WO2008013370A1 - Ethanolamine recovery method with physicochemical process - Google Patents
Ethanolamine recovery method with physicochemical process Download PDFInfo
- Publication number
- WO2008013370A1 WO2008013370A1 PCT/KR2007/003384 KR2007003384W WO2008013370A1 WO 2008013370 A1 WO2008013370 A1 WO 2008013370A1 KR 2007003384 W KR2007003384 W KR 2007003384W WO 2008013370 A1 WO2008013370 A1 WO 2008013370A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethanolamine
- wastewater
- tower
- evaporation
- exchange resin
- Prior art date
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 238000000034 method Methods 0.000 title claims abstract description 70
- 230000008569 process Effects 0.000 title claims abstract description 49
- 238000011084 recovery Methods 0.000 title description 2
- 239000002351 wastewater Substances 0.000 claims abstract description 58
- 238000001704 evaporation Methods 0.000 claims abstract description 44
- 230000008020 evaporation Effects 0.000 claims abstract description 43
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 15
- 239000003456 ion exchange resin Substances 0.000 claims description 15
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- -1 stainless steel Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Definitions
- the present invention relates to treatment of ethanolamine-containing wastewater.
- this invention relates to a method that withdraws expensive ethanolamine contained in wastewater, in which the ethanolamine-containing wastewater, discharged from nuclear power plants and thermal power plants, undergoes an ethanolamine capturing and condensing process using a cation exchange resin; the ethanolamine captured and condensed wastewater undergoes a first evaporation process heating it to 60- 100 0 C; and the wastewater having undergone the first evaporation process undergoes a second evaporation process heating it to 100 ⁇ 200°C.
- Nuclear power plants and thermal power plants use water as an energy transfer medium to obtain electric energy from nuclear energy or fossil fuels.
- water/ vapor circulation systems in the plants vaporize water to rotate a turbine that produces electricity, and then condense the vapor to water, continually repeating this circulation.
- the circulated and condensed water may corrode parts included in the system.
- chemicals such as a pH control agent and a chemical-potential control agent, etc., are injected into the circulating water, thereby controlling electrochemical corrosion of the metal parts of the system.
- the water/vapor circulation system of the nuclear power plant and thermal power plant is installed with an ion-exchange resin tower. Chemicals that are injected into the water/vapor circulation system to control corrosion are removed, along with some impurities as well, while circulating throughout water/vapor in the water/vapor circulation system. After this, the chemicals must be injected into the system again. That is, at each water/vapor circulation cycle, the chemicals are removed by an ion exchange resin and then chemicals are newly injected into the system. Such a process is repeated.
- a technique needs to treat the ethanolamine-containing wastewater discharged from a nuclear power plant or thermal power plant in a way that meets the environmental discharge standard, and then discharge the treated wastewater.
- the present invention has been made in view of the above problems, and it is an object of the present invention to provide a method that withdraws expensive ethanolamine in ethanolamine-containing wastewater discharged from a nuclear power plant or a thermal power plant and allows the withdrawn ethanolamine to be recycled, thereby enhancing its industrial usefulness.
- the ethanolamine is captured and condensed by the cation exchange resin (2) that fills an ion exchange tower (1) while the wastewater passes through the ion exchange tower (1), and the ethanolamine captured and condensed wastewater is transferred to an evaporation tower (8).
- the wastewater which flowed into the evaporation tower (8), undergoes a first heating to 60- 100 0 C, vapor generated by the first heating passes through an adsorption tower (6) that fills with zeolite to adsorb the ethanolamine, and the vapor from which the ethanolamine has been removed by the zeolite is discharged into the air.
- the wastewater, from which foreign materials have been removed by the first evaporation process undergoes a second heating to 100 ⁇ 200°C, and vapor generated by the second heating is transferred to a cooling tower (10) and cooled to 10 ⁇ 25°C.
- the method for withdrawing ethanolamine according to the present invention originally treats the ethanolamine causing biochemical oxygen demand and total nitrogen concentration in wastewater discharged from nuclear power plants or thermal power plants when ion-exchange resin is recycled. As such, this method does not cause the load of the conventional wastewater treatment plant to be increased nor require further improvement of the conventional wastewater treatment plant.
- the method of the present invention can withdraw and recycle the ethanolamine that must be continuously injected to prevent the water/vapor circulation systems of nuclear power plants or thermal power plants from being corroded, the plants can be managed cost-effectively.
- Figure 1 is a schematic block diagram describing a method for withdrawing ethanolamine from wastewater using a combination process according to an embodiment of the present invention.
- Figure 2 is a view depicting a system adopting a method for withdrawing ethanolamine from wastewater, according to an embodiment of the present invention.
- Figure 1 is a schematic block diagram describing a method for withdrawing ethanolamine from wastewater using a combination process according to an embodiment of the present invention.
- the method withdraws ethanolamine in wastewater through an ethanolamine capturing and condensing process (SlO), a first evaporation process (S20), and a second evaporation process (S30).
- SlO ethanolamine capturing and condensing process
- S20 first evaporation process
- S30 second evaporation process
- the ethanolamine is captured by a cation exchange resin while the wastewater passes through the cation exchange resin, sodium hydroxide and air are injected into the cation exchange resin capturing ethanolamine so that the ethanolamine is eluted and the wastewater is condensed, and the condensed wastewater is transferred to an evaporation tower.
- the wastewater which flowed into the evaporation tower, undergoes a first heating to generate vapor, the vapor passes through an adsorption tower filled with zeolite to adsorb the ethanolamine, and the vapor from which the ethanolamine has been removed using the zeolite is discharged into the air.
- Figure 2 is a view depicting a system adopting a method for withdrawing ethanolamine from wastewater, according to an embodiment of the present invention.
- the system performs an ethanolamine capturing and condensing process (SlO), a first evaporation process (S20), and a second evaporation process (S30).
- SlO ethanolamine capturing and condensing process
- S20 first evaporation process
- S30 second evaporation process
- the ethanolamine capturing and condensing process is performed in such a way that: while the wastewater passes through an ion exchange resin tower 1 filling with cation exchange resin 2, sodium hydroxide solution 4 from a sodium hydroxide tank 3 and air 5 are injected into the ion exchange resin tower 1 so that the cation exchange resin 2 is mixed with them and the ethanolamine is condensed.
- the first evaporation process (S20) is performed in such a way that: the ethanolamine captured and condensed wastewater is transferred to an evaporation tower 8; the influx wastewater undergoes a first heating of 60- 100 0 C by a heater 9 to generate vapor; the vapor passes through adsorption agent 7 in an adsorption tower 6 to adsorb the ethanolamine; and the vapor removing the ethanolamine is discharged into the air.
- the second evaporation process (S30) is performed in such a way that: the wastewater from which foreign materials have been removed by the first heating undergoes a second heating to 100 ⁇ 200°C to generate vapor; the vapor generated by the second heating is transferred to a cooling tower 10 and is cooled to and condensed at 10 ⁇ 25°C; and the ethanolamine is withdrawn by a withdrawal tank 11.
- the ion exchange resin tower 1 is made of a polymeric material or metals, such as stainless steel, so as not to be corroded by a strong base resin.
- the cation exchange resin 2 is preferably implemented with sulfonic acid cation exchange resin based on divinylbenzene styrene copolymer.
- a sodium hydroxide solution 4 from the sodium hydroxide tank 3 and air 5 are injected into the ion exchange resin tower 1 and the cation exchange resin 2 is stirred therein.
- the ethanolamine capturing and condensing process refers to a process where regenerated wastewater is produced in the ion exchange resin tower 1 as the sodium hydroxide solution 4 of the sodium hydroxide tank 3 and air 5 pass through the ion exchange resin.
- ethanolamine-containing wastewater which flows into the tank initially, is relatively highly concentrated in the range of 1/10,000 ⁇ 1/20,000, and the amount of wastewater is reduced.
- an adsorption tower 6 is installed to one side of the ion exchange resin tower 1 to prevent ethanolamine from discharging into the air.
- the adsorption tower 6 fills with an adsorbent agent 7, such as a zeolite adsorbent.
- the zeolite is formed to have a micro-porous structure allowing it to combine with chemical materials physically or chemically. Therefore, the zeolite adsorbent can adsorb gaseous water and ethanolamine while they are passing therethrough together with air.
- the reduced wastewater obtained through the ethanolamine capturing and condensing process is transferred to an evaporation tower 8 that serves to evaporate the regeneration wastewater of the ion exchange resin tower 1 through first and second steps.
- the evaporation tower 8 is made of stainless steel or aluminum whose thermal conductivity is excellent, so as not to be corroded by a strong base resin.
- the wastewater is heated to 60- 100 0 C to thus generate vapor; and the vapor and a small amount of ethanolamine generated when the vapor is generated are passed through the adsorption tower 6 and then are discharged into the air.
- the first evaporation process is performed at 60- 100 0 C. This is because, when the water containing ethanolamine is heated, the water, along with the ethanolamine, is evaporated. That is, although the boiling points of water and ethanolamine are 100 0 C and 17O 0 C, respectively, when water is heated to 100 0 C, a small amount of ethanolamine is also evaporated.
- the vapor and gaseous ethanolamine generated in the first evaporation process are adsorbed by the adsorbent agent 7 filled in the adsorption tower 6, between the evaporation tower 8 and the cooling tower 9, to prevent the ethanolamine from being discharged into the air.
- the adsorbent agent 7 adsorbing the ethanolamine is digested in pure water to recycle the adsorbent agent 7.
- the adsorbent agent 7 is preferably implemented with zeolite that is formed to have a micro-porous structure so that it can adsorb gaseous water and ethanolamine.
- the wastewater is heated to 100 ⁇ 200°C. This is because, if the wastewater is heated to greater than 100 0 C, the water disappears by evaporation and only ethanolamine becomes evaporating. The evaporated ethanolamine is transferred to the cooling tower 10. After evaporation is completed, the inside of the evaporation tower 8 is washed by pure water.
- the cooling tower 10 serves to condense the vapor and gaseous ethanolamine from the evaporation tower 8. If the cooling temperature of the cooling tower 10 is equal to or less than 1O 0 C, it is difficult to withdraw the ethanolamine because the freezing point of the ethanolamine is 1O 0 C. As when using tap water, groundwater, and sea water whose freezing points are generally less than 25 0 C, the cooling tower 10 maintains its cooling temperature at preferably 10 ⁇ 25°C.
- the cooling tower 10 is made of metals, such as iron, etc., which does not include a copper component whose thermal conductivity is excellent, so as not to be corroded by a strong base resin.
- the cooling tower 10 employs air, water, and refrigerant as a heat sink.
- the ethanolamine condensed by the cooling tower 10 is collected in a withdrawal tank 11. Such a collected ethanolamine solution is injected into the evaporation tower.
- the ethanolamine containing wastewater can be treated to meet the biochemical oxygen demand and nitrogen concentration that are defined in the environmental discharge standard and discharged to the environment, and, at the same time, the expensive ethanolamine is withdrawn from the ethanolamine containing wastewater.
Abstract
A method for withdrawing ethanolamine using a physicochemical process is disclosed. The method withdraws expensive ethanolamine contained in wastewater as follows. The ethanolamine-containing wastewater discharged from nuclear power plants and thermal power plants undergoes an ethanolamine capturing and condensing process using a cation exchange resin. The ethanolamine captured and condensed wastewater undergoes a first evaporation process heating it to 60- 1000C. The wastewater having undergone the first evaporation process undergoes a second evaporation process heating it to 100~200°C.
Description
Description
ETHANOLAMINE RECOVERY METHOD WITH PHYSIC-
OCHEMICAL PROCESS
Technical Field
[1] The present invention relates to treatment of ethanolamine-containing wastewater.
More particularly, this invention relates to a method that withdraws expensive ethanolamine contained in wastewater, in which the ethanolamine-containing wastewater, discharged from nuclear power plants and thermal power plants, undergoes an ethanolamine capturing and condensing process using a cation exchange resin; the ethanolamine captured and condensed wastewater undergoes a first evaporation process heating it to 60- 1000C; and the wastewater having undergone the first evaporation process undergoes a second evaporation process heating it to 100~200°C.
[2]
Background Art
[3] Nuclear power plants and thermal power plants use water as an energy transfer medium to obtain electric energy from nuclear energy or fossil fuels. Generally, water/ vapor circulation systems in the plants vaporize water to rotate a turbine that produces electricity, and then condense the vapor to water, continually repeating this circulation.
[4] The circulated and condensed water may corrode parts included in the system. To prevent corrosion, chemicals, such as a pH control agent and a chemical-potential control agent, etc., are injected into the circulating water, thereby controlling electrochemical corrosion of the metal parts of the system.
[5] The water/vapor circulation system of the nuclear power plant and thermal power plant is installed with an ion-exchange resin tower. Chemicals that are injected into the water/vapor circulation system to control corrosion are removed, along with some impurities as well, while circulating throughout water/vapor in the water/vapor circulation system. After this, the chemicals must be injected into the system again. That is, at each water/vapor circulation cycle, the chemicals are removed by an ion exchange resin and then chemicals are newly injected into the system. Such a process is repeated.
[6] When chemicals with high volatility were injected into the systems, they were discharged into the air while the wastewater was treated. Therefore, heavy metals, etc., discharged from the plants can be treated through a simple physicochemical process. However, with the adoption of ethanolamine as a pH control agent in recent year, a lot of regenerating wastewater including chemical oxygen demand (COD) and total
nitrogen component is discharged, causing it to be difficult to meet wastewater discharge standard.
[7] If the ethanolamine of a chemical formula NH CH CH OH, consisting of carbon, hydrogen, oxygen and nitrogen, exists in wastewater, it causes an increase in biological oxygen demand (BOD), biochemical oxygen demand (BCOD), and nitrogen concentration whose values are defined in the environmental discharge standard. Therefore, the ethanolamine, which is also expensive, must be treated in the wastewater.
[8] A technique needs to treat the ethanolamine-containing wastewater discharged from a nuclear power plant or thermal power plant in a way that meets the environmental discharge standard, and then discharge the treated wastewater.
[9]
Disclosure of Invention Technical Problem
[10] Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a method that withdraws expensive ethanolamine in ethanolamine-containing wastewater discharged from a nuclear power plant or a thermal power plant and allows the withdrawn ethanolamine to be recycled, thereby enhancing its industrial usefulness.
[H]
Technical Solution
[12] In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a method for withdrawing ethanolamine contained in wastewater including: an ethanolamine capturing and condensing process, and first and second evaporation processes.
[13] In the ethanolamine capturing and condensing process, the ethanolamine is captured and condensed by the cation exchange resin (2) that fills an ion exchange tower (1) while the wastewater passes through the ion exchange tower (1), and the ethanolamine captured and condensed wastewater is transferred to an evaporation tower (8).
[14] In the first evaporation process, the wastewater, which flowed into the evaporation tower (8), undergoes a first heating to 60- 1000C, vapor generated by the first heating passes through an adsorption tower (6) that fills with zeolite to adsorb the ethanolamine, and the vapor from which the ethanolamine has been removed by the zeolite is discharged into the air.
[15] In the second evaporation process, the wastewater, from which foreign materials have been removed by the first evaporation process, undergoes a second heating to 100~200°C, and vapor generated by the second heating is transferred to a cooling
tower (10) and cooled to 10~25°C.
Advantageous Effects
[16] As described above, the method for withdrawing ethanolamine according to the present invention originally treats the ethanolamine causing biochemical oxygen demand and total nitrogen concentration in wastewater discharged from nuclear power plants or thermal power plants when ion-exchange resin is recycled. As such, this method does not cause the load of the conventional wastewater treatment plant to be increased nor require further improvement of the conventional wastewater treatment plant.
[17] In addition, since the method of the present invention can withdraw and recycle the ethanolamine that must be continuously injected to prevent the water/vapor circulation systems of nuclear power plants or thermal power plants from being corroded, the plants can be managed cost-effectively.
[18]
Brief Description of the Drawings
[19] The above and other objects, features, and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
[20] Figure 1 is a schematic block diagram describing a method for withdrawing ethanolamine from wastewater using a combination process according to an embodiment of the present invention; and
[21] Figure 2 is a view depicting a system adopting a method for withdrawing ethanolamine from wastewater, according to an embodiment of the present invention.
[22] <Brief Description of Symbols in the Drawings>
[23] 1: ion-exchange resin tower
[24] 2: cation exchange resin
[25] 3: sodium hydroxide tank
[26] 4: sodium hydroxide solution
[27] 5: air
[28] 6: adsorption tower
[29] 7: adsorption agent
[30] 8: evaporation tower
[31] 9: heater
[32] 10: cooling device
[33] 11 : withdrawal tank
[34]
Mode for the Invention
[35] Preferred embodiments of a method for withdrawing ethanolamine from wastewater according to the present invention will be described in detail with reference to the accompanying drawings.
[36] Figure 1 is a schematic block diagram describing a method for withdrawing ethanolamine from wastewater using a combination process according to an embodiment of the present invention. The method withdraws ethanolamine in wastewater through an ethanolamine capturing and condensing process (SlO), a first evaporation process (S20), and a second evaporation process (S30).
[37] In the ethanolamine capturing and condensing process (SlO), the ethanolamine is captured by a cation exchange resin while the wastewater passes through the cation exchange resin, sodium hydroxide and air are injected into the cation exchange resin capturing ethanolamine so that the ethanolamine is eluted and the wastewater is condensed, and the condensed wastewater is transferred to an evaporation tower.
[38] In the first evaporation process (S20), the wastewater, which flowed into the evaporation tower, undergoes a first heating to generate vapor, the vapor passes through an adsorption tower filled with zeolite to adsorb the ethanolamine, and the vapor from which the ethanolamine has been removed using the zeolite is discharged into the air.
[39] In the second evaporation process (S30), the wastewater having undergone the first evaporation process undergoes a second heating to generate vapor, the vapor is then transferred to a cooling tower and is condensed so that the ethanolamine can be condensed.
[40] Figure 2 is a view depicting a system adopting a method for withdrawing ethanolamine from wastewater, according to an embodiment of the present invention. The system performs an ethanolamine capturing and condensing process (SlO), a first evaporation process (S20), and a second evaporation process (S30).
[41] The ethanolamine capturing and condensing process (SlO) is performed in such a way that: while the wastewater passes through an ion exchange resin tower 1 filling with cation exchange resin 2, sodium hydroxide solution 4 from a sodium hydroxide tank 3 and air 5 are injected into the ion exchange resin tower 1 so that the cation exchange resin 2 is mixed with them and the ethanolamine is condensed.
[42] The first evaporation process (S20) is performed in such a way that: the ethanolamine captured and condensed wastewater is transferred to an evaporation tower 8; the influx wastewater undergoes a first heating of 60- 1000C by a heater 9 to generate vapor; the vapor passes through adsorption agent 7 in an adsorption tower 6 to adsorb the ethanolamine; and the vapor removing the ethanolamine is discharged into the air.
[43] The second evaporation process (S30) is performed in such a way that: the
wastewater from which foreign materials have been removed by the first heating undergoes a second heating to 100~200°C to generate vapor; the vapor generated by the second heating is transferred to a cooling tower 10 and is cooled to and condensed at 10~25°C; and the ethanolamine is withdrawn by a withdrawal tank 11.
[44] In the ethanolamine capturing and condensing process, ethanolamine present in the wastewater is captured through the cation exchange resin 2 which fills the ion exchange resin tower 1. Here, the ion exchange resin tower 1 is made of a polymeric material or metals, such as stainless steel, so as not to be corroded by a strong base resin. The cation exchange resin 2 is preferably implemented with sulfonic acid cation exchange resin based on divinylbenzene styrene copolymer. If the ion-exchange ability of the cation exchange resin 2 is decreased, a sodium hydroxide solution 4 from the sodium hydroxide tank 3 and air 5 are injected into the ion exchange resin tower 1 and the cation exchange resin 2 is stirred therein.
[45] The ethanolamine capturing and condensing process refers to a process where regenerated wastewater is produced in the ion exchange resin tower 1 as the sodium hydroxide solution 4 of the sodium hydroxide tank 3 and air 5 pass through the ion exchange resin. In particular, ethanolamine-containing wastewater, which flows into the tank initially, is relatively highly concentrated in the range of 1/10,000 ~ 1/20,000, and the amount of wastewater is reduced.
[46] As shown in FIG. 2, an adsorption tower 6 is installed to one side of the ion exchange resin tower 1 to prevent ethanolamine from discharging into the air. The adsorption tower 6 fills with an adsorbent agent 7, such as a zeolite adsorbent. The zeolite is formed to have a micro-porous structure allowing it to combine with chemical materials physically or chemically. Therefore, the zeolite adsorbent can adsorb gaseous water and ethanolamine while they are passing therethrough together with air.
[47] Next, the reduced wastewater obtained through the ethanolamine capturing and condensing process is transferred to an evaporation tower 8 that serves to evaporate the regeneration wastewater of the ion exchange resin tower 1 through first and second steps. The evaporation tower 8 is made of stainless steel or aluminum whose thermal conductivity is excellent, so as not to be corroded by a strong base resin.
[48] In the first evaporation process, the wastewater is heated to 60- 1000C to thus generate vapor; and the vapor and a small amount of ethanolamine generated when the vapor is generated are passed through the adsorption tower 6 and then are discharged into the air. It is preferable that the first evaporation process is performed at 60- 1000C. This is because, when the water containing ethanolamine is heated, the water, along with the ethanolamine, is evaporated. That is, although the boiling points of water and ethanolamine are 1000C and 17O0C, respectively, when water is heated to 1000C, a
small amount of ethanolamine is also evaporated.
[49] The vapor and gaseous ethanolamine generated in the first evaporation process are adsorbed by the adsorbent agent 7 filled in the adsorption tower 6, between the evaporation tower 8 and the cooling tower 9, to prevent the ethanolamine from being discharged into the air. The adsorbent agent 7 adsorbing the ethanolamine is digested in pure water to recycle the adsorbent agent 7. The adsorbent agent 7 is preferably implemented with zeolite that is formed to have a micro-porous structure so that it can adsorb gaseous water and ethanolamine.
[50] In the second heating process, the wastewater is heated to 100~200°C. This is because, if the wastewater is heated to greater than 1000C, the water disappears by evaporation and only ethanolamine becomes evaporating. The evaporated ethanolamine is transferred to the cooling tower 10. After evaporation is completed, the inside of the evaporation tower 8 is washed by pure water.
[51] The cooling tower 10 serves to condense the vapor and gaseous ethanolamine from the evaporation tower 8. If the cooling temperature of the cooling tower 10 is equal to or less than 1O0C, it is difficult to withdraw the ethanolamine because the freezing point of the ethanolamine is 1O0C. As when using tap water, groundwater, and sea water whose freezing points are generally less than 250C, the cooling tower 10 maintains its cooling temperature at preferably 10~25°C.
[52] The cooling tower 10 is made of metals, such as iron, etc., which does not include a copper component whose thermal conductivity is excellent, so as not to be corroded by a strong base resin. The cooling tower 10 employs air, water, and refrigerant as a heat sink.
[53] As such, the ethanolamine condensed by the cooling tower 10 is collected in a withdrawal tank 11. Such a collected ethanolamine solution is injected into the evaporation tower.
[54] As described above, through the ethanolamine capturing and condensing process and first and second evaporation process according to the present invention, the ethanolamine containing wastewater can be treated to meet the biochemical oxygen demand and nitrogen concentration that are defined in the environmental discharge standard and discharged to the environment, and, at the same time, the expensive ethanolamine is withdrawn from the ethanolamine containing wastewater.
[55] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
[56]
[57]
Claims
[1] A method for withdrawing ethanolamine contained in wastewater comprising: an ethanolamine capturing and condensing process (SlO) where the ethanolamine is captured and condensed by the cation exchange resin (2) that fills an ion exchange tower (1) while the wastewater passes through the ion exchange tower (1), and the ethanolamine captured and condensed wastewater is transferred to an evaporation tower (8); a first evaporation process (S20) where the wastewater, which flowed into the evaporation tower (8), undergoes a first heating to 60- 1000C, vapor generated by the first heating passes through an adsorption tower (6) that fills with zeolite to adsorb the ethanolamine, and the vapor from which the ethanolamine has been removed by the zeolite is discharged into the air; and a second evaporation process (S30) where the wastewater, from which foreign materials have been removed by the first evaporation process, undergoes a second heating to 100~200°C, and vapor generated by the second heating is transferred to a cooling tower (10) and cooled to 10~25°C.
[2] The method according to claim 1, wherein the ethanolamine capturing and condensing process (SlO) comprises: capturing the ethanolamine-containing wastewater using the cation exchange resin (2); and eluting the ethanolamine from the ethanolamine-containing wastewater using sodium hydroxide solution (4) injected from a sodium hydroxide tank (3) installed to one side of the ion exchange resin tower (1) to reduce the volume of the ethanolamine-containing wastewater.
[3] The method according to claim 1, further comprising: by the zeolite filing the adsorption tower (6) installed in one side of the ion exchange resin tower (1), adsorbing gaseous ethanolamine generated in the ethanolamine capturing and condensing process to prevent the gaseous ethanolamine from discharging into the air; and digesting the zeolite adsorbing the ethanolamine in pure water to recycle the zeolite.
[4] The method according to claim 1, wherein the evaporation tower (8) is filled with activated charcoal to prevent organic matter and solid bodies in the wastewater from carrying over with the gases.
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KR1020060071411A KR100722942B1 (en) | 2006-07-28 | 2006-07-28 | Ethanolamine recovery method with physicochemical process |
KR10-2006-0071411 | 2006-07-28 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011521781A (en) * | 2008-05-28 | 2011-07-28 | スンチュンヒャン ユニバーシティ インダストリー アカデミー コオペレーション ファウンデーション | Amine recovery method from amine-containing wastewater |
US20120029233A1 (en) * | 2010-07-27 | 2012-02-02 | Soonchunhyang University Industry Academy Cooperation Foundation | Method and apparatus for recovery of amine from amine-containing waste water and regeneration of cation exchange resin |
CN105565599A (en) * | 2015-12-21 | 2016-05-11 | 河海大学 | Stepped water purification system based on vegetation type biochemical absorption balls |
Families Citing this family (1)
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KR100926797B1 (en) | 2007-12-04 | 2009-11-12 | 금호석유화학 주식회사 | The recovery method of Alcohols or Ethers from waste water by Activated carbon fiber Adsorption Towers |
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KR19980048346A (en) * | 1996-12-17 | 1998-09-15 | 백운화 | Treatment method of hardly degradable wastewater |
US6123850A (en) * | 1997-05-15 | 2000-09-26 | Elf Atochem | Process for the purification of virtually anhydrous organic liquids |
JP2005066544A (en) * | 2003-08-27 | 2005-03-17 | Japan Organo Co Ltd | Method for recovering monoethanolamine |
JP2006069960A (en) * | 2004-09-02 | 2006-03-16 | Nippon Refine Kk | Method for separation and purification of mixture system containing dimethyl sulfoxide and monoethanolamine |
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2006
- 2006-07-28 KR KR1020060071411A patent/KR100722942B1/en not_active IP Right Cessation
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- 2007-07-12 WO PCT/KR2007/003384 patent/WO2008013370A1/en active Application Filing
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KR19980048346A (en) * | 1996-12-17 | 1998-09-15 | 백운화 | Treatment method of hardly degradable wastewater |
US6123850A (en) * | 1997-05-15 | 2000-09-26 | Elf Atochem | Process for the purification of virtually anhydrous organic liquids |
JP2005066544A (en) * | 2003-08-27 | 2005-03-17 | Japan Organo Co Ltd | Method for recovering monoethanolamine |
JP2006069960A (en) * | 2004-09-02 | 2006-03-16 | Nippon Refine Kk | Method for separation and purification of mixture system containing dimethyl sulfoxide and monoethanolamine |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011521781A (en) * | 2008-05-28 | 2011-07-28 | スンチュンヒャン ユニバーシティ インダストリー アカデミー コオペレーション ファウンデーション | Amine recovery method from amine-containing wastewater |
US8545704B2 (en) | 2008-05-28 | 2013-10-01 | Soonchunhyang University Industry Academy Cooperation Foundation | Method for recovering amine from amine-containing waste water |
US20120029233A1 (en) * | 2010-07-27 | 2012-02-02 | Soonchunhyang University Industry Academy Cooperation Foundation | Method and apparatus for recovery of amine from amine-containing waste water and regeneration of cation exchange resin |
US8859811B2 (en) * | 2010-07-27 | 2014-10-14 | Soonchunhyang University Industry Academy Cooperation Foundation | Method and apparatus for recovery of amine from amine-containing waste water and regeneration of cation exchange resin |
CN105565599A (en) * | 2015-12-21 | 2016-05-11 | 河海大学 | Stepped water purification system based on vegetation type biochemical absorption balls |
CN105565599B (en) * | 2015-12-21 | 2017-12-26 | 河海大学 | Step water cleaning systems based on vegetation type biochemistry adsorbing sphere |
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