CN110759565A - Method for removing heat-stable salt in ionic liquid - Google Patents
Method for removing heat-stable salt in ionic liquid Download PDFInfo
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- CN110759565A CN110759565A CN201910978365.4A CN201910978365A CN110759565A CN 110759565 A CN110759565 A CN 110759565A CN 201910978365 A CN201910978365 A CN 201910978365A CN 110759565 A CN110759565 A CN 110759565A
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- ionic liquid
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- 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
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- 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
- C02F1/22—Treatment of water, waste water, or sewage by freezing
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- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
- C02F1/385—Treatment of water, waste water, or sewage by centrifugal separation by centrifuging suspensions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
Abstract
The invention provides a method for removing heat-stable salt in ionic liquid, which is characterized in that in the running process of a desulfurization system, when the heat-stable salt concentration of the ionic liquid is higher, the ionic liquid led out from the outlet of a barren solution cooler of the ionic liquid system is subjected to freezing crystallization, and finally, the solution is cooled to the required temperature and forms crystals through heat exchange between a refrigerant and the ionic liquid containing high-salt substances; introducing the formed suspension mixture into a cyclone separator for concentration, introducing the concentrated solid phase into a centrifugal separator for further liquid-solid separation, recovering the ionic liquid to the maximum extent, returning the separated ionic liquid to a desulfurization system for reuse, removing the separated crystal at regular intervals, and forming an open circuit by the heat-stable salt along with the removal of the crystal. The invention meets the open-circuit requirement of ionic liquid under the condition of salt substance concentration fluctuation in the operation process, and solves the problem that the operation of the waste gas desulfurization system is influenced due to overhigh salt content in the absorbent.
Description
Technical Field
The invention belongs to the technical field of organic amine ionic liquid desulfurization, and particularly relates to a method for removing heat-stable salt in an ionic liquid.
Background
Along with the enhancement of the current national environmental protection policy, a plurality of waste gas pollutant treatment methods are increasing, economic and environmental protection technical means are continuously emerging, more than ten technologies are provided according to the actual production conditions of various enterprises, and the technology for circularly absorbing sulfur dioxide by ionic liquid (organic amine substances) is widely applied because the technology has the advantages of high absorption efficiency, high absorption speed, mild absorption conditions, large absorption capacity, complete analysis, repeated cyclic utilization and the like, in the actual production and operation process of an ionic liquid system, because of the production organization of the front-stage process and the control reason of the technology, the contents of sulfur trioxide and acid mist in waste gas entering an ionic liquid desulfurization system are increased, so that stable sulfate substances are formed, in the cyclic absorption process, the concentration of sulfate is continuously enriched, on one hand, the absorption effect of the ionic liquid is influenced, on the other hand, when the concentration of sulfate in the ionic liquid circulating agent reaches saturation or the air temperature is reduced, the ionic liquid is crystallized, and a process pipeline and equipment facilities are blocked seriously, so that the operation of an ionic liquid desulfurization system is influenced.
Disclosure of Invention
The invention provides a method for removing heat-stable salt in an ionic liquid, aiming at the defects that the ionic liquid is crystallized due to concentration enrichment of salt in the existing organic amine ionic liquid desulfurization process, process pipelines and equipment facilities are blocked when the ionic liquid is serious, and the operation of an ionic liquid desulfurization system is influenced.
The invention is realized by the following technical scheme:
a method for removing heat stable salts from ionic liquids comprising the steps of:
s1: in the operation process of the desulfurization system, when the concentration of ionic liquid heat-stable salt (mainly sulfate substances such as sodium sulfate) reaches 150-200 g/L, leading out the ionic liquid containing high-salt substances from an outlet of a barren solution cooler of the ionic liquid system according to 10-15 m plantation/h for freezing crystallization.
The led-out flow can influence the heat exchange crystallization efficiency and crystallization effect, the heat exchange crystallization cannot be completely crystallized if the flow is too large, the temperature required by the heat exchange crystallization can be increased, and the using amount of a refrigerant is increased.
S2: and (3) putting the ionic liquid containing high-salt substances into a storage tank of a crystallization kettle with a stirring device, and stirring at 40-90 r/min to perform heat exchange crystallization on the ionic liquid to obtain a crystal suspension mixture.
A jacket is arranged outside the crystallization kettle, and ethylene glycol flows through the jacket; the glycol exchanges heat with the ionic liquid containing high-salt substances in the storage tank, so that the ionic liquid is cooled to-5 to-15 ℃ to form a crystal suspension mixture.
The glycol after heat exchange is introduced into a glycol refrigerating unit through a refrigerating fluid circulating pump to be cooled and then enters a jacket for circulating heat exchange.
S3: introducing the crystallized suspension mixture into a cyclone separator through a slurry pump for first solid-liquid separation, and removing water to obtain a primary crystal; sending the primary mixture into a centrifugal separator for further solid-liquid separation, removing water to obtain a secondary crystal, washing the secondary crystal through a water hose for 10-15 s, removing the washed crystal, and recovering the washing liquid carrying the ionic liquid; the rinsing time is not suitable for a long time, so that excessive moisture in the crystals is prevented, and the water content of the rinsed secondary crystals is preferably 5-10 mL/g.
S4: and returning the ionic liquid separated by the cyclone separator and the centrifuge from the discharge pipe to a desulfurization system to be used as an absorbent for secondary use, and periodically removing the separated crystal.
The method comprises a whole set of process flow, wherein in the operation process of a desulfurization system, the ionic liquid containing high-concentration heat-stability salt is frozen and crystallized, the heat-stability salt is discharged after being crystallized, the ionic liquid flows back to the desulfurization system for continuous desulfurization, and the process flow is repeatedly circulated, so that the recycling of the ionic liquid is improved, the heat-stability salt impurities in the ionic liquid are removed, an effective open circuit is formed by the heat-stability salt substances, and the problem that the operation of related processes is influenced by the heat-stability salt substances is thoroughly solved; meanwhile, in the process of the invention, soft water is additionally added for washing, so that the ionic liquid is further effectively recovered.
As a further improvement of the invention, the number of the cyclone separators is at least two.
The centrifugal separation crystal also contains a small amount of ionic liquid, and a plurality of cyclone separators are arranged to be combined with a soft water flushing system to carry out secondary recovery and separation on the ionic liquid contained in the centrifugal separation crystal, so that the recovery rate of the ionic liquid is further improved.
As a further improvement of the invention, the washing liquid with the ionic liquid in the step S3 is recycled to the cyclone separator and/or the centrifugal separator for further separation.
As a further improvement of the invention, the refrigerant after heat exchange in the step S2 is introduced into the glycol refrigeration unit, exchanges heat with the process circulating water, and then returns to the jacket.
The invention has the beneficial effects that:
1. according to the invention, freezing crystallization is utilized to remove impurities from part of ionic liquid containing high-concentration heat-stability salt in a desulfurization system, and the ionic liquid is recycled for secondary use by combining cyclone separation, centrifugal separation and soft water washing, so that a process flow of recycling the ionic liquid after impurity removal is formed, so that heat-stability salt substances form an effective open circuit, the problem of blockage of equipment facilities of the desulfurization system by crystals formed by the ionic liquid is solved, the labor intensity of operators is reduced, the optimized operation of related processes is ensured, and the use cost of the ionic liquid is reduced.
2. According to the invention, by combining the multistage cyclone and the soft water flushing system, the recovery of the ionic liquid and the removal of heat stability salt are further improved, the purity of the recovered ionic liquid is optimized, and the efficiency of the desulfurization system is further improved.
Drawings
FIG. 1 is a process flow diagram of the present invention for removing heat stable salts from ionic liquids.
Reference numerals: 1-a crystallization kettle, 2-a cyclone separator, 3-a centrifugal separator, 4-a water hose, 5-a discharge pipe, 6-a stirring device, 7-an ethylene glycol refrigerating unit, 8-a refrigerating fluid circulating pump, 9-a jacket, 10-a slurry pump and 11-process circulating water.
Detailed Description
The invention will be further explained with reference to the drawings.
Example 1
A method for removing heat-stable salt in ionic liquid is characterized in that: the method comprises the following steps:
s1: in the operation process of the desulfurization system, when the concentration of the ionic liquid heat-stable salt reaches 150-200 g/L, leading out the ionic liquid containing high-salt substances from an outlet of a barren solution cooler of the ionic liquid system according to 10m year/h for freezing crystallization;
the led-out flow can influence the heat exchange crystallization efficiency and crystallization effect, the heat exchange crystallization cannot be completely crystallized if the flow is too large, the temperature required by the heat exchange crystallization can be increased, and the using amount of a refrigerant is increased.
S2: putting the ionic liquid containing high-salt substances into a storage tank of a crystallization kettle 1 with a stirring device 6, and stirring at 40r/min to carry out heat exchange crystallization on the ionic liquid to obtain a crystal suspension mixture;
a jacket 9 is arranged outside the crystallization kettle 1, and glycol flows through the jacket 9; the glycol exchanges heat with the ionic liquid containing high-salt substances in the storage tank, so that the ionic liquid is cooled to-5 ℃ and a crystal suspension mixture is formed;
the glycol after heat exchange is introduced into a glycol refrigerating unit 7 through a refrigerating fluid circulating pump 8 for cooling, and then enters a jacket 9 for circulating heat exchange.
S3: introducing the crystallized suspension mixture into a cyclone separator 2 through a slurry pump 10 for first solid-liquid separation, and removing water to obtain a first crystal; and sending the primary mixture into a centrifugal separator 3 for further solid-liquid separation, removing water to obtain a secondary crystal, washing the secondary crystal through a soft water pipe 4 for 10s, removing the washed crystal, and recovering the washing liquid carrying the ionic liquid.
The washing time is determined according to the amount of the secondary crystal, and the water content of the washed secondary crystal is preferably 5-10 mL/g.
S4: and returning the ionic liquid separated by the cyclone separator 2 and the centrifuge 3 from the discharge pipe 5 to a desulfurization system to be used as an absorbent for secondary use, and periodically removing separated crystals.
Example 2
Compared with embodiment 1, the present embodiment is different in that:
the flow rate of the ionic liquid containing high-salt substances led out from the barren liquor cooler of the ionic liquid system is 15 m/h;
cooling the ionic liquid to-15 ℃ to form a crystal suspension;
the number of the cyclone separators 2 is 3;
the secondary crystal washing time was 15 s.
Example 3
Compared with embodiment 1, the present embodiment is different in that:
the flow rate of the ionic liquid containing high-salt substances led out from the barren liquor cooler of the ionic liquid system is 12 m/h;
cooling the ionic liquid to-10 ℃ to form a crystal suspension;
the number of the cyclone separators 2 is 2;
the secondary crystal washing time was 12 s.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made thereto by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should be considered as falling within the scope of the present invention.
Claims (4)
1. A method for removing heat-stable salt in ionic liquid is characterized in that: the method comprises the following steps:
s1: in the operation process of the desulfurization system, when the concentration of the ionic liquid heat-stability salt reaches 150-200 g/L, leading out the ionic liquid containing high-salt substances from an outlet of an ionic liquid system barren solution cooler according to 10-15 m year/h for freezing crystallization;
s2: putting the ionic liquid containing high-salt substances into a storage tank of a crystallization kettle (1) with a stirring device (6), and stirring at 40-90 r/min to perform heat exchange crystallization on the ionic liquid to obtain a crystal suspension mixture;
a jacket (9) is arranged outside the crystallization kettle (1), and glycol flows through the jacket (9); the glycol exchanges heat with the ionic liquid containing high-salt substances in the storage tank, so that the ionic liquid is cooled to-5 to-15 ℃ to form a crystal suspension mixture;
the glycol after heat exchange is introduced into a glycol refrigerating unit (7) through a refrigerating fluid circulating pump (8) for cooling, and then enters a jacket (9) for circulating heat exchange;
s3: introducing the crystallized suspension mixture into a cyclone separator (2) through a slurry pump (10) for first solid-liquid separation, and removing water to obtain a first crystal; sending the primary mixture into a centrifugal separator (3) for further solid-liquid separation, removing water to obtain secondary crystals, washing the secondary crystals through a flexible water pipe (4) for 10-15 s, removing the washed crystals, and recovering the washing liquid carrying the ionic liquid;
s4: and returning the ionic liquid separated by the cyclone separator (2) and the centrifuge (3) from the discharge pipe (5) to a desulfurization system to be used as an absorbent for secondary use, and periodically removing the separated crystal.
2. The method of claim 1 for removing heat stable salts from ionic liquids, comprising: the number of the cyclone separators (2) is at least 2.
3. The method for removing heat stable salts from ionic liquids according to claim 1 or 2, characterized in that: the washing liquid with the ionic liquid in the step S3 is recovered to the cyclone separator (2) and/or the centrifugal separator (3) to continue the separation.
4. The method of claim 3 for removing heat stable salts from ionic liquids, comprising: the refrigerant subjected to heat exchange in the step S2 is introduced into the glycol refrigeration unit (7), exchanges heat with cold water (11), and then returns to the jacket (9).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910978365.4A CN110759565A (en) | 2019-10-15 | 2019-10-15 | Method for removing heat-stable salt in ionic liquid |
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| CN201910978365.4A CN110759565A (en) | 2019-10-15 | 2019-10-15 | Method for removing heat-stable salt in ionic liquid |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5683587A (en) * | 1992-03-30 | 1997-11-04 | Ferrara; Marcello | Process for treating industrial wastes |
| WO2008113387A1 (en) * | 2007-03-20 | 2008-09-25 | Larox Oy | Process for separating a mixture containing salt |
| CN105294384A (en) * | 2015-10-29 | 2016-02-03 | 中石化南京工程有限公司 | Device for separating p-xylene crystal |
| CN205061595U (en) * | 2015-09-28 | 2016-03-02 | 中国石油化工股份有限公司 | Prevent stifled embrane method denitrification facility |
| CN205386413U (en) * | 2016-01-29 | 2016-07-20 | 铜陵有色金属集团股份有限公司铜冠冶化分公司 | Amine liquid crystallizer of sodium salt among organic amine liquid of desorption |
| CN206188558U (en) * | 2016-11-02 | 2017-05-24 | 盛发环保科技（厦门）有限公司 | Desulphurization waste water treatment system based on multistage fluidized bed crystallization |
| CN107930346A (en) * | 2017-10-17 | 2018-04-20 | 广西金川有色金属有限公司 | A kind of ionic liquid thermal regeneration device |
| CN209317084U (en) * | 2018-11-21 | 2019-08-30 | 内蒙古兴安铜锌冶炼有限公司 | A kind of freeze crystallization removes the device of sulfate ion in ionic liquid |
-
2019
- 2019-10-15 CN CN201910978365.4A patent/CN110759565A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5683587A (en) * | 1992-03-30 | 1997-11-04 | Ferrara; Marcello | Process for treating industrial wastes |
| WO2008113387A1 (en) * | 2007-03-20 | 2008-09-25 | Larox Oy | Process for separating a mixture containing salt |
| CN205061595U (en) * | 2015-09-28 | 2016-03-02 | 中国石油化工股份有限公司 | Prevent stifled embrane method denitrification facility |
| CN105294384A (en) * | 2015-10-29 | 2016-02-03 | 中石化南京工程有限公司 | Device for separating p-xylene crystal |
| CN205386413U (en) * | 2016-01-29 | 2016-07-20 | 铜陵有色金属集团股份有限公司铜冠冶化分公司 | Amine liquid crystallizer of sodium salt among organic amine liquid of desorption |
| CN206188558U (en) * | 2016-11-02 | 2017-05-24 | 盛发环保科技（厦门）有限公司 | Desulphurization waste water treatment system based on multistage fluidized bed crystallization |
| CN107930346A (en) * | 2017-10-17 | 2018-04-20 | 广西金川有色金属有限公司 | A kind of ionic liquid thermal regeneration device |
| CN209317084U (en) * | 2018-11-21 | 2019-08-30 | 内蒙古兴安铜锌冶炼有限公司 | A kind of freeze crystallization removes the device of sulfate ion in ionic liquid |
Non-Patent Citations (3)
| Title |
|---|
| 农业部工人技术培训教材编审委员会: "《乳品生产技术II》", 31 March 1997, 中国农业出版社 * |
| 邱正秋: "胺法脱二氧化硫溶液中热稳定性盐去除实验研究", 《天然气化工》 * |
| 金其荣等: "《有机酸发酵工艺学》", 30 June 1989, 轻工业出版社 * |
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Application publication date: 20200207 |