WO2016068677A1 - 증류 장치 - Google Patents
증류 장치 Download PDFInfo
- Publication number
- WO2016068677A1 WO2016068677A1 PCT/KR2015/011654 KR2015011654W WO2016068677A1 WO 2016068677 A1 WO2016068677 A1 WO 2016068677A1 KR 2015011654 W KR2015011654 W KR 2015011654W WO 2016068677 A1 WO2016068677 A1 WO 2016068677A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- distillation column
- distillation
- column
- formula
- region
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
- B01J12/02—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor for obtaining at least one reaction product which, at normal temperature, is in the solid state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/107—Alkenes with six carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
Definitions
- the present application relates to a distillation apparatus for separating and recovering a solvent and an unreacted monomer used in the polymerization process of a polyolefin elastomer.
- Polyolefin elastomers are used not only as physical reinforcing materials such as impact and flexural strength of automobile interior and exterior materials, but also in various advanced textile and sports industries due to their excellent elasticity and toughness.
- the polyolefin elastomer is polymerized by a solution polymerization method in which an olefin monomer is dissolved in a solvent and then polymerized using a catalyst, and the solvent is recovered from the polymerization solution and then commercialized through a drying process.
- a solution polymerization method in which an olefin monomer is dissolved in a solvent and then polymerized using a catalyst, and the solvent is recovered from the polymerization solution and then commercialized through a drying process.
- a large amount of solvent is used compared to the amount of the olefin monomer introduced, a large amount of energy is consumed in the process for recovering the solvent and the unreacted monomer after polymerization.
- the solvent containing the solvent and the unreacted monomer was recovered using a distillation apparatus in which two distillation columns were sequentially connected, but a large amount of energy was consumed in this process. Occurred.
- the installation cost of the distillation apparatus can be reduced, and a process for recovering a solvent and an unreacted monomer capable of separating a high purity compound is required.
- the present application relates to a distillation apparatus.
- a process for purifying a raw material including an olefin monomer and a solvent for example, 1-octene, iso-octene and n-hexane, used in a polymerization process of a polyolefin elastomer
- a solvent for example, 1-octene, iso-octene and n-hexane
- the process economy can be improved by minimizing the energy loss in the process and by separating the product to high purity.
- the distillation apparatus of the present application provides temperature and pressure conditions optimized for the separation of 1-octene, iso-octene and n-hexane using two distillation units, whereby the distillation apparatus of the present application is used.
- the solvent and unreacted olefin monomer used in the polymerization process of the polyolefin elastomer can be separated with high purity and high efficiency.
- the exemplary distillation apparatus includes two distillation units 10, 20 and a heat exchanger 30, for example, the distillation apparatus comprises a first distillation unit 10, a second one.
- the first distillation unit 10 includes a first distillation column 100, a first condenser 101, a storage tank 102, and a first reboiler 103, wherein the second distillation unit 20 is ,
- the first distillation column 100 and the second distillation column 200 are devices capable of separating the multi-component materials included in the raw materials by the difference in boiling points.
- a distillation column having various forms can be used in the distillation apparatus of the present application.
- the specific kind of distillation column that can be used in the distillation apparatus of the present application is not particularly limited, and for example, a distillation column having a general structure as shown in FIG. 1 or a dividing wall distillation column having a dividing wall therein may be used.
- the interior of the first distillation column 100 and the second distillation column 200 is shown in Figure 1, the upper region (110, 210), lower region (130, 230) and the middle region (120, 220).
- the term "upper region” means a relatively upper portion in the structures of the first distillation column 100 and the second distillation column 200, and, for example, the first distillation column 100 and the second distillation column ( In the case of dividing into three equal parts in the height or length direction of each distillation column, it may mean the uppermost part of the three divided regions.
- the "lower region” means a relatively lower portion in the structures of the first distillation column 100 and the second distillation column 200, for example, the first distillation column 100 and the second distillation column.
- the third dividing in the height or length direction of the distillation column may mean the lowest portion of the three areas divided.
- the "middle region” may refer to a middle region among three regions divided when divided into three equal heights or lengths of the distillation columns in the structures of the first distillation column 100 and the second distillation column 200. And may mean a region between the upper regions 110 and 210 and the lower regions 130 and 220 of the first distillation column 100 and the second distillation column 200.
- the upper region, the lower region and the middle region of the distillation column may be used as a concept relative to each other.
- the tops of the first distillation column 100 and the second distillation column 200 are included in the upper region, and the bottoms of the first distillation column 100 and the second distillation column 200 are included in the lower region.
- the upper region is used in the same sense as the top region, and the lower region is used in the same sense as the bottom region.
- distillation columns having 10 to 30 stages, 12 to 28 stages, or 15 to 25 stages of theoretical stages may be used.
- “theoretical stage number” means the number of virtual regions or stages in which the two phases, such as gaseous phase and liquid phase, are in equilibrium with each other in the first distillation column 100 and the second distillation column 200.
- the first distillation unit 10 is, as shown in Figure 1, the first condenser 101, the first condenser 101, each connected to the first distillation column 100, the storage tank ( 102 and a first reboiler 103, wherein the second distillation unit 20 is connected to the second distillation column 200 and the second distillation column 200, respectively, as shown in FIG.
- a second condenser 201, a storage tank 202 and a second reboiler 203 are included.
- the first distillation column 100, the first condenser 101, the storage tank 102, and the first reboiler 103 may be fluidized with each other so that the fluid introduced into the first distillation column 100 may flow.
- the second distillation column 200, the second condenser 201, the storage tank 202 and the second reboiler 203 may be fluidically connected, and the fluid introduced into the second distillation column 200. May be fluidically connected to each other to allow flow.
- the first distillation column 100 and the second distillation column 200 are fluidly connected to each other such that the bottom flow of the first distillation column 100 flows into and flows into the middle region 220 of the second distillation column 200. may be fluidically connected).
- the "condenser" is a device separately installed outside the distillation column, and means a device for cooling the flow out of the column top of the distillation column in contact with the cooling water introduced from the outside.
- the first condenser 101 of the first distillation column 100 is a device for condensing the first overhead stream F 1-2 flowing out of the top region 110 of the first distillation column 100.
- the second condenser 201 of the second distillation column 200 may be a device for condensing the second overhead stream F 2-2 flowing out of the top region 210 of the second distillation column 200.
- the "reboiler” is a heating device installed separately from the outside of the distillation column, it may mean a device for heating and evaporating the flow of the high boiling point component flowed out from the bottom of the distillation column.
- the first reboiler 103 of the first distillation column 100 is a device for heating the bottoms flow (F 1-3 ) flowing out of the bottom region 130 of the first distillation column 100
- the second reboiler 203 of the second distillation column 200 to be described later may be a device for heating the bottom flow (F 2-3 ) flowing out of the bottom region 230 of the second distillation column 200.
- the "storage tank” means a tank or a water tank temporarily storing the flow out of the distillation column, and various tanks or water tanks known in the art may be used without limitation.
- the first overhead stream F 1-2 flowing out of the overhead region 110 of the first distillation column 100 is introduced into the storage tank 102 after being condensed in the first condenser 101 and stored.
- the second overhead stream F 2-2 discharged from the overhead region 210 of the second distillation column 200 may be introduced into and stored in the storage tank 202 after condensing in the second condenser 201. Can be.
- the first distillation column 100 includes a first supply port 121
- the second distillation column 200 includes a second supply port 221.
- the first supply port 121 is located in the middle region 120 of the first distillation column 100
- the second supply port 221 is the middle region of the second distillation column 200. Located at 220.
- the raw material F 1-1 including the compound of Formula 1 and the compound of Formula 2 is introduced into the first supply port 121 of the first distillation column 100.
- R 1 is an alkyl group having 4 to 12 carbon atoms
- R 2 to R 4 are each independently hydrogen or an alkyl group having 4 to 12 carbon atoms
- R 5 is an alkyl group having 1 to 4 carbon atoms, and n is 1 to 4.
- the compound of Formula 1 may be, for example, one or more selected from the group consisting of 1-octene, iso-octene, and mixtures thereof, and the compound of Formula 2 may be n-hexane,
- the present invention is not limited thereto.
- the raw material F 1-1 introduced into the first supply port 121 of the first distillation column 100 is transferred to the middle region 120 of the first distillation column 100.
- the raw material (F 1-1 ) introduced into the middle region 120 of the first distillation column 100 is the top flow and the first distillation column flowing out of the top region 110 of the first distillation column (100).
- the bottom stream flowing out from the bottom region 130 of the first distillation column 100 may be separated into at least one flow and flow out.
- the raw material F 1-1 introduced into the first distillation column 100 flows out of the first column top flow F 1-2 and the bottom region 130 of the first distillation column 100.
- the first bottom stream (F 1-3 ), the second bottom stream (F 1-4 ) and the third bottom stream (F 1-5 ) may be separated and outflow.
- the first overhead stream F 1-2 flowing out of the overhead region 110 of the first distillation column 100 flows into the first condenser 101 and passes through the first condenser 101. Some or all of the overhead streams F 1-2 may be refluxed to the overhead zone 110 of the first distillation column 100 or may be stored as a product. In one example, the flow out of the first condenser may be refluxed into the first distillation column 100 after being stored in the storage tank 102 or stored as a product.
- the first column bottom flow F 1-3 flowing out of the column bottom region 130 of the first distillation column 100 flows into the first reboiler 103 and the first reboiler 103
- the first bottom stream F 1-3 that has passed may be introduced into the bottom region 130 of the first distillation column 100.
- the first column bottom flows F 1-3 introduced into the first reboiler 103 may be heated by high pressure steam passing through the first reboiler 103, which will be described later.
- the amount of the high pressure steam can be appropriately adjusted. For example, when sufficient heat exchange occurs in the heat exchanger 30, the high pressure steam may not be used at all, but when the heat exchange does not occur smoothly due to the flow rate of the raw material or the process disturbance, the separation efficiency may drop sharply. Can be. Accordingly, an appropriate amount of high pressure steam may be temporarily used to maintain robust separation efficiency against disturbances.
- the second bottom stream F 1-4 flowing out of the bottom region 130 of the first distillation column 100 flows into the second supply port 221 of the second distillation column 200.
- the second column bottom stream F 1-4 introduced into the second supply port 221 of the second distillation column 200 flows into the middle region 220 of the second distillation column 200, and the second distillation column
- the second bottom stream F 1-4 introduced into the middle region 220 of the 200 is the top stream flowing out of the top region 210 of the second distillation column 200 and the second distillation column 200.
- Each is separated into the bottom flow flowing out from the bottom region 230 and flows out.
- the bottom stream flowing out of the bottom region 230 of the second distillation column 200 may be separated into at least one flow and flow out.
- the flow introduced into the second distillation column 200 is the second tower flow F 2-2 and the fourth column bottom flow F 2 flowing out of the bottom region 230 of the second distillation column 200. -3 ) and the fifth bottom stream (F 2-4 ) can be separated and outflow, respectively.
- the fourth bottom stream F 2-3 flowing out of the bottom region 230 of the second distillation column 200 flows into the second reboiler 203 and passes through the second reboiler 203.
- the fourth bottom stream F 2-3 flows into the bottom region 230 of the second distillation column 200 and flows out of the bottom region 230 of the second distillation column 200.
- 2-4 can be stored as a product.
- the third column bottom stream F 1-5 flowing out of the column bottom region 130 of the first distillation column 100 and the second column top stream F 2 flowing out of the column top region 210 of the second column 200. -2 ) is introduced into the heat exchanger (30).
- the "heat exchanger" is a device installed separately from the outside of the distillation column, and performs heat exchange so that heat transfer occurs smoothly between two fluid flows having different temperatures.
- the heat exchanger 30 is the first distillation column.
- the third column bottom stream F 1-5 flowing out of the column bottom region 130 of the column 100 and the second column top stream F 2-2 flowing out of the column top region 210 of the second distillation column 200 are obtained. It may be a device for heat exchange.
- the third tower bottom stream F 1-5 and the top column region 210 of the second distillation column 200 which are high boiling point streams flowing out from the bottom region 130 of the first distillation column 100.
- the second overhead stream (F 2-2 ) which is a low boiling point flow flowing out from the heat exchanger (30)
- the energy required in the condensation and heating process using the condenser or reboiler can be reduced, 1-octene / iso-octene and n-hexane can be separated and recovered.
- the heat exchanger 30 is directly connected to a pipe through which the third column bottom flow F 1-5 of the first distillation column 100 and the second column top flow F 2-2 of the second distillation column 200 flow. Or indirectly connected. In one example, the heat exchanger 30 flows through the third column bottom flow F 1-5 of the first distillation column 100 and the second column top flow F 2-2 of the second distillation column 200. By directly connecting to the pipe, it is possible to efficiently heat exchange the third column bottom flow (F 1-5 ) and the second column top flow (F 2-2 ).
- the third column bottom flow F 1-5 and the second column top flow F 2-2 introduced into the heat exchanger 30 are heat-exchanged, and the third column bottom flow F 1 passed through the heat exchanger 30. 5 ) is refluxed to the bottom region 130 of the first distillation column 100, and the second overhead flow F 2-2 passing through the heat exchanger 30 is introduced into the second condenser 201, Some or all of the second overhead stream F 2-2 passing through the second condenser 201 may be refluxed to the overhead region 210 of the second distillation column 200 or may be stored as a product. In one example, the flow out of the second condenser 201 may be refluxed into the second distillation column 200 after being stored in the storage tank 202 or stored as a product.
- the third column bottom stream F 1-5 may be heat-exchanged with the second column head stream F 2-2 before being returned to the first distillation column 100.
- the overhead stream F 2-2 may be heat-exchanged with the third column bottom stream F 1-5 before entering the second condenser 201.
- the second overhead stream F 2-2 which is a flow of the low boiling point component flowing out of the overhead region 210 of the second distillation column 200, is refluxed to the overhead region 210 of the second distillation column 200.
- the heat is supplied to the heat exchanger (30). Accordingly, the second overhead stream F 2-2 flowing out of the second distillation column 200 may be refluxed to the second distillation column 200 at a relatively low temperature.
- the amount of heat required to condense the second overhead stream F 2-2 flowing out of the overhead region 210 of the second distillation column 200 may be reduced, and the condensation process using the second condenser 201 may be performed.
- the third column bottom stream F 1-5 which is a flow of the high boiling point component flowing out of the column bottom region 130 of the first distillation column 100, is refluxed to the column bottom region 130 of the first column 100. Before passing through the heat exchanger 30, at this time, it may be supplied with heat transferred from the second overhead stream (F 2-2 ).
- the second overhead stream F 2-2 supplies heat to the bottom region 130 of the first distillation column 100, and flows out of the top region 130 of the first distillation column 100.
- the cost can be reduced by reducing the amount of steam used in the first reboiler 103 to heat the first bottom stream F 1-3 .
- a relatively low boiling point component, n-hexane-rich stream of the components contained in the raw material (F 1-1 ) introduced into the first supply port 121 is the top of the first distillation column (100)
- the first bottom streams F 1-3 , the second bottom streams F 1-4 , and the third bottom streams F 1-5 may be discharged.
- the first overhead stream F 1-2 flowed out from the overhead region 110 of the first distillation column 100 passes through the first condenser 101 and enters the storage tank 102, and the storage tank ( Part of the flow outflow from 102 may be refluxed to the top region 110 of the first distillation column 100 and the other part may be stored as a product.
- the product may be high purity n-hexane.
- the first bottom flow (F 1-3 ) flowed out of the bottom region 130 of the first distillation column 100 is passed through the first reboiler 103, the bottom region 130 of the first distillation column 100 ), And the second column bottom stream F 1-4 may be introduced into the second supply port 221 of the second distillation column 200.
- the third column bottom stream F 1-5 is heat-exchanged with the second column top stream F 2-2 of the second distillation column 200 in the heat exchanger 30, and then, the first distillation column 100 is provided. It may be refluxed to the bottom region 130.
- the second bottom stream F 1-4 introduced into the second supply port 221 is a flow including 1-octene and / or iso-octene and a high boiling point component, and thus the second tower bottom stream.
- a relatively low boiling point component, 1-octene and / or iso-octene, among the components included in (F 1-4 ), is the second columnar stream in the columnar region 210 of the second distillation column 200.
- F 2-2 the flow of relatively high boiling components (heavy components) is the fourth bottom stream (F 2-3 ) and fifth in the bottom region 230 of the second distillation column (200) May flow to the bottom stream F 2-4 .
- the outflowing second overhead stream F 2-2 is heat-exchanged with the third column bottom stream F 1-5 of the first distillation column 100 in the heat exchanger 30, and then the second condenser 201 Passed through to the storage tank 202, a portion of the flow exited from the storage tank 202 may be refluxed to the top region 210 of the second distillation column 200 and the other portion may be stored as a product.
- the product may be high purity 1-octene and / or iso-octene.
- the flow of the high boiling point component having a relatively high boiling point among the components included in the second column top flow (F 2-2 ) is the fourth column bottom stream (F) in the bottom region 230 of the second distillation column (200).
- the fifth bottom stream F 2-4 may be utilized as fuel.
- the fifth bottom stream F 2-4 may be, for example, octenes and / or high boiling point components.
- low boiling point flow refers to a flow in which a relatively low boiling point component is rich in the raw material stream F 1-1 including low boiling point and high boiling point components, and the low boiling point flow is, for example, Means a flow out of the top region 210 of the first distillation column 100 and the second distillation column 200.
- high boiling point flow means a flow in which a relatively high boiling point component is rich among the raw material streams F 1-1 including low boiling point and high boiling point components, and the high boiling point flow is, for example.
- a relatively high boiling point component flowing out of the bottom region 230 of the first distillation column 100 and the second distillation column 200 means a rich flow.
- the term “rich flow” refers to the top region 210 of the first distillation column 100 and the second distillation column 200 than the content of the low boiling point component and the high boiling point component included in the raw material F 1-1 . It means that the content of each of the low boiling point components included in the flow flowing out from the high boiling point components included in the flow out in the bottom region 230 of the first and second distillation column 100 and 200 distillation column. .
- the low boiling point component included in the first overhead stream F 1-2 of the first distillation column 100 and the low boiling point contained in the second overhead stream F 2-2 of the second distillation column 200 are examples of the low boiling point component included in the first overhead stream F 1-2 of the first distillation column 100 and the low boiling point contained in the second overhead stream F 2-2 of the second distillation column 200.
- Each stream represented by the component means at least 50 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt% or at least 99 wt%, or the first bottom stream F of the first distillation column 100 (F). 1-3 ), the high boiling point components included in the second bottom stream (F 1-4 ) and the third bottom stream (F 1-5 ) and the fourth bottom stream (F 2-3 ) of the second distillation column (200). And a flow in which each content represented by the high boiling point component included in the fifth bottom stream F 2-4 is 50% by weight, 80% by weight, 90% by weight, 95% by weight or 99% by weight or more. can do.
- a portion of the fifth bottom stream F 2-4 flowing out of the bottom region 230 of the second distillation column 200 may be a bottom region 130 of the first distillation column 100, for example.
- the number of theoretical stages may be introduced into 13 to 23 stages of the first distillation column 100 having 15 to 25 stages. Accordingly, 1-octene and / or iso-octene, which may remain partially in the fifth column bottom stream F 2-4 , may be supplied to the column bottom region 130 of the first distillation column 100, thereby providing higher purity.
- 1-octene and / or iso-octene can be prepared with In this case, the bottom region 130 of the first distillation column 100 with respect to the flow rate (kg / hr) of the fifth bottom flow F 2-4 flowing out of the bottom region 230 of the second distillation column 200.
- the ratio of the flow rate (kg / hr) of the flow flowing into) may be 1: 0.8 to 1: 0.95, the ratio of the flow rate of the flow flowing into the column bottom region 130 of the first distillation column 100 in the above range
- the distillation apparatus of the present application satisfies the following general formula (1).
- T t -2 represents the temperature of the second columnar stream F 2-2
- T b -3 represents the temperature of the third columnar stream F 1-5 .
- the compound of Formula 1 and the compound of Formula 2 in particular, 1-octene / iso-octene and n- Hexanes can be separated with good efficiency and high purity. That is, in the distillation apparatus, by adjusting the temperature difference between the temperature of the second overhead stream F 2-2 and the third overhead stream F 1-5 to satisfy the general formula 1, the second overhead stream It is possible to maximize the heat exchange efficiency between the temperature of (F 2-2 ) and the third column bottom flow (F 1-5 ), accordingly, the compound of formula 1 and the compound of formula 2, in particular, 1-octene, iso -Octene or mixtures thereof and n-hexane can be separated with good efficiency and high purity.
- the temperature of the second overhead stream (F 2-2 ) flowing out of the top region 210 of the second distillation column 200 and the top of the bottom region 130 of the first distillation column 100 The difference in temperature of the third column bottom flow F 1-5 is not particularly limited as long as the general formula 1 is satisfied. For example, at least 8 ° C, at least 9 ° C, at least 10 ° C, at least 13 ° C, or 15 It may be at least °C.
- the temperature of the second overhead stream F 2-2 flowing out of the tower region 210 of the second distillation column 200 and the third tower bottom stream flowing out of the bottom region 130 of the first distillation column 100 ( Since the greater the difference in temperature of F 1-5 ), the better the heat exchange efficiency, the upper limit value of the difference is not particularly limited, and, for example, the agent flowing out of the top region 210 of the second distillation column 200.
- the difference between the temperature of the second column flow F 2-2 and the temperature of the third column bottom stream F 1-5 flowing out of the column bottom region 130 of the first distillation column 100 is 100 in consideration of process efficiency. Or less.
- the distillation apparatus of the present application satisfies the following general formula (2).
- P 1 represents the pressure (Kg / cm 2 g) of the top region 110 of the first distillation column 100
- P 2 is the pressure of the top region 210 of the second distillation column (200). (Kg / cm 2 g) is shown.
- the distillation apparatus of the present application satisfies the general formula (2), by using a distillation apparatus having a series structure as described above, the compound of formula 1 1-octene, iso-octene or a mixture thereof and the compound of formula 2 n-hexane can be separated with good efficiency and high purity.
- the distillation apparatus by adjusting the ratio of the pressure of the top region 110 of the first distillation column 100 and the pressure of the top region 210 of the second distillation column 200 to satisfy the general formula 2, It is possible to maximize the heat exchange efficiency between the temperature of the second overhead stream (F 2-2 ) and the third column bottom stream (F 1-5 ), accordingly, the compound of formula 1 1-octene, iso-octene Or a mixture thereof and n-hexane, a compound of Formula 2, can be separated with excellent efficiency and high purity.
- the temperature inside the first distillation column 100 may be maintained lower than the temperature inside the second distillation column 200.
- the pressure in the top region 110 of the first distillation column 100 may be maintained lower than the pressure in the top region of the second distillation column 200.
- the ratio of the pressure of the top region 110 of the first distillation column 100 and the pressure of the top region 210 of the second distillation column 200 is particularly limited as long as the general formula 2 is satisfied. It may be, for example, 3.0 or more, 4.0 or more, 5.0 or more, or 8.0 or more.
- the ratio of the pressure of the top region 110 of the first distillation column 100 and the pressure of the top region 210 of the second distillation column 200 is 200 or less in consideration of process efficiency, or 100 or less.
- the temperature of the second overhead stream F 2-2 flowing out of the overhead region 210 of the second distillation column 200 is not particularly limited as long as the general formula 1 is satisfied, and 125 ° C. to 170 ° C., for example.
- the temperature may be 130 ° C to 168 ° C or 140 ° C to 165 ° C.
- the temperature of the third column bottom stream F 1-5 discharged from the column bottom region 130 of the first distillation column 100 is not particularly limited as long as the general formula 1 is satisfied, and 120 ° C. to 145 ° C.
- the temperature may be 122 ° C to 140 ° C or 125 ° C to 135 ° C.
- the pressure in the top region 110 of the first distillation column 100 is not particularly limited as long as the general formula 2 is satisfied, and 0.05 to 0.2 Kg / cm 2 g and 0.08 to 0.18 Kg / cm 2 g or 0.1 to 0.16 Kg / cm 2 g.
- the pressure of the top region 210 of the second distillation column 200 is not particularly limited as long as the general formula 2 is satisfied, and 1.0 to 2.0 Kg / cm 2 g, 1.1 to 1.8 Kg / cm 2 g or 1.2 to 1.6 Kg / cm 2 g.
- the temperature of the top region 110 of the first distillation column 100 may be 60 °C to 80 °C, for example, 62 °C to 78 °C or 64 °C to 76 °C, the first distillation column
- the temperature of the bottom region 130 of 100 may be 120 ° C. to 145 ° C., for example, 122 ° C. to 140 ° C. or 124 ° C. to 135 ° C., but is not limited thereto.
- the temperature of the top region 210 of the second distillation column 200 may be 125 ° C to 170 ° C, for example, 130 ° C to 168 ° C or 140 ° C to 165 ° C, and the second distillation column
- the temperature of the bottom region 230 of 200 may be 130 ° C to 180 ° C, for example, 135 ° C to 175 ° C or 140 ° C to 170 ° C, but is not limited thereto.
- the present application also relates to a distillation process for separating the solvent used in the polymerization process of the polyolefin elastomer from the unreacted olefin monomer.
- Exemplary distillation method of the present application may be carried out using the above-described distillation apparatus, and therefore, descriptions overlapping with those described in the above-described distillation apparatus will be omitted.
- a raw material (F 1-1 ) comprising a compound of the formula (1) and a compound of the formula (2) to the first supply port 121 of the first distillation column (100) Inflowing; b) a first overhead stream (F 1-2 ) flowing out of the introduced raw material (F 1-1 ) in the overhead region 110 of the first distillation column (100); Flowing out the first bottom stream (F 1-3 ), the second bottom stream (F 1-4 ), and the third bottom stream (F 1-5 ), respectively, flowing out of the bottom region of the first distillation column; c) introducing the first column bottom stream (F 1-3 ) into a second supply port (221) of a second distillation column (200); e) a second overhead stream (F 2-2 ) flowing out of the flow introduced into the second supply port (221) from the overhead region (210) of the second distillation column (200); And draining the fourth bottom stream (F 2-3 ) and the fifth bottom stream (F 2-4 ) respectively
- R 1 is an alkyl group having 4 to 12 carbon atoms
- R 2 to R 4 are each independently hydrogen or an alkyl group having 4 to 12 carbon atoms
- R 5 is an alkyl group having 1 to 4 carbon atoms, and n is 1 to 4.
- the distillation method may be performed using the above-described distillation apparatus, and the description relating to the distillation apparatus is the same as described above, and thus will be omitted.
- each boundary is not clearly distinguished in the order of time, and thus, each of the steps a) to g) It may be performed sequentially or may be performed independently of each other at the same time.
- distillation method satisfies the following general formulas 1 and 2, and the description thereof will be omitted as it is the same as described above.
- T t -2 represents the temperature of the second overhead stream (F 2-2 )
- T b -3 represents the temperature of the third tower bottom stream (F 1-5 )
- P 1 represents the pressure (Kg / cm 2 g) of the top region 110 of the first distillation column 100
- P 2 is the pressure of the top region 210 of the second distillation column (200). (Kg / cm 2 g) is shown.
- the energy loss generated during the purification of the raw material including the olefin monomer and the solvent, for example, 1-octene / iso-octene and n-hexane, used in the polymerization process of the polyolefin elastomer is minimized.
- the economical efficiency of the process can be improved by separating the product into high purity.
- FIG. 1 is a view showing an exemplary distillation apparatus according to an embodiment of the present application.
- 1-octene, iso-octene and n-hexane were separated using the distillation apparatus of FIG. Specifically, the raw material containing 1-octene, iso-octene, and n-hexane flowed into the 1st supply port located in the 15th stage of the 1st distillation column of 21 stages of theoretical stages.
- a portion of the first overhead stream exiting the overhead region of the first distillation column was refluxed to the overhead region of the first distillation column via a first condenser.
- the remaining portion of the first overhead stream was separated and stored as a product including n-hexane, and the first bottom stream discharged from the bottom region of the first distillation column was passed through the first reboiler to the bottom region of the first distillation column. It was refluxed.
- the second column bottom stream flowing out of the column bottom region of the first distillation column flowed into a second feed port located at seven stages of the second column having 12 theoretical stages.
- the third column bottom stream flowing out from the bottom region of the first distillation column was introduced into the heat exchanger, and after heat exchange with the second column top flow of the second distillation column introduced into the heat exchanger, and then through the heat exchanger to the bottom region of the first distillation column. It was refluxed.
- the operating pressure of the column top region of the first distillation column was adjusted to 0.16 Kg / cm 2 g
- the operating temperature was adjusted to 75 °C
- the operating temperature of the column bottom region of the first distillation column was adjusted to 130 °C. .
- the second overhead stream discharged from the overhead region of the second distillation column is introduced into a heat exchanger, and after exchanging heat with the third overhead stream, a part of the overhead region of the second distillation column is passed through the heat exchanger and the second condenser. And the remaining part was separated into an octene product comprising 1-octene and iso-octene. In this case, the purity of 1-octene and iso-octene was 94%.
- the fourth column bottom stream discharged from the bottom region of the second distillation column was refluxed to the column bottom region of the second distillation column via a second reboiler, and the fifth effluent stream discharged from the column bottom region of the second distillation column was partially octene and It was separated into fuel products containing high boiling point components.
- the operating pressure of the column top region of the second distillation column was adjusted to 1.4 Kg / cm 2 g
- the operating temperature was adjusted to be 155 °C
- the operating temperature of the column bottom region of the second distillation column is adjusted to 160 °C. It was.
- Example 1 Example 2 Example 3 Example 4 Top zone pressure (Kg / cm 2 g) First distillation tower 0.16 0.13 0.15 0.05 Second Distillation Tower 1.4 1.1 1.2 1.2 Column temperature (°C) (top / bottom) First distillation tower 75/130 72/126 74/130 71/127 Second Distillation Tower 155/160 149/155 151/157 151/157 Energy (Gcal / hr) First distillation tower 0.7 0.83 0.88 0.74 Second Distillation Tower 0.73 0.74 0.74 0.74 Recovery 0.7 0.63 0.62 0.67 Total 0.73 0.94 1.00 0.81 Savings 0.59 0.38 0.32 0.51 Energy saving rate (%) 44.7 28.8 24.2 38.6 Product purity (%) 1-octene + iso-octene 94 94 94 n-hexane 99.3 99.3 99.3 99.3 99.3
- the difference between the bottom temperature of the first distillation column and the top temperature of the second distillation column is controlled within a specific range, the pressure of the top region of the first distillation column and the pressure of the top region of the second distillation column. It can be seen that 1-octene, iso-octene and n-hexane can be separated with high purity and high efficiency by controlling the content within a specific range.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
실시예 1 | 실시예 2 | 실시예 3 | 실시예 4 | ||
탑정 영역 압력(Kg/cm2g) | 제1증류탑 | 0.16 | 0.13 | 0.15 | 0.05 |
제2증류탑 | 1.4 | 1.1 | 1.2 | 1.2 | |
컬럼 온도(℃) (탑정/탑저) | 제1증류탑 | 75/130 | 72/126 | 74/130 | 71/127 |
제2증류탑 | 155/160 | 149/155 | 151/157 | 151/157 | |
에너지(Gcal/hr) | 제1증류탑 | 0.7 | 0.83 | 0.88 | 0.74 |
제2증류탑 | 0.73 | 0.74 | 0.74 | 0.74 | |
회수량 | 0.7 | 0.63 | 0.62 | 0.67 | |
Total | 0.73 | 0.94 | 1.00 | 0.81 | |
절감량 | 0.59 | 0.38 | 0.32 | 0.51 | |
에너지 절감율(%) | 44.7 | 28.8 | 24.2 | 38.6 | |
제품 순도(%) | 1-옥텐+iso-옥텐 | 94 | 94 | 94 | 94 |
n-헥산 | 99.3 | 99.3 | 99.3 | 99.3 |
비교예 1 | 비교예 2 | 비교예 3 | ||
탑정 영역 압력(Kg/cm2g) | 제1증류탑 | 0.3 | 0.75 | 0.75 |
제2증류탑 | 0.2 | 1.2 | 2.0 | |
컬럼 온도(℃) (탑정/탑저) | 제1증류탑 | 80/135 | 88/144 | 88/144 |
제2증류탑 | 130/135 | 151/157 | 166/172 | |
에너지(Gcal/hr) | 제1증류탑 | 0.73 | 1.73 | 1.73 |
제2증류탑 | 0.59 | 0.74 | 0.96 | |
회수량 | - | 0.45 | 0.45 | |
Total | 1.32 | 2.02 | 2.24 | |
절감량 | - | - | - | |
에너지 절감율(%) | - | - | - | |
제품 순도(%) | 1-옥텐+iso-옥텐 | 94 | 94 | 94 |
n-헥산 | 99.3 | 99.3 | 99.3 |
비교예 4 | 비교예 5 | ||
탑정 영역 압력(Kg/cm2g) | 제1증류탑 | 0.75 | 0.68 |
제2증류탑 | 1.23 | 1.15 | |
컬럼 온도(℃) (탑정/탑저) | 제1증류탑 | 88/144 | 86/143 |
제2증류탑 | 152/160 | 151/159 | |
에너지(Gcal/hr) | 제1증류탑 | 1.73 | 1.58 |
제2증류탑 | 0.77 | 0.70 | |
회수량 | 0.45 | 0.45 | |
Total | 2.05 | 1.83 | |
절감량 | - | - | |
에너지 절감율(%) | - | - | |
제품 순도(%) | 1-옥텐+iso-옥텐 | 94 | 94 |
n-헥산 | 99.3 | 99.3 |
Claims (12)
- 제 1 응축기, 제 1 재비기 및 제 1 증류탑을 포함하는 제 1 증류 유닛; 상기 제 1 증류탑과 유체 연결되며, 제 2 응축기, 제 2 재비기 및 제 2 증류탑을 포함하는 제 2 증류 유닛; 및 열교환기를 포함하고,하기 화학식 1의 화합물 및 하기 화학식 2의 화합물을 포함하는 원료가 상기 제 1 증류탑의 제 1 공급 포트로 유입되며,상기 제 1 증류탑의 제 1 공급 포트로 유입된 원료는, 상기 제 1 증류탑의 탑정 영역에서 유출되는 제 1 탑정 흐름; 및 상기 제 1 증류탑의 탑저 영역에서 유출되는 제 1 탑저 흐름, 제 2 탑저 흐름 및 제 3 탑저 흐름으로 각각 분리되어 유출되고,상기 제 1 탑정 흐름은 상기 제 1 응축기로 유입되며, 상기 제 1 응축기를 통과한 제 1 탑정 흐름의 일부 또는 전부는 상기 제 1 증류탑의 탑정 영역으로 환류되며,상기 제 1 탑저 흐름은 상기 제 1 재비기로 유입되고, 상기 제 1 재비기를 통과한 제 1 탑저 흐름은 상기 제 1 증류탑의 탑저 영역으로 환류되며,상기 제 2 탑저 흐름은 상기 제 2 증류탑의 제 2 공급 포트로 유입되고,상기 제 2 증류탑의 제 2 공급 포트로 유입된 흐름은, 상기 제 2 증류탑의 탑정 영역에서 유출되는 제 2 탑정 흐름; 및 상기 제 2 증류탑의 탑저 영역에서 유출되는 제 4 탑저 흐름 및 제 5 탑저 흐름으로 각각 분리되어 유출되며,상기 제 4 탑저 흐름은 상기 제 2 재비기로 유입되고, 상기 제 2 재비기를 통과한 제 4 탑저 흐름은 상기 제 2 증류탑의 탑저 영역으로 환류되며,상기 제 2 탑정 흐름 및 상기 제 3 탑저 흐름은 상기 열교환기로 유입되고, 상기 열교환기를 통과한 제 3 탑저 흐름은 제 1 증류탑의 탑저 영역으로 환류되며, 상기 열교환기를 통과한 제 2 탑정 흐름은 상기 제 2 응축기로 유입되고, 상기 제 2 응축기를 통과한 제 2 탑정 흐름은 상기 제 2 증류탑의 탑정 영역으로 환류되며,하기 일반식 1 및 하기 일반식 2를 만족하는 증류 장치:[화학식 1][화학식 2]상기 화학식 1에서 R1은 탄소수 4 내지 12의 알킬기이고, R2 내지 R4는, 각각 독립적으로, 수소 또는 탄소수 4 내지 12의 알킬기이며,상기 화학식 2에서 R5는, 탄소수 1 내지 4의 알킬기이고, n은 1 내지 4이며;[일반식 1]Tt-2 - Tb-3 ≥ 8℃[일반식 2]P2/P1 ≥3.0상기 일반식 1에서, Tt -2는 제 2 탑정 흐름의 온도를 나타내고, Tb -3은 제 3 탑저 흐름의 온도를 나타내며,상기 일반식 2에서, P1은 제 1 증류탑의 탑정 영역의 압력(Kg/cm2g)을 나타내고, P2는 제 2 증류탑의 탑정 영역의 압력(Kg/cm2 g)을 나타낸다.
- 제 1 항에 있어서, 화학식 1의 화합물은 1-옥텐, iso-옥텐 및 이들의 혼합물로 이루어진 군으로부터 선택되는 1종 이상이고, 화학식 2의 화합물은 n-헥산인 증류 장치.
- 제 2 항에 있어서, 제 1 탑정 흐름 내의 n-헥산의 함량이 90% 이상이고, 제 2 탑정 흐름 내의 1-옥텐, iso-옥텐 또는 이들의 혼합물의 함량이 90% 이상인 증류 장치.
- 제 1 항에 있어서, 제 2 탑정 흐름의 일부가 열교환기로 유입되고, 나머지 일부는 제 2 응축기로 유입되며, 상기 열교환기를 통과한 제 2 탑정 흐름의 일부는 상기 제 2 응축기로 유입되고, 상기 제 2 응축기를 통과한 제 2 탑정 흐름의 일부 또는 전부가 제 2 증류탑의 탑정 영역으로 유입되는 증류 장치.
- 제 1 항에 있어서, 제 1 증류탑의 탑정 영역의 압력은 0.05 내지 0.2 Kg/cm2g인 증류 장치.
- 제 1 항에 있어서, 제 2 증류탑의 탑정 영역의 압력은 1.0 내지 2.0 Kg/cm2g인 증류 장치.
- 제 1 항에 있어서, 제 1 증류탑의 탑정 영역의 온도는 60 내지 80℃인 증류 장치.
- 제 1 항에 있어서, 제 1 증류탑의 탑저 영역의 온도는 120 내지 145℃인 증류 장치.
- 제 1 항에 있어서, 제 2 증류탑의 탑정 영역의 온도는 125 내지 170℃인 증류 장치.
- 제 1 항에 있어서, 제 2 증류탑의 탑저 영역의 온도는 130 내지 180℃인 증류 장치.
- 제 1 항에 있어서, 화학식 2의 화합물은 폴리올레핀 엘라스토머의 중합 반응에 사용되는 용매인 증류 장치.
- 제 1 증류탑의 제 1 공급 포트로 하기 화학식 1의 화합물 및 하기 화학식 2의 화합물을 포함하는 원료를 유입하는 단계;상기 유입된 원료를 상기 제 1 증류탑의 탑정 영역에서 유출되는 제 1 탑정 흐름 및; 및 상기 제 1 증류탑의 탑저 영역에서 유출되는 제 1 탑저 흐름, 제 2 탑저 흐름 및 제 3 탑저 흐름으로 각각 유출시키는 단계;상기 제 1 탑저 흐름을 제 2 증류탑의 제 2 공급 포트로 유입시키는 단계;상기 제 2 공급 포트로 유입된 흐름을, 상기 제 2 증류탑의 탑정 영역에서 유출되는 제 2 탑정 흐름; 및 상기 제 2 증류탑의 탑저 영역에서 유출되는 제 4 탑저 흐름 및 제 5 탑저 흐름으로 각각 유출시키는 단계;상기 제 2 탑정 흐름과 상기 제 3 탑저 흐름을 열교환시키는 단계; 및상기 제 1 증류탑의 탑정 영역에서 상기 화학식 2의 화합물을 분리하고, 상기 제 2 증류탑의 탑정 영역에서 상기 화학식 1의 화합물을 분리하는 단계를 포함하며,하기 일반식 1 및 하기 일반식 2를 만족하는 증류 방법:[화학식 1][화학식 2]상기 화학식 1에서 R1은 탄소수 4 내지 12의 알킬기이고, R2 내지 R4는, 각각 독립적으로, 수소 또는 탄소수 4 내지 12의 알킬기이며,상기 화학식 2에서 R5는, 탄소수 1 내지 4의 알킬기이고, n은 1 내지 4이며;[일반식 1]Tt-2 - Tb-3 ≥ 8℃[일반식 2]P2/P1 ≥ 3.0상기 일반식 1에서, Tt -2는 제 2 탑정 흐름의 온도를 나타내고, Tb -3은 제 3 탑저 흐름의 온도를 나타내며,상기 일반식 2에서, P1은 제 1 증류탑의 탑정 영역의 압력(Kg/cm2g)을 나타내고, P2는 제 2 증류탑의 탑정 영역의 압력(Kg/cm2g)을 나타낸다.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/510,134 US10464867B2 (en) | 2014-10-31 | 2015-11-02 | Distillation method |
JP2017512720A JP6450454B2 (ja) | 2014-10-31 | 2015-11-02 | 蒸留装置 |
EP15855758.7A EP3213813B1 (en) | 2014-10-31 | 2015-11-02 | Distillation method |
CN201580055407.7A CN106794385B (zh) | 2014-10-31 | 2015-11-02 | 蒸馏装置 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20140150672 | 2014-10-31 | ||
KR10-2014-0150672 | 2014-10-31 | ||
KR1020150153088A KR101804637B1 (ko) | 2014-10-31 | 2015-11-02 | 증류 장치 |
KR10-2015-0153088 | 2015-11-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016068677A1 true WO2016068677A1 (ko) | 2016-05-06 |
Family
ID=55857879
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2015/011654 WO2016068677A1 (ko) | 2014-10-31 | 2015-11-02 | 증류 장치 |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2016068677A1 (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108603125A (zh) * | 2016-09-13 | 2018-09-28 | 株式会社Lg化学 | 选择性蒸馏设备及蒸馏方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR950011388A (ko) * | 1993-10-08 | 1995-05-15 | 프랑스와 앙드레프 | 두개의 추출 증류 단계를 포함하는, 4개 또는 5개의 탄소원자를 갖는 공급원료로부터 삼차에테르를 제조하는 방법 |
KR20070025556A (ko) * | 2005-09-02 | 2007-03-08 | 주식회사 엘지화학 | 2-에틸헥산올 공장 부산물 중 2-에틸헥산올과 2-에틸헥실2-에틸헥사노에이트의 정제방법 |
KR20140092785A (ko) * | 2013-01-16 | 2014-07-24 | 주식회사 엘지화학 | 알칸올의 제조 장치 |
KR20140092783A (ko) * | 2013-01-16 | 2014-07-24 | 주식회사 엘지화학 | 알칸올의 제조 장치 |
KR20140098138A (ko) * | 2011-11-18 | 2014-08-07 | 유오피 엘엘씨 | 올레핀 제조를 위한 방법 및 시스템 |
-
2015
- 2015-11-02 WO PCT/KR2015/011654 patent/WO2016068677A1/ko active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR950011388A (ko) * | 1993-10-08 | 1995-05-15 | 프랑스와 앙드레프 | 두개의 추출 증류 단계를 포함하는, 4개 또는 5개의 탄소원자를 갖는 공급원료로부터 삼차에테르를 제조하는 방법 |
KR20070025556A (ko) * | 2005-09-02 | 2007-03-08 | 주식회사 엘지화학 | 2-에틸헥산올 공장 부산물 중 2-에틸헥산올과 2-에틸헥실2-에틸헥사노에이트의 정제방법 |
KR20140098138A (ko) * | 2011-11-18 | 2014-08-07 | 유오피 엘엘씨 | 올레핀 제조를 위한 방법 및 시스템 |
KR20140092785A (ko) * | 2013-01-16 | 2014-07-24 | 주식회사 엘지화학 | 알칸올의 제조 장치 |
KR20140092783A (ko) * | 2013-01-16 | 2014-07-24 | 주식회사 엘지화학 | 알칸올의 제조 장치 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108603125A (zh) * | 2016-09-13 | 2018-09-28 | 株式会社Lg化学 | 选择性蒸馏设备及蒸馏方法 |
CN108603125B (zh) * | 2016-09-13 | 2020-07-24 | 株式会社Lg化学 | 选择性蒸馏设备及蒸馏方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6450454B2 (ja) | 蒸留装置 | |
WO2017217708A1 (ko) | 용매 회수 장치 및 용매 회수 방법 | |
WO2016200111A1 (ko) | 증류 장치 | |
WO2018226056A1 (ko) | 증류 장치 및 증류 방법 | |
WO2014112808A1 (ko) | 알칸올의 제조 장치 | |
WO2011081385A2 (ko) | 트리클로로실란의 정제 방법 및 정제 장치 | |
WO2014038892A2 (ko) | 이소프로필 알코올의 제조 방법 및 장치 | |
WO2021261682A1 (ko) | 이소프로필 알코올 제조방법 | |
WO2013070042A1 (ko) | 트리할로실란의 정제 장치 | |
WO2022119127A1 (ko) | 아크릴산 제조방법 | |
WO2018066838A2 (ko) | 용매 분리 장치 및 용매 분리 방법 | |
WO2016068677A1 (ko) | 증류 장치 | |
WO2013070043A1 (ko) | 트리할로실란의 정제 장치 | |
WO2015115725A1 (ko) | 방향족 카르복시산 제조시 초산 회수 방법 | |
KR101804006B1 (ko) | 증류 장치 | |
WO2016003215A1 (ko) | 부타디엔 제조 공정 내 에너지 재활용 방법 | |
WO2022255575A1 (ko) | 이소프로필 알코올 제조방법 | |
WO2022235025A1 (ko) | 이소프로필 알코올 제조방법 | |
WO2022255576A1 (ko) | 이소프로필 알코올 제조방법 | |
WO2015026161A1 (ko) | 이소프로필 알코올의 정제 방법 | |
WO2016105156A1 (en) | Method and apparatus for purification of dimethyl carbonate using pervaporation | |
KR102673700B1 (ko) | 이소프로필 알코올 제조방법 | |
WO2024039022A1 (ko) | 이소프로필 알코올의 제조 방법 | |
KR102673698B1 (ko) | 이소프로필 알코올 제조방법 | |
WO2024049103A1 (ko) | 고순도 (메트)아크릴산의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15855758 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2015855758 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015855758 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2017512720 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15510134 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |