CN1517144A - Method and device for concentrating material higher than boiling point in exhaust - Google Patents
Method and device for concentrating material higher than boiling point in exhaust Download PDFInfo
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- CN1517144A CN1517144A CNA031483461A CN03148346A CN1517144A CN 1517144 A CN1517144 A CN 1517144A CN A031483461 A CNA031483461 A CN A031483461A CN 03148346 A CN03148346 A CN 03148346A CN 1517144 A CN1517144 A CN 1517144A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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Abstract
The method comprises steps of introducing exhaust gas containing substances of higher boiling points than that of water into a plate column having a plurality of stages of trays, which has the structure where gas cannot escape to an upper part without passing through water existent on the trays or into a packed column packed with a hydrophilic filler from a lower part thereof and meanwhile feeding water from an upper part of the column; concentrating the substances of higher boiling points than that of water based on the gas-liquid equilibrium relation between the exhaust gas and water at the lower part of the column; and shifting the residual substances in the exhaust gas into water at the upper part of the column.
Description
Technical field
The present invention relates to utilize the high material of the ratio water boiling point that contains in the exhaust and the boiling-point difference of water to concentrate, when reclaiming, make the method for exhaust gas purification.
Background technology
In the past, in the exhaust gas purification that contains the water-soluble solvent higher than water boiling point is handled, be blown into the exhaust that contains water-soluble solvent, and flowed into a large amount of water from top, absorption tower and wash above-mentioned exhaust from the bottom, absorption tower.So except that washing needs a large amount of water, also because the solvent strength that contains in the draining is extremely low, and solvent recovery will spend cost, and solvent recovery is impossible in fact, also there is the problem that needs to handle waste water in washing methods.
As another prior art, be that cylinder adsorbents such as sepiolite, horizontal has been filled in the limit rotation, the limit is by being cooled to the above-mentioned exhaust about room temperature, a part of former state by gas is put into atmosphere, once more by having filled cylinder adsorbents such as sepiolite, horizontal, free being adsorbed processing gas that solvent high concentration that agent adsorbing contains the solvent of freeing and reclaiming solvent after the other parts heating (for driving the composition that is adsorbed agent absorption out of) through cooling once more.Because this method also is a coolant exhaust once, heat after the adsorption treatment, for reclaiming the operation that solvent cools off once more, so the efficiency extreme difference.
For example, in order to remove the N-N-methyl-2-2-pyrrolidone N-(NMP) that from the exhaust that the drying process of lithium electrode is discharged, contains, though use existing absorption method, but make the adsorption efficiency of N-N-methyl-2-2-pyrrolidone N-significantly low when existing owing to moisture, so refrigerating work procedure of the high-temperature exhaust air that need discharge from above-mentioned drying process, after making adsorbents adsorb N-N-methyl-2-2-pyrrolidone N-,, need opposite heating operation specifically again in order to remove the N-N-methyl-2-2-pyrrolidone N-from adsorbent.So existing activity list is shown among Fig. 2.
According to existing method, need so-called refrigerating work procedure, absorption process, free three operations of operation, and, heat once more after the exhaust of the equivalent temperature cooling, there is the problem of following huge energy loss.
Summary of the invention
First purpose of the present invention provides the high volatile chemical of ratio water boiling point that contains in the exhaust, for example by water-soluble solvent and steam displacement, in the time of high efficiente callback, makes the method and apparatus of exhaust gas purification.
Second purpose of the present invention is the heat that utilizes usually by 100 ℃～120 ℃ of high-temperature exhaust airs of discharges such as lithium ion cell electrode manufacturing process, by making the outside make-up water evaporation that imports, make the ratio water boiling point that contains in the exhaust high, water-soluble volatile chemical concentrates, be composition and the water displacement in the exhaust, in the time of high efficiente callback, by adding adsorption effect, make the method and apparatus of exhaust gas purification by the low temperature make-up water.
The 3rd purpose of the present invention is from the exhaust that contains the powder such as active carbon that adsorbed chemical substances such as dioxins, reclaims to have adsorbed the powder such as active carbon of chemical substances such as dioxins, makes the method and apparatus of exhaust gas purification.
The present invention first relates to concentrate the method for material higher than water boiling point in the exhaust, it is characterized in that, by not passing the water that is present on the column plate, section tower that the column plate of the structure that gas just can not run away from top constitutes through multistage design or the bottom of having filled the packed column of hydrophilic filling, importing contains the exhaust of the material higher than water boiling point, on the other hand, supply with the water (water of normal temperature normally by tower top, need not the energy that heats or cool off), when the tower bottom is by the concentrated above-mentioned material higher than water boiling point of the vapor-liquid equilibrium relationship of row's G﹠W, the above-mentioned substance in the remaining exhaust is further transferred in the water on tower top.
The present invention second relates to the method for material higher than water boiling point in the concentrated exhaust of the present invention first record, and the wherein above-mentioned material higher than water boiling point is (a) volatile chemical or (b) powdered substance.
The present invention the 3rd relates to the method for material higher than water boiling point in the concentrated exhaust of the present invention's first record, the wherein above-mentioned material higher than water boiling point is pulverous material, and the amount of supplying with water from tower top is to control, control the concentration of the above-mentioned substance that reclaims from the tower bottom at 1～30 weight % according to the concentration information of tower bottom.
The present invention the 4th relates to the method for material higher than water boiling point in the concentrated exhaust of the present invention's the 3rd record, and wherein above-mentioned powdered substance is the powder that has adsorbed dioxins.
The present invention the 5th relates to the method for material higher than water boiling point in the concentrated exhaust of the present invention's first record, the wherein above-mentioned material higher than water boiling point is hydrophily, volatile chemical, and the amount of supplying with water from tower top is that the concentration of the hydrophily controlling, reclaim from the control of tower bottom according to the concentration information of tower bottom, volatile chemical is at 20～100 weight %.
The present invention the 6th relates to the method for material higher than water boiling point in the concentrated exhaust of the present invention's the 5th record, wherein above-mentioned hydrophily, volatile chemical are from NMP (N-methyl pyrrolidone), DMF (N, dinethylformamide), DMAC (N, the N-dimethylacetylamide), DMSO (dimethyl sulfoxide (DMSO)), EG (ethylene glycol), DEG (diethylene glycol (DEG)), TEG (triethylene glycol), PGME (propane diols monoethyl ether), PG (propane diols), 1, the solvent based of selecting among the group of 4-BD (butanediol), MEA (MEA) and DGME (diglycol monotertiary methyl ether).
The present invention the 7th relates to concentrate the device of material higher than water boiling point in the exhaust, it is characterized in that, be by
(1) section tower that constitutes through the multistage design by the column plate that does not pass the water that is present on the column plate, structure that gas just can not run away from top or the packed column of having filled hydrophilic filling,
(2) above above-mentioned multistage column plate, the water supply means are set in above-mentioned section tower or above packed layer, in the above-mentioned packed column, the water supply means are set,
(3) top of section tower or the top set handling gas discharge outlet of packed layer,
(4) bottom of section tower or the bottom set handling liquid material outlet of packed layer,
(5) irritate by the liquid material storage that contains the material higher that pipe connects from the liquid material outlet than water boiling point,
(6) in the section tower or the mensuration means that are provided with in the packed column for concentration in the system that detects high material than water boiling point,
(7) control the means of the output of above-mentioned water supply means according to the information of said determination means, formation.
The simple declaration of accompanying drawing
Fig. 1 is the recovery method flow chart of the present invention that expression is used for embodiment 1.
Fig. 2 is the heat budget analysis chart of expression embodiment 1 and the flow chart of material budget.
Fig. 3 is the flow chart that expression is used for the recovery method of existing adsorbent.
The specific embodiments of invention
The present invention effectively utilizes to have the heat of exhaust of suitable high-temperature (for example 80～120 ℃) usually more, make an operation of the exhaust section of passing through tower, realize the recovery of the material that the ratio water boiling point that contains in the exhaust is high and the utmost point effective method and the device of pump-down process simultaneously.
When the present invention is particularly suitable as the exhaust gas purification of lithium ion cell electrode manufacturing works, the method and apparatus that the N-methyl pyrrolidone is reclaimed, be by by not passing the water that is present on the column plate, section tower that the column plate of the structure that gas just can not run away from top constitutes through multistage design or the bottom of having filled the packed column of hydrophilic filling, importing is by the exhaust of 100 ℃～120 ℃ of high temperature that contain the N-methyl pyrrolidone of lithium ion cell electrode manufacturing process discharge, on the other hand, supply with water by tower top, utilize heat of exhaust to make the water evaporation of supply in the tower bottom, make the ratio water boiling point that contains in the exhaust high on the contrary, water miscible N-methyl pyrrolidone cooling, fall the tower bottom, the above-mentioned N-methyl pyrrolidone in the remaining exhaust is further transferred in the water.
The amount of above-mentioned supply water is that the water yield (B) of discharging from system that contains in the gas with the processing of being discharged by Duan Ta top after the pump-down process and the water yield (C) of discharging from the tower bottom with the condensate of the volatile chemical higher than water boiling point are quantity delivered (A).In other words, can be
A B+C compares with the pump-down process method of passing through washing of prior art, and the use amount of water is few especially, is not only this point, when realizing saving resource, does not produce the draining that needs wastewater treatment in fact in addition, also is bigger usefulness.
The temperature of top of tower is set than outer temperature degree height.Because saturation moisture content increases with temperature is high, so often be under the saturation point, supply with water even add by the moisture in the gas in the simple section of the making tower, also can making sends as an envoy to satisfies the condition of Xac≤Xs.The temperature of supplying with water on the absorption efficiency with low for well, but the water shortage that flows down in the tower when crossing when hanging down not only also needs the energy that cools off.In addition, outer gas is unsaturated usually, owing to do not represent that to reach humidity saturated moisture content exists, the amount of supplying with water is many during than saturation state.
As the material higher of the present invention, be (a) volatile chemical or (b) powdered substance than water boiling point.
As the volatile chemical higher than water boiling point (a), the special water-soluble solvent higher than water boiling point is the material of representative.
As such solvent based, it is preferred NMP (N-methyl pyrrolidone, BP:197 ℃), DMF (N, dinethylformamide, BP:153 ℃), DMAC (N, the N-dimethylacetylamide, BP:165 ℃), DMSO (dimethyl sulfoxide (DMSO), BP:189 ℃), EG (ethylene glycol, BP:197 ℃), DEG (diethylene glycol (DEG), BP:245 ℃), TEG (triethylene glycol, BP:278 ℃), PGME (propane diols monoethyl ether), PG (propane diols, BP:188 ℃), 1,4-BD (butanediol, BP:235 ℃), MEA (MEA, BP:170.5 ℃) and DGME (diglycol monotertiary methyl ether) etc. have not the material with the water azeotropic properties.
As the powdered substance of above-mentioned (b), can lift the active carbon powdery body of the dioxins of having adsorbed in the combustion furnace exhaust etc.
As the column plate that does not pass the water that exists in the above-mentioned column plate, structure that gas just can not run away from top, except that the valve gap column plate that always uses very early (bubble clock plate), also can lift the sieve column plate (porous plate) of back exploitation etc.From the stability aspect with the valve gap column plate for well, but from the expense aspect with the sieve column plate for well.
Hydrophilic filling in the packed column of having filled above-mentioned hydrophilic filling can be the shape of regular filler, also can be the shape of irregular filler, preference rule filler during from the consideration pressure loss.These fillers be hydrophilic, surface area is big, the porosity of being made by hydrophilic material for example, the concrete porous ceramics lifted, porous carbon etc.
The present invention is particularly suitable in lithium ion cell electrode manufacturing works, is the processing of the exhaust of discharging from drying process of removing N-N-methyl-2-2-pyrrolidone N-(NMP) solvent.As shown in Figure 1,, outside factory, draw common air, after the air filtration, transmit the wind of heating to drying process by pressure fan for removing N-N-methyl-2-2-pyrrolidone N-(NMP) solvent.
Usually the air of drawing outside factory is:
Outer temperature degree t
Flow V Nm
3/ min
Water content Xa kg/m
3
Amount of moisture VXa kg/min is blown into from the bottom of section tower (water displacement tower) for the exhaust of discharging from drying process of removing N-N-methyl-2-2-pyrrolidone N-(NMP) solvent is following condition in lithium ion battery manufacturing works:
Exhaust concentration t
1=100～120 ℃
NMP content Cn=0.0005～0.01kg/m
3
(113～2260ppm，vol./vol.)
NMP flow VCn kg/min
Extraction flow V Nm
3/ min
The epimere of valve gap column plate that amount of moisture VXa kg/min is provided with from multistage water displacement tower or sieve column plate etc. is supplied with for example t of common normal temperature with the flow of M kg/min
3℃ supply water.Gas (the gas temperature t of the processing of emitting from water displacement tower top
2), with the rate of recovery (weight rate) of R as volatile chemicals such as NMP:
Discharging amount V Nm
3/ min
Calculate water content VXa+[M-VCnR (1/Xn-1)] kg/min
Calculate moisture content Xac=Xa+[m-VCnR (1/Xn-1)]/Vkg/m
3
Temperature is t
2The time, gas saturated aqueous rate: Xs
This device can run well during as controlled condition Xac≤Xs.
On the other hand, reclaim N-N-methyl-2-2-pyrrolidone N-(the liquid temperature t that contains water from water displacement tower bottom
4).
Embodiment
The present invention is described by the following examples, but the present invention is not subjected to its any restriction.As not specializing, the % among the embodiment is meant weight %.
N-N-methyl-2-2-pyrrolidone N-(NMP) solvent for the removal lithium ion battery shown in Figure 1, the air of drawing in drying process is:
T=15 ℃ of outer temperature degree
Flow V=4Nm
3/ min
Water content Xa=0.0128kg/m
3(being assumed to be saturation state)
Amount of moisture VXa=0.0512kg/min is blown into from the bottom of section tower (water displacement tower) for the exhaust of discharging from drying process of removing N-N-methyl-2-2-pyrrolidone N-(NMP) solvent is following condition in lithium ion battery manufacturing works:
Exhaust concentration t
1=120 ℃
NMP content Cn=0.0031kg/m
3
(700ppm，vol./vol.)
NMP flow VCn=0.0124kg/min
Extraction flow V=4Nm
3/ min
The epimere of the valve gap column plate that amount of moisture VXa=0.0512kg/min is provided with from multistage water displacement tower is supplied with for example t of common normal temperature with the flow of M=0.1786kg/min
3=20 ℃ supply water.Gas (the gas temperature t of the processing of emitting from water displacement tower top
2=42 ℃),
Discharging amount V=4Nm
3/ min
Calculate water content VXa+[M-VCnR (1/Xn-1)]=0.2180kg/min
Calculate moisture content Xac=Xa+[m-VCnR (1/Xn-1)]/V=0.0545kg/m
3
Temperature is t
2In the time of=42 ℃, gas saturated aqueous rate: Xs=0.0565kg/m
3Therefore, Xac=0.0545kg/m
3≤ Xs=0.0565kg/m
3
NMP content Cn (1-R)=0.00015kg/m
3The time, this device can run well.
On the other hand, reclaim N-N-methyl-2-2-pyrrolidone N-(the liquid temperature t that contains water with following condition recovery from water displacement tower bottom
4=80 ℃):
t
4＝80℃
Collect water VCnR (the 1/Xn-1)=0.0118kg/min in the liquid
Collect the NMP VCnR=0.0118kg/min in the liquid
The rate of recovery R=0.95 of NMP (weight rate)
NMP concentration Xn=0.50 (weight rate)
In addition, the goods and materials revenue and expenditure of water displacement tower as shown in Figure 2.
The effect of invention
(1) significant operation simplification and energy-saving have been realized by the present invention.
(2) in the conventional method, employing answers recovered solvent to become to grade by top for feeding water, making solvent molten Defluent means among the Xie Zaishui. In this case, because making when high, system temperature is dissolved in the water Solvent again volatilize, so need will to supply with in advance being water-cooled to about room temperature of scrubbing tower. Cause This, cooling needs energy. On the other hand, because the present invention is the heat of effectively utilizing exhaust, supply with The exhaust of enrichment facility need not heating or cooling, can directly supply with, so the thermal efficiency is high.
(3) according to the present invention, the water that reclaim to use only trace for feedwater just can, but in the prior art Because use washings, so compare with existing method in the present invention, the use amount of water can be lacked To about about one thousandth.
Claims (7)
1, concentrate the method for material higher in the exhaust than water boiling point, it is characterized in that, by not passing the water that is present on the column plate, section tower that the column plate of the structure that gas just can not run away from top constitutes through multistage design or the bottom of having filled the packed column of hydrophilic filling, importing contains the exhaust of the material higher than water boiling point, on the other hand, supply with the water (water of normal temperature normally by tower top, need not the energy that heats or cool off), when the tower bottom is by the concentrated above-mentioned material higher than water boiling point of the vapor-liquid equilibrium relationship of row's G﹠W, the above-mentioned substance in the remaining exhaust is further transferred in the water on tower top.
2, the method for the material higher than water boiling point in the concentrated exhaust of claim 1 record, the wherein above-mentioned material higher than water boiling point are (a) volatile chemical or (b) powdered substance.
3, the method for the material higher in the concentrated exhaust of claim 1 record than water boiling point, the wherein above-mentioned material higher than water boiling point is pulverous material, and the amount of supplying with water from tower top is to control, control the concentration of the above-mentioned substance that reclaims from the tower bottom at 1～30 weight % according to the concentration information of tower bottom.
4, the method for the material higher than water boiling point in the concentrated exhaust of claim 3 record, wherein above-mentioned powdered substance is the powder that has adsorbed dioxins.
5, the method for the material higher in the concentrated exhaust of claim 1 record than water boiling point, the wherein above-mentioned material higher than water boiling point is hydrophily, volatile chemical, and the amount of supplying with water from tower top is that the concentration of the hydrophily controlling, reclaim from the control of tower bottom according to the concentration information of tower bottom, volatile chemical is at 20～100 weight %.
6, the method for the material higher in the concentrated exhaust of claim 5 record than water boiling point, wherein above-mentioned hydrophily, volatile chemical are from NMP (N-methyl pyrrolidone), DMF (N, dinethylformamide), DMAC (N, the N-dimethylacetylamide), DMSO (dimethyl sulfoxide (DMSO)), EG (ethylene glycol), DEG (diethylene glycol (DEG)), TEG (triethylene glycol), PGME (propane diols monoethyl ether), PG (propane diols), 1, the solvent based of selecting among the group of 4-BD (butanediol), MEA (MEA) and DGME (diglycol monotertiary methyl ether).
7, concentrate the device of material higher in the exhaust than water boiling point, it is characterized in that, be section tower that constitutes through the multistage design by the column plate that does not pass the water that is present on the column plate, structure that gas just can not run away from top by (1) or the packed column of having filled hydrophilic filling
(2) above above-mentioned multistage column plate, the water supply means are set in above-mentioned section tower or above packed layer, in the above-mentioned packed column, the water supply means are set,
(3) top of section tower or the top set handling gas discharge outlet of packed layer,
(4) bottom of section tower or the bottom set handling liquid material outlet of packed layer,
(5) irritate by the liquid material storage that contains the material higher that pipe connects from the liquid material outlet than water boiling point,
(6) in the section tower or the mensuration means that are provided with in the packed column for concentration in the system that detects high material than water boiling point,
(7) control the means of the output of above-mentioned water supply means according to the information of said determination means, formation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003020725A JP4030439B2 (en) | 2003-01-29 | 2003-01-29 | Method and apparatus for concentrating substances having higher boiling point than water in exhaust gas |
| JP020725/2003 | 2003-01-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1517144A true CN1517144A (en) | 2004-08-04 |
| CN100563788C CN100563788C (en) | 2009-12-02 |
Family
ID=32950276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031483461A Expired - Lifetime CN100563788C (en) | 2003-01-29 | 2003-06-30 | Concentrate the method and apparatus of material higher in the exhaust than water boiling point |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4030439B2 (en) |
| KR (1) | KR100981073B1 (en) |
| CN (1) | CN100563788C (en) |
| TW (1) | TWI255732B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4593264B2 (en) * | 2004-01-30 | 2010-12-08 | 三菱化学エンジニアリング株式会社 | N-methyl-2-pyrrolidone recovery device and recovery method thereof |
| JP4778403B2 (en) * | 2006-11-08 | 2011-09-21 | 日本リファイン株式会社 | A method and apparatus for purifying exhaust gas by collecting and concentrating VOC from exhaust gas containing VOC. |
| CN101791509B (en) * | 2010-03-31 | 2011-12-28 | 苏州巨联科技有限公司 | Ternary cycle DMF waste gas recovery method and device |
| JP6180704B2 (en) | 2011-12-12 | 2017-08-16 | 日本リファイン株式会社 | Gas-liquid contact device |
| JP6665063B2 (en) | 2015-11-24 | 2020-03-13 | 株式会社西部技研 | Drying equipment |
| CN107715651A (en) * | 2017-10-17 | 2018-02-23 | 华南理工大学 | A kind of efficient low damage solvent for being used to absorb toluene and flow |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2134890Y (en) * | 1992-07-31 | 1993-06-02 | 张家港市化肥厂 | Ring-edge sealed bubble-cap tower |
| JPH11253733A (en) * | 1997-12-25 | 1999-09-21 | Chiyoda Corp | Method for two stage wet detoxification treatment of incinerator gas |
| JP4183331B2 (en) * | 1999-03-05 | 2008-11-19 | 日本リファイン株式会社 | Shelf type gas-liquid contact device |
| JP2003024736A (en) * | 2001-07-11 | 2003-01-28 | Fuji Photo Film Co Ltd | Gas-liquid contact apparatus and freezing, concentration, and separation method |
-
2003
- 2003-01-29 JP JP2003020725A patent/JP4030439B2/en not_active Expired - Lifetime
- 2003-05-29 TW TW092114542A patent/TWI255732B/en not_active IP Right Cessation
- 2003-06-30 CN CNB031483461A patent/CN100563788C/en not_active Expired - Lifetime
- 2003-07-04 KR KR1020030045180A patent/KR100981073B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| JP4030439B2 (en) | 2008-01-09 |
| JP2004230265A (en) | 2004-08-19 |
| TW200413077A (en) | 2004-08-01 |
| CN100563788C (en) | 2009-12-02 |
| KR100981073B1 (en) | 2010-09-08 |
| KR20040069939A (en) | 2004-08-06 |
| TWI255732B (en) | 2006-06-01 |
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