conductivity in the 1st evaporator 12 falls and processing efficiency as a whole Is expected to drop slightly.

Although the configuration for controlling the valve V5 based on the amount of the concentrate held in the second gas-liquid separation container 21 shown in FIG. 1 has been described, the change speed of the liquid level of the concentrate (the speed at which the liquid level rises) The valve 5 may be controlled based on
For example, the control means 30 reads out the liquid level data of the liquid level gauge S2. Then, the control means 30 compares the rate of change of the liquid level of the concentrate in the second evaporator 22 calculated from the read liquid level data with the predetermined speed stored in the storage unit. Control may be performed such that the valve V5 is closed → opened at the timing when the rate of change of the liquid surface of the concentrate becomes less than a predetermined speed.

When the non-volatile component (photoresist) contained in the liquid L1 to be treated is a component containing a sulfur atom, for example, a resist comprising a 1,2-naphthoquinone diazide sulfonic acid ester (NQD) compound which is a photosensitizer In the second gas-liquid separation container 21, the “nonvolatile component amount” and the “viscosity” may be measured as described below.
The measurement of the NQD-based compound (nonvolatile component) contained in the concentrated liquid of the second gas-liquid separation container 21 can be calculated from data obtained using a fluorescent X-ray sulfur analyzer. Here, since sulfur atoms emit fluorescent X-rays of energy of about 2.3 keV by irradiation of fluorescent X-rays, quantitative analysis of sulfur concentration by measuring X-ray dose by sulfur atoms in the spectrum. It can be performed. Then, based on the result of quantitative analysis of the sulfur concentration and a calibration curve prepared in advance, the “nonvolatile component amount” and “viscosity” in the concentrated liquid of the second gas-liquid separation container 21 can be calculated.
In addition, when performing such a measurement, while providing piping which extracts and returns a part of concentrates in the lower part of the 2nd gas-liquid separation container 21, a T-shaped joint and a valve are provided in the said piping, By connecting a pipe that supplies a fluorescent X-ray sulfur analyzer with a T-shaped wire hand, it can be configured to be able to measure continuously.
Then, the valve V5 is controlled based on the “nonvolatile component amount” and the “viscosity” obtained by measuring the concentrate in the second gas-liquid separation container 21 (when the nonvolatile component amount is a predetermined amount or more Alternatively, the valve V5 may be closed → open at timing when the viscosity becomes equal to or higher than a predetermined value.

  Next, examples of the present invention will be described.

Example 1
(Liquid to be treated)
A liquid to be treated comprising 5% by mass of water, 28.2% by mass of monoethanolamine, 65.8% by mass of diethylene glycol monobutyl ether, and 1% by mass of a photoresist as a nonvolatile component was prepared.

(Preliminary examination)
The liquid to be treated was subjected to an evaporation concentration test (preliminary test) under a pressure condition of 2 kPaabs, and the distillation rate, the concentration of nonvolatile components (in the distillate) and the temperature of the concentrate (boiling point) were confirmed. In addition, while confirming the timing when precipitation of the non-volatile component starts during this test, the timing at which the increase in the distillation rate stagnates was identified as the evaporation limit.
The results of this pre-test are shown in Figures 3A-C.

(Pre-test: results)
In the preliminary test, the distillation rate was 83%, and the rise in temperature of the concentrate stagnated, and at this timing, the precipitation of the non-volatile components could be confirmed. And the concentrate temperature at a distillation rate of 83% was 97.7 ° C.
It was also confirmed that the distillation rate stagnated at 95%. And, the liquid temperature at a distillation rate of 95% was 99.4 ° C.
From the above results, the “first distillation rate” in the first gas-liquid separation step in this test is set to 80%, the “first concentrate temperature” is set to 97 ° C., and the “limit in the second gas-liquid separation step is The concentrate temperature "was set to 99 ° C.

(Main test: solution processing device)
In this test of Example 1, the solution processing apparatus 1A shown in FIG. 1 was used. And the liquid contact point (heat transfer surface of the inner wall of the tube heated by the heat medium H) of the multi-tube type heat exchanger which is the second evaporator 22 has a surface roughness of 0.7 μm at the beginning It electropolished to 0.1 micrometer.

(Main test: control)
Regarding control of the solution processing apparatus 1A, in the steady state, the distillation rate of the first gas-liquid separation vessel 11 is 80% or less of the “first distillation rate” and the concentration held in the first gas-liquid separation vessel 11 The heating temperature of the first evaporator 12 and the opening / closing levels of the valves V1, V2, and V3 were set (controlled) such that the temperature of the liquid was 97 ° C. or less of the “first concentrate temperature”. In addition, the amount of the concentrate held in the first gas-liquid separation container 11 was monitored so as not to exceed a predetermined amount.
Further, with regard to control of the solution processing apparatus 1A, in the steady state, the valve V5 is opened at the timing when the temperature of the concentrate held in the second gas-liquid separation container 21 reaches 99 ° C. of “limit concentrate temperature”. Control was performed to withdraw the concentrate to a predetermined liquid level.
Then, the flow rate of the pump P2 was set such that the flow rate of the concentrate in the second evaporator 22 was 0.5 m / s.

(Main examination: Results)
According to the main test of Example 1, the final distillation rate (= distilled vapor G4 amount / liquid L1 amount × 100) could be increased to 95%. Further, the recovery rate of the organic solvent (= the amount of the organic solvent in the distillate vapor G4 / the amount of the organic solvent in the liquid to be treated L1 × 100) was 96%. Moreover, the density | concentration of the non-volatile component in the concentrate L2 discharged | emitted outside was 20 mass%.
And within the processing time (about 1000 hours) of the main test of Example 1, fixation of the deposited non-volatile component in the wet part of the 2nd evaporator 22 was not able to be checked.
From the above results, according to the solution processing apparatus and the solution processing method according to Example 1, it was confirmed that excellent processing efficiency can be exhibited.

Example 2
About Example 2, only a different point from Example 1 mentioned above is shown below.

(Main test: control)
The control based on the temperature of the concentrate held in the second gas-liquid separation container 21 was not performed for the control of the solution processing apparatus 1A. Instead, the valve V5 was controlled based on the rate of change of the liquid level of the concentrate held in the second gas-liquid separation container 21 (the rate of rise of the liquid level). Specifically, the valve V5 was opened at the timing when the rate of change of the liquid surface of the concentrate became significantly slow, and the concentrate was extracted to a predetermined liquid level.

(Main examination: Results)
According to the test of Example 2, the final distillation rate could be increased to 94%. Moreover, the density | concentration of the non-volatile component in the concentrate L2 discharged | emitted outside was 17 mass%.
And in the processing time (about 1000 hours) of the main test of Example 2, fixation of the deposited non-volatile component in the wet part of the 2nd evaporator 22 was not able to be checked.
From the above results, it was confirmed that the solution processing apparatus and the solution processing method according to Example 2 can exhibit excellent processing efficiency.

«Comparative Example 1»
About the comparative example 1, only a different point from Example 1 mentioned above is shown below.

(Main test: solution processing device)
The surface roughness of the wetted portion (heat transfer surface of the inner wall of the tube heated by the heat medium H) of the multitubular heat exchanger, which is the second evaporator 22 of Comparative Example 1, remains at 0.7 μm. Met.

(Main examination: Results)
According to the main test of Comparative Example 1, since the pressure of the pump P2 started to rise when the distillation rate exceeded 85%, the operation of the apparatus was stopped. After that, when the liquid contact point (heat transfer surface of the inner wall of the tube heated by the heat medium H) of the multi-tubular heat exchanger which is the second evaporator 22 was confirmed, the deposited non-volatile component was sticking. , The concentrate did not flow.

Example 3
(Liquid to be treated)
As a to-be-processed liquid, the solution which contained the inorganic particle (suspension substance) and resin which generate | occur | produce at the manufacturing process of a semiconductor integrated circuit in the organic solvent of isopropyl alcohol ethylbenzene was prepared.
In addition, although the density | concentration of the non-volatile component (total of an inorganic particle and resin) contained in to-be-processed liquid was 3 mass%, the non-volatile component (resin) which is melt | dissolving using a filtration filter is test | inspected As a result, it was confirmed that the concentration of the resin contained in the liquid to be treated was 0.3% by mass.

(Preliminary examination)
The first evaporation and concentration test (preliminary test) was carried out under the pressure condition of normal pressure for the liquid to be treated, and the distillation rate, non-volatile component concentration (in the distillate), and concentrated liquid temperature (boiling point) were confirmed. . Moreover, the timing which precipitation of a non-volatile component started during this test was confirmed.
Moreover, while using the concentrate obtained as distillation rate 60% in the above-mentioned 1st evaporation concentration test, the 2nd evaporation concentration test is conducted using an evaporator in which the wetted part is coated with a fluorine resin, and concentration The timing at which the fluidity of the liquid can not be secured was identified as the evaporation limit.
The results of this first evaporation concentration test are shown in Figures 4A-C.

(Pre-test: results)
In the first evaporation concentration test, precipitation of the non-volatile components could be confirmed at a timing when the distillation rate was 64%. The concentrate temperature was 91.7 ° C. when the distillation rate was 64%.
Furthermore, in the second evaporation concentration test, when the viscosity of the concentrate exceeds 0.3 Pa · s, the flowability is degraded, and the predetermined conditions specified by the capacity of the pump and the size of the pipe due to increase in pressure loss such as pipe friction However, it has been confirmed that if the concentration of the non-volatile component in the concentrate is 23% by mass or less, the flowability above a certain level can be ensured. The distillation rate was 85% when the concentration of the non-volatile component in the concentrate was 23% by mass.
From the above results, the “first distillation rate” in the first gas-liquid separation step in the present test was set to 60%, and the “first concentrate temperature” was set to 90 ° C. In addition, the “limit concentrate temperature” in the second gas-liquid separation step in this test was set to 100 ° C., which is the temperature at which the viscosity of the concentrate becomes 0.3 Pa · s.

(Main test: solution processing device)
In this test of Example 3, a solution processing apparatus 1B shown in FIG. 2 was used. Then, the wetted portion (heat transfer surface of the inner wall of the plate heated by the heat medium H) of the plate type heat exchanger which is the second evaporator 202 was coated with a fluorine resin layer having a thickness of 20 μm.

(Main test: control)
Regarding control of the solution processing apparatus 1B, in the steady state, the distillation rate of the first gas-liquid separation vessel 101 is 60% or less of the “first distillation rate” and the concentration held in the first gas-liquid separation vessel 101 The heating temperature of the first evaporator 102 and the opening / closing levels of the valves V1, V2, and V3 were set (controlled) such that the temperature of the liquid was 90 ° C. or less of the “first concentrate temperature”. In addition, the amount of the concentrate held in the first gas-liquid separation container 11 was monitored so as not to exceed a predetermined amount.
Further, with regard to control of the solution processing apparatus 1B, in the steady state, the open / close level of each valve such that the temperature of the concentrate held in the second gas-liquid separation container 201 becomes 100 ° C. or less of the “critical concentration temperature”. Was set (controlled).
Then, the flow rate of the pump P12 was set (controlled) such that the flow rate of the concentrate in the second evaporator 202 was 0.5 m / s.

(Main examination: Results)
According to this test of Example 3, the distillation rate could be increased to 85%.
Then, within the processing time (about 2000 hours) of the main test of Example 3, although the fixation of the non-volatile component deposited at the wetted part of the second evaporator 202 can be slightly confirmed, the processing capacity is lowered. I was able to finish the test.
From the above results, it was confirmed that the solution processing apparatus and the solution processing method according to Example 3 can exhibit excellent processing efficiency.

«Comparative Example 2»
About the comparative example 2, only a different point from Example 3 mentioned above is shown below.

(Main test: control)
The flow rate of the pump P12 was set (controlled) such that the flow rate of the concentrate in the second evaporator 202 was 0.1 m / s.

(Main examination: Results)
According to the main test of Comparative Example 2, since the pressure of the pump P12 gradually increased, the operation of the apparatus was stopped. After stopping the apparatus, when the second evaporator 202 was confirmed, at the wetted part farthest from the solution supply side of the plate type heat exchanger 202, although deposition components are not adhered, they are deposited by deposition. It was confirmed that the department was closed.
Although the liquid to be treated used in Comparative Example 2 had low viscosity and density, the resin deposited in the middle of heating contained suspended substances (average particle diameter: 0.18 μm). It is assumed that the flocculated suspended matter has sedimented and deposited.

1A, 1B Solution Processing Apparatus 10, 100 First Gas-Liquid Separation Means 11, 101 First Gas-Liquid Separation Container 12, 102 First Evaporator 13, 103 Gas-Liquid Separator 20, 200 Second Gas-Liquid Separation Means 21, 201 Second gas-liquid separation vessel 22, 202 Second evaporator 30, 300 Control means 40 Solid removal means L1 Liquid to be treated L2 Concentrated liquid G4 Distilled vapor F Flow meter S Liquid level meter T Thermometer V Valve t Piping

Claims (8)

A solution processing apparatus for separating an organic solvent as distillate vapor from a liquid to be treated containing an organic solvent and a non-volatile component,
A first gas-liquid separation unit that heats the liquid to be treated, distills off the vapor, and can partially release the concentrated liquid to be held;
A second gas-liquid separation unit that heats the concentrate discharged from the first gas-liquid separation unit to distill a vapor and allows a part of the retained concentrate to be drained;
Control means for controlling the first gas-liquid separation means such that non-volatile components contained in the liquid to be treated are not precipitated in the first gas-liquid separation means;
Wetted portion in contact with the concentrate as well as a portion for heating the concentrated liquid of the second gas-liquid separation means, and coloration of the anti-adhesive properties with respect to non-volatile components,
The control means controls the distillation rate of the first gas-liquid separation means so as to obtain a distillation rate lower than a distillation rate at which precipitation of the non-volatile components contained in the liquid to be treated starts. Solution processing equipment. A pump for feeding the concentrate inside the second gas-liquid separation means at a predetermined flow rate,
2. The solution processing apparatus according to claim 1, wherein the control means controls the pump such that the predetermined flow rate is a flow rate at which the deposited non-volatile component is not deposited. The control means is configured such that the timing at which the liquid temperature of the concentrate held in the second gas-liquid separation means reaches a predetermined temperature, and the amount of the concentrate held in the second gas-liquid separation means At a timing when at least one of the timing at which the predetermined amount is reached is satisfied, control is performed so that the concentrated liquid held by the second gas-liquid separation unit can be canned until the predetermined amount is reached. The solution processing apparatus according to claim 1 or 2 , characterized in that: The solution treatment according to any one of claims 1 to 3 , wherein the liquid contact portion is in a state of being covered with an adhesion resistant material or in a state of a surface roughness of 1 μm or less. apparatus. A solution processing method for separating an organic solvent as distillate vapor from a liquid to be treated containing an organic solvent and a non-volatile component,
A first gas-liquid separation step of heating the liquid to be treated and distilling off the vapor, and partially releasing the retained concentrate;
And heating the concentrated solution in the first gas-liquid separation step to distill a vapor and a second gas-liquid separation step in which a portion of the retained concentrate is decanted.
In the first gas-liquid separation step, control is performed so that non-volatile components contained in the liquid to be treated are not precipitated,
In the second gas-liquid separation step, wetted portion in contact with the concentrate as well as a portion for heating the concentrate, and coloration of the anti-adhesive properties with respect to non-volatile components,
A solution processing method characterized in that a distillation rate in the first gas-liquid separation step is a distillation rate lower than a distillation rate at which precipitation of non-volatile components contained in the liquid to be treated starts . The solution processing method according to claim 5 , wherein in the second gas-liquid separation step, the flow rate of the concentrate is a flow rate at which the deposited non-volatile component is not deposited. In the second gas-liquid separation step, at least one of the timing at which the liquid temperature of the retained concentrate reaches a predetermined temperature, and the timing at which the amount of the retained concentrate reaches a predetermined amount The solution processing method according to claim 5 or 6 , characterized in that the concentrate is decanted until the amount of the retained concentrate reaches a predetermined amount at the timing when the above is satisfied. The solution treatment according to any one of claims 5 to 7 , wherein the wetted portion is in a state of being covered with an adhesion resistant material or in a state of a surface roughness of 1 μm or less. Method.

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