EP2624928A1 - Low energy distillation system and method - Google Patents
Low energy distillation system and methodInfo
- Publication number
- EP2624928A1 EP2624928A1 EP11770624.2A EP11770624A EP2624928A1 EP 2624928 A1 EP2624928 A1 EP 2624928A1 EP 11770624 A EP11770624 A EP 11770624A EP 2624928 A1 EP2624928 A1 EP 2624928A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- section
- fluid
- feed
- stripper
- rectifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000004821 distillation Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims description 18
- 239000012530 fluid Substances 0.000 claims abstract description 59
- 238000012546 transfer Methods 0.000 claims abstract description 28
- 238000004891 communication Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000012809 cooling fluid Substances 0.000 claims abstract description 6
- 230000005484 gravity Effects 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 238000013461 design Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/28—Evaporating with vapour compression
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/007—Energy recuperation; Heat pumps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
Definitions
- the presently disclosed subject matter relates to energy efficient distillation systems and methods, including energy efficient distillation systems and methods for use in petrochemical refining operations or the like.
- HIDiC Heat Integrated Distillation Columns
- FIG. 1 depicts a conventional distillation operation 1000.
- a condenser 1010 located on top of the column 1020, removes heat from the vapor-rich process stream 1030 to produce a liquid product stream 1040 rich in a higher volatile ("lighter") product.
- the condenser also produces a reflux stream 1050 employed to improve the quality of the vapor- liquid staged separation process.
- the heat removed at the condenser is not recovered, but is discharged to the cooling water or air, thereby resulting in a low energy efficiency of distillation.
- the Second Law Thermodynamic Efficiency, also referred to as Exergy efficiency, in a distillation column is generally less than 10%.
- the Exergy efficiency defines how efficient the system is relative to a thermodynamically perfect system performing the same operation starting with same input feeds and producing the same product streams
- the rectifier section 1060 is located, in vertical proximity, above the stripping section 1070 in a conventional distillation column.
- the column shown in Figure 1 is also provided with a reboiler 1080 which receives a feed rich in less-volatile ("heavier") components, in which heat is employed to vaporize more volatile components. Heavier liquid products remaining after the input of heat are withdrawn from the column 1090, while some heavier vaporized product 1 100 is recycled back to the column to improve the quality of the separation.
- a reboiler 1080 which receives a feed rich in less-volatile (“heavier”) components, in which heat is employed to vaporize more volatile components. Heavier liquid products remaining after the input of heat are withdrawn from the column 1090, while some heavier vaporized product 1 100 is recycled back to the column to improve the quality of the separation.
- Figure 2 depicts a HIDiC unit operation 2000 described in J. of Chem. Tech. and Biotech., 78:241-248 (2003), which is hereby incorporated by reference in its entirety.
- the rectifier and the stripper sections 2060 and 2030, respectively, in Figure 2 are located in a lateral position with additional provision for heat transfer from the rectifier to the stripper sections.
- a compressor 2010 is employed to compress the vapor from the stream 2020 exiting the stripping section 2030, which is the section defined by area below the feed 2040. The compression results in a higher temperature in the rectifier section 2060, which is generally the column 2080 shown on the right of Figure 2.
- a valve 2090 is provided to control the flow of the stream 2100 exiting the bottom of the rectifying section to a location in close proximity to the feed.
- the upper portion of the second column 2080 yields a vapor-rich stream 2110 which is directed to a condenser 2120 that yield a low volatile product 2130 and a reflux stream 2140, which is returned to the rectifier section 2060.
- the stream 2100 providing liquid reflux functionality is generated.
- the "reflux ratio" of the stream 2100 providing liquid reflux functionality is set by the column heat balance with proximate control based on level in the rectification section bottoms by valve 2090.
- FIG. 3 Another proposed HIDiC operation 3000 is depicted in Figure 3, which is taken from Z. OCSI et al, Energy 31 :3083-3096 (2006), and hereby incorporated by reference in its entirety.
- Figure 3 illustrates a concentric tray design with the stripping section located outside of the rectifier section, with heat transfer panels 3030 placed in between trays. Lateral heat transfer occurs between two parallel or concentric columns, which can be provided by, for example, an inner rectifying section 3010 surrounded by an outer stripping section 3020.
- FIG 4 depicts a conceptual design 4000 in which heat pipes 4010 transfer heat from a rectifier section 4040 to a stripping section 4030, which are separated by a partition 4020. The heat pipes are in a lateral position, as shown in Figure 4.
- HIDiC designs have not been commercialized to date.
- One aspect of the presently disclosed subject matter provides a distillation system for separating at least two components of a multi-component fluid feed.
- the system includes a stripper section including (i) an inlet to receive a feed of fluid containing at least two components, (ii) a compressor in fluid communication with a more volatile portion of the fluid within the stripper section to provide an output feed, and (iii) a reboiler to receive a heating fluid and in fluid communication with a less volatile portion of fluid within the stripper section.
- the distillation system also includes a rectifier section aligned vertically with and disposed below the stripper section, the rectifier section to receive the output feed from the compressor and further including (i) a condenser to receive a cooling fluid and in fluid communication with a more volatile portion of the output feed from the compressor, the condenser including an exit to remove at least one component from the more volatile portion of the output feed, and (ii) an outlet to recycle a less volatile portion of the output feed from the compressor for recycle back to the stripper section.
- a rectifier section aligned vertically with and disposed below the stripper section, the rectifier section to receive the output feed from the compressor and further including (i) a condenser to receive a cooling fluid and in fluid communication with a more volatile portion of the output feed from the compressor, the condenser including an exit to remove at least one component from the more volatile portion of the output feed, and (ii) an outlet to recycle a less volatile portion of the output feed from the compressor for recycle back to the stripper section.
- Another aspect of the presently disclosed subject matter provides a distillation method for separating at least two components of a multi-component fluid feed.
- the method includes introducing a feed of fluid containing at least two components to a stripper section, the stripper section including (i) an inlet to receive the feed of the fluid, (ii) a compressor in fluid communication with a more volatile portion of the fluid within the stripper section to provide an output feed, and (iii) a reboiler to receive a heating fluid and in fluid communication with a less volatile portion of fluid within the stripper section.
- the distillation method also includes directing the output feed from the compressor to a rectifier section aligned vertically with and disposed below the stripper section, the rectifier section including (i) a condenser to receive a cooling fluid and in fluid communication with a more volatile portion of the output feed from the compressor, the condenser including an exit to remove at least one component from the more volatile portion of the output feed, and (ii) an outlet to recycle a less volatile portion of the output feed from the compressor to the stripper section.
- FIG. 1 is a schematic view of a conventional distillation column with a rectifying section located above the stripping section, in which energy removed at the condenser is not recovered.
- FIG. 2 is a schematic view of a conventional HIDiC concept.
- FIG. 3 is a schematic view of a concentric HIDiC design with heat transfer from the inner rectifier to outer stripper section.
- FIG. 4 is a schematic view of a HIDiC design with heat pipes for heat transfer from the rectifier section to the stripper section in lateral positions.
- FIG. 5 is a schematic view of a representative embodiment of the distillation system of the presently disclosed subject matter.
- FIG. 6 is a schematic view of another representative embodiment of the distillation system of the presently disclosed subject matter.
- the Exergy efficiency defines how efficient the separation is relative to a thermodynamically perfect system.
- the Exergy of each stream is the theoretical maximum amount of work it can produce, determined by taking it through a series of reversible steps to bring it into equilibrium with ambient surrounding.
- the increase in Exergy content of the products versus the feed inputs represents the minimum amount of work needed.
- the Exergy efficiency is defined as the ratio of this minimum amount of work divided by the total Exergy expended in actually doing the separation
- the term "produced in an industrial scale” refers to a production scheme in which end products are produced on a continuous basis (with the exception of necessary outages for plant maintenance) over an extended period of time (e.g., over at least a week, or a month, or a year) with the expectation of generating revenues from the sale or distribution of the end product.
- Production at an industrial scale is distinguished from laboratory or pilot plant settings which are typically maintained only for the limited period of the experiment or investigation, and are conducted for research purposes and not with the expectation of generating revenue from the sale or distribution of end products.
- a distillation system is provided for separating at least two components of a multi-component fluid feed.
- the distillation system includes a stripper section including (i) an inlet to receive a feed of fluid containing at least two components, (ii) a compressor in fluid communication with a more volatile portion of the fluid within the stripper section to provide an output feed, and (iii) a reboiler to receive a heating fluid and in fluid communication with a less volatile portion of fluid within the stripper section.
- the distillation system also includes a rectifier section aligned vertically with and disposed below the stripper section, the rectifier section to receive the output feed from the compressor and further including (i) a condenser to receive a cooling fluid and in fluid communication with a more volatile portion of the output feed from the compressor, the condenser including an exit to remove at least one component from the more volatile portion of the output feed, and (ii) an outlet to recycle a less volatile portion of the output feed from the compressor for recycle back to the stripper section.
- a rectifier section aligned vertically with and disposed below the stripper section, the rectifier section to receive the output feed from the compressor and further including (i) a condenser to receive a cooling fluid and in fluid communication with a more volatile portion of the output feed from the compressor, the condenser including an exit to remove at least one component from the more volatile portion of the output feed, and (ii) an outlet to recycle a less volatile portion of the output feed from the compressor for recycle back to the stripper section.
- a distillation method for separating at least two components of a multi-component fluid feed.
- the distillation method includes introducing a feed of fluid containing at least two components to a stripper section, the stripper section including (i) an inlet to receive the feed of the fluid, (ii) a compressor in fluid communication with a more volatile portion of the fluid within the stripper section to provide an output feed, and (iii) a reboiler to receive a heating fluid and in fluid communication with a less volatile portion of fluid within the stripper section.
- the distillation method also includes directing the output feed from the compressor to a rectifier section aligned vertically with and disposed below the stripper section, the rectifier section including (i) a condenser to receive a cooling fluid and in fluid communication with a more volatile portion of the output feed from the compressor, the condenser including an exit to remove at least one component from the more volatile portion of the output feed, and (ii) an outlet to recycle a less volatile portion of the output feed from the compressor to the stripper section.
- liquid portions rich in less volatile components flow down the column, and gaseous portions rich in more volatile components of the feed flow up toward a gas compressor 5150.
- a partition 5200 is provided to prevent the liquid portions rich in heavier components of the feed from traveling further down the column into the rectifier section 5500.
- the section between the feed and the partition constitute the stripping or stripper section 5250 of the distillation column.
- a reboiler 5300 which is supplied with a source of steam or other heating fluid, inputs heat to the column and yields a bottoms product, 5350, rich in less volatile (“heavier”) products and a stream, 5400 that is returned to the stripping section 5250.
- Compressed vapors 5450 exiting the compressor 5150 are directed to the bottom of the rectifier section 5500.
- the compression of the gases results in a higher temperature in the rectifier section 5500 as compared to the stripper section 5250, which consists of the section of the column below the partition 5200.
- the rectifier section 5500 is operated at a higher average temperature than the stripper section 5250.
- liquid components 5600 are drawn from the bottom of the column and introduced into the stripper section 5250 in the feed 5100 or to the feed tray 5120 by means of, for example, a throttle valve or pump 5650.
- a condenser 5700 is provided at the top of the rectifying section, which receives a supply of cooling water and yields a product, 5750, rich in lighter products and a reflux stream, 5800 which is redirected to the column into the rectifying section.
- the composition exiting the condenser can include, or consist of primarily the light, low boiling components of the feed 5100.
- end products derived from the methods and systems of the presently disclosed subject matter are produced in an industrial scale.
- the rectifier section 5500 in operated at a higher temperature than the stripping section 5250. Having the stripper section 5250 located, in vertical proximity, above the rectifier section 5500 allows the use of one or more heat pipes 5850 to transfer heat from the rectifier section 5500 to the stripper section 5250 and reduce the heat load on the reboiler.
- the system includes at least one heat pipe traversing between at least a portion of the rectifier section and at least a portion of the stripper section to transfer heat from the rectifier section to the stripper section.
- the heat pipe 5850 can be oriented substantially perpendicular to a base of the rectifier section, as shown in Figure 5, to direct condensate inside the heat pipe 5800 to the rectifier section via gravity.
- the system 5000 can be further provided with at least one hollow distillation tray 5900, 5950 located at least one end of the heat pipe.
- the system can include, for example, two hollow distillation trays 5900, 5950 that are located on both ends of the heat pipe.
- the hollow distillation trays 5900, 5950 can be further provided with fins (not shown) to enhance the heat transfer area to and from the heat pipe.
- the compression provided by the compressor 5150 results in a higher temperature in the rectifier section 5500.
- Heat is transferred from the rectifier section 5500 to the stripping section 5250 via one or more heat pipes. This heat transfer reduces and/or eliminates the heat discharged at the condenser.
- the heat duty of the reboiler 5300 at the bottom of the stripping section 5250 is reduced, thus resulting in an overall improvement in exergetic efficiency (e.g., up to and exceeding 50%).
- the heat pipe in the rectification section 5950 acts as an inter-condenser, with the heat pipe in the stripping section 5900 acting as an inter-reboiler.
- the working fluid inside the heat pipe 5850 condenses in the stripping section 5900 and vaporizes in the rectification section 5950, which transfers heat from the rectifier section to the stripper selection.
- process liquid the material being distilled
- process vapor in the rectification section is condensed.
- the stream providing liquid reflux functionality is formed as the heat pipe working fluid condenses in going from the warmer rectifier section to the cooler stripper section, and the working fluid flows back to the rectifier section via gravity.
- the amount of heat pipe heat transfer is set by the design of the heat pipe including the choice of working fluid, the temperature differential, the working fluid pressure level, the physical layout including surface area of both heat transfer sections and the gravity driving force.
- the heat pipe design determines the amount of inter- condenser generated reflux and inter-reboiler generated vaporization.
- packed towers can be preferred due to pressure drop considerations in situations involving debottlenecking of distillation units. Also packed towers may offer more capacity to compensate for the lost area if the heat pipe is installed internal to the column. A packed rectification section with a lower pressure drop will also allow a lower compression ratio for the compression of the stripper section overhead to feed the rectification section. Heat pipes can be used, for example, to transfer heat from different sections of the rectifier to corresponding sections of the stripper.
- a corresponding section would be a section that maintains the same delta temperature between the rectification section inter-condenser and the stripping section inter-reboiler. This means that an upper inter-condenser would transfer heat to an upper inter-reboiler and a lower inter-condenser would transfer heat to a lower inter reboiler as shown in the system 6000 in Figure 6.
- These heat pipes can have, according to one non-limiting embodiment, heat exchangers with radially extending fins on both ends of the heat pipe.
- the presently disclosed subject matter such as the embodiment shown in Figure 5 or Figure 6, provides a more practical column configuration where, unlike conventional distillation, the rectifier section is vertically below the stripper section.
- Heat transport from the rectifier section 6500 to the stripper section 6250 can be achieved using one or more heat pipes, and the heat is transferred mostly in the axial direction.
- the vertical configuration allows gravitational force to return the condensate in the heat pipe from the stripper section to the rectifier section below.
- Heat integration is achieved in a single column, making it easier to retrofit existing columns and reducing the plot area that would be needed for a second column.
- Figure 6 illustrates an embodiment of the present invention using external heat pipes in a thermo siphon orientation with a vapor riser 6851 and liquid return 6852, which allows the heat pipe working fluid to segregate and help avoid flooding.
- the riser 6851 and the return 6852 are operatively coupled to internal heat transfer surfaces 6853.
- the internal heat transfer surfaces 6853 can be a hollow distillation tray, a structural packing in a plate or frame type configuration or any other suitable heat transfer device that promotes heat transfer without restricting column capacity.
- the same concept can also be achieved with external heat pipe with a single connection with countercurrent vapor and liquid flow provided the heat pipe is sized adequately to avoid flooding.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US39035810P | 2010-10-06 | 2010-10-06 | |
PCT/US2011/054854 WO2012047953A1 (en) | 2010-10-06 | 2011-10-05 | Low energy distillation system and method |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2624928A1 true EP2624928A1 (en) | 2013-08-14 |
Family
ID=44802411
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11770624.2A Withdrawn EP2624928A1 (en) | 2010-10-06 | 2011-10-05 | Low energy distillation system and method |
Country Status (8)
Country | Link |
---|---|
US (1) | US20120085126A1 (en) |
EP (1) | EP2624928A1 (en) |
KR (1) | KR20130143577A (en) |
CN (1) | CN103237580B (en) |
BR (1) | BR112013008394A2 (en) |
CA (1) | CA2813892A1 (en) |
SG (2) | SG10201507750XA (en) |
WO (1) | WO2012047953A1 (en) |
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US20140183027A1 (en) * | 2011-05-09 | 2014-07-03 | Fluor Technologies Corporation | Internal heat exchanger for distillation column |
JP6266876B2 (en) * | 2012-11-15 | 2018-01-24 | 東洋エンジニアリング株式会社 | Distillation apparatus and control method thereof |
JP6033050B2 (en) | 2012-11-16 | 2016-11-30 | 東洋エンジニアリング株式会社 | Aromatic hydrocarbon production equipment |
US20140262729A1 (en) * | 2013-03-14 | 2014-09-18 | Elwha Llc | Heat transfer between a distillation column and a temperature source |
DE102013214765A1 (en) * | 2013-07-29 | 2015-01-29 | Wacker Chemie Ag | Process and apparatus for the distillative separation of a three- or multi-component mixture |
JP6140591B2 (en) * | 2013-11-21 | 2017-05-31 | 東洋エンジニアリング株式会社 | Distillation equipment |
JP6289112B2 (en) * | 2014-01-17 | 2018-03-07 | 東洋エンジニアリング株式会社 | Distillation tower |
CN105884103A (en) * | 2014-09-03 | 2016-08-24 | 中石化洛阳工程有限公司 | Acidic water stripping method |
DE102014220539A1 (en) | 2014-10-09 | 2016-04-14 | Wacker Chemie Ag | Purification of chlorosilanes by distillation and adsorption |
CN104524800B (en) * | 2014-12-31 | 2016-06-22 | 石家庄工大化工设备有限公司 | A kind of thermal coupling with heat exchange column plate is sprayed and flows tower |
US20160216040A1 (en) * | 2015-01-23 | 2016-07-28 | Indigo Power Systems Llc | Heat exchanger |
JP6566876B2 (en) * | 2016-01-26 | 2019-08-28 | 東洋エンジニアリング株式会社 | Heat exchange amount adjustment method for internal heat exchange distillation column |
CN106693425B (en) * | 2016-12-13 | 2023-04-07 | 浙江科茂能源科技有限公司 | Efficient energy-saving plate type heat exchange distillation device |
US10539364B2 (en) * | 2017-03-13 | 2020-01-21 | General Electric Company | Hydrocarbon distillation |
CN113274755B (en) * | 2021-05-24 | 2022-05-13 | 大连理工大学 | Process and device for preparing oxygen by phase thermal decomposition of sulfuric acid in iodine-sulfur cycle |
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EP2486965A1 (en) * | 2009-10-05 | 2012-08-15 | National Institute of Advanced Industrial Science And Technology | Heat-exchange-type distillation apparatus |
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-
2011
- 2011-10-03 US US13/251,624 patent/US20120085126A1/en not_active Abandoned
- 2011-10-05 CA CA2813892A patent/CA2813892A1/en not_active Abandoned
- 2011-10-05 KR KR1020137011371A patent/KR20130143577A/en not_active Application Discontinuation
- 2011-10-05 CN CN201180058527.4A patent/CN103237580B/en not_active Expired - Fee Related
- 2011-10-05 BR BR112013008394A patent/BR112013008394A2/en not_active IP Right Cessation
- 2011-10-05 SG SG10201507750XA patent/SG10201507750XA/en unknown
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Publication number | Priority date | Publication date | Assignee | Title |
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EP2486965A1 (en) * | 2009-10-05 | 2012-08-15 | National Institute of Advanced Industrial Science And Technology | Heat-exchange-type distillation apparatus |
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CN103237580B (en) | 2015-08-19 |
SG189260A1 (en) | 2013-05-31 |
CN103237580A (en) | 2013-08-07 |
KR20130143577A (en) | 2013-12-31 |
US20120085126A1 (en) | 2012-04-12 |
CA2813892A1 (en) | 2012-04-12 |
SG10201507750XA (en) | 2015-10-29 |
BR112013008394A2 (en) | 2016-06-21 |
WO2012047953A1 (en) | 2012-04-12 |
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