CN105214450A - A kind of selective absorbing SO 2absorbent and absorb SO 2process - Google Patents
A kind of selective absorbing SO 2absorbent and absorb SO 2process Download PDFInfo
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- CN105214450A CN105214450A CN201510661913.2A CN201510661913A CN105214450A CN 105214450 A CN105214450 A CN 105214450A CN 201510661913 A CN201510661913 A CN 201510661913A CN 105214450 A CN105214450 A CN 105214450A
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- absorbent
- mass fraction
- selective absorbing
- ionic liquid
- acid
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Abstract
The invention discloses a kind of selective absorbing SO
2absorbent and absorb SO
2process.The composition of described absorbent comprises: the ionic liquid of 30% ~ 70% mass fraction; The activator of 0.1% ~ 4.0% mass fraction; The antioxidant of 0.1% ~ 0.5% mass fraction; The corrosion inhibiter of 0.1% ~ 0.5% mass fraction; Surplus is water.Utilize described absorbent to SO
2the process of carrying out absorbing is: the flue gas after washing is passed into absorption tower from bottom, and the absorbent described in utilization absorbs SO
2; Then SO will be absorbed with
2rich solution enter regenerator from top again, to SO
2carry out desorb; Separate the SO of sucking-off
2send into lower workshop section, directly synthesize H
2sO
4.Described absorbent provided by the invention is to SO
2good absorbing effect, selective height; Ionic liquid wherein adopts organic acid, low to equipment corrosion, more friendly to environment.Described process stable performance, desulfuration efficiency more than 99%, the SO of absorption
2easy desorption and regeneration.
Description
Technical field
The invention belongs to SO
2gas handling techniques field, is specifically related to a kind of selective absorbing SO
2absorbent and absorb SO
2process.
Background technology
China is a producing coal and uses coal big country, and its reserves are only second to the U.S. and Russia.China is a developing country, and the burning of current coal remains the topmost energy that we rely on.Inevitably SO is produced during coal burning
2deng dusty gas, thus directly affect the ecological environment that we depend on for existence.
To reform and open up to the outside world the rapid economic development brought along with China, the consumption of coal also grows with each passing day.At present, China becomes SO
2pollute one of country the most serious.From 11th Five-Year, China has taked control SO
2the related measure of discharge, but it is limited to produce effects.2014, national sulfur dioxide (SO2) emissions total amount was 1974.4 ten thousand tons, falls 3.4% on a year-on-year basis, but situation is still severe.SO
2be a kind of sour gas, it not only can the ecosystem such as damage to land, forest, rivers, also can cause irremediable harm to the building of the mankind, industrial plants, cultural relics and historic sites etc. simultaneously.In addition, the health for human body also has very large impact.Therefore, how effectively control SO
2gas purging is extremely urgent.At present, the flue gas desulfurization technique of countries in the world research and development reaches more than 200 and plants, but the application of the business of reality is considerably less.Current, the prevailing technology processing this flue gas is that ammonia absorption process is called for short the ammonia process of desulfurization, or lime stone slurry absorption process is called for short wet method lime absorption.The ammonia process of desulfurization is chemical fertilizer because of raw material ammonia, and originate valuable, cost is high, causes certain production loss to ammonia enterprise.And ammonia is volatile, easily cause top to emit white cigarette, produce aerosol secondary pollution.Lime stone absorbs, and originate convenient, production cost is low, but the gypsum produced is the one of solid waste, and economic worth is low, and device water consumption is large.Therefore, develop a set of green flue gas desulfurization technique capable of circulation and seem particularly important.
So-called ionic liquid (IonicLiquid, IL), refer to the material being in a liquid state near room temperature temperature or low temperature, being made up of ion completely, be also called ionic liquid at room temperature (RoomTemperatureIonicLiquid) or room temperature molten salt (RoomTemperatureMoltenSalt) or organic ion liquid.Its maximum feature is almost do not have vapour pressure, and has good chemical stability and heat endurance.In addition, ionic liquid has good solubility property for multiple organic or inorganic gas, and differs greatly, and this shows that ionic liquid is as a kind of environmentally friendly green solvent, has huge application prospect in the separation of gas.Adopt ionic liquid as absorbent to SO
2carry out absorbing and be treated as a new research direction.
Summary of the invention
The object of the invention is, a kind of selective absorbing SO is provided
2absorbent and absorb SO
2process, mainly solve SO in prior art
2processing method from energy-conserving and environment-protective and assimilation effect aspect still dissatisfactory technical problem.
The technical scheme that the present invention is adopted for achieving the above object is as follows:
A kind of selective absorbing SO
2absorbent, the composition of this absorbent comprises: the ionic liquid of 30% ~ 70% mass fraction; The activator of 0.1% ~ 4.0% mass fraction; The antioxidant of 0.1% ~ 0.5% mass fraction; The corrosion inhibiter of 0.1% ~ 0.5% mass fraction; Surplus is water.Wherein the content of water is preferably 35% ~ 65%.The content of ionic liquid is preferably 35% ~ 55%.
Described ionic liquid is cation by nitrogenous type organic matter, and organic acid is formed by anion.Further preferably, the cation of described ionic liquid is selected from one or more in guanidine salt, alcamines, imidazoles, pyridines, four azoles, quaternary ammonium salt, thiazoles, dicyandiamide class material; Described anion be selected from lactic acid, tartaric acid, citric acid, pyrovinic acid, malic acid, oxalic acid, acetic acid one or more.This ionic liquid can the absorption SO of high selectivity
2, for other sour gas, as CO
2, absorb hardly.
Described activator is one or both in organic alcohols material.Preferably, described activator is selected from n-butanol, n-hexyl alcohol, n-octyl alcohol.
Described antioxidant is have one or both compositions in the phenols of week reduction or quinones substance.Preferably, described antioxidant is selected from hydroquinones, dibutyl hydroxy toluene, TBHQ, naphthoquinones, anthraquinone and derivative thereof.
Described corrosion inhibiter is one or both compositions in inorganic salts material.Preferably, corrosion inhibiter is selected from one or both in basic copper carbonate, potassium metavanadate, arsenic trioxide, trichloride antimony.
As a kind of preferred embodiment, consisting of of described absorbent: TMG tartrate 45%, n-butanol 0.3%, hydroquinones 0.15%, basic copper carbonate 0.2%, all the other are water.
The present invention also provides a kind of and absorbs SO
2process, the method is: by washing after flue gas pass into absorption tower from bottom, adopt above-mentioned selective absorbing SO
2absorbent absorb SO
2; Then SO will be absorbed with
2rich solution enter regenerator from top again, to SO
2carry out desorb.
Preferably, in described process, the condition on absorption tower is temperature 10 ~ 110 DEG C, and pressure is 0.01 ~ 0.2MPa, is preferably 40 ~ 90 DEG C, 0.05 ~ 0.2MPa; The condition of described regenerator is temperature 100 ~ 150 DEG C, and pressure is 0.01 ~ 0.2MPa, is preferably 110 ~ 140 DEG C, 0.05 ~ 0.2MPa.
Preferably, the SO of described solution sucking-off
2send into lower workshop section, directly synthesize H
2sO
4.
In process of the present invention, described absorbent solution volume flow and flue gas volume flow-rate ratio are 1:20 ~ 1:20000, are preferably 1:100 ~ 1:10000.
In process of the present invention, the SO of generation
2concentration can reach more than 95%.If by SO
2mix with steam, can directly pass into next workshop section, the H of synthesis high concentration
2sO
4byproduct.As SO in raw material flue gas
2content reaches 10000mg/Nm
3time, work off one's feeling vent one's spleen middle SO
2content will be less than 100mg/Nm
3, desulfuration efficiency is up to more than 99%.
Below by the present invention is based on the absorbent that ionic liquid is main body, selective absorbing SO
2technique be described in more detail:
Absorbent based on ionic liquid provided by the invention, for SO
2gas has good absorption and desorption ability, and this desulphurization mechanism is as follows:
Net reaction:
In above formula, R represents absorbent, and net reaction is reversible reaction.Under low temperature, reaction is carried out from left to right; Under high temperature, reaction is carried out from right to left.This technique utilizes this principle just, at low temperatures sulfur dioxide absorption, is desorbed by sulfur dioxide under high temperature from absorbent.Thus reach the object removed with sulfur dioxide in recovered flue gas.
According to an embodiment of invention, ionic liquid selective absorbing SO provided by the invention
2technological process and method of operating as follows:
See Fig. 1, this figure is the process chart that described absorbent carries out flue gas desulfurization.As shown in Figure 1, first flue gas is after booster fan boosting, enters bottom water scrubber 1.After water scrubber 1 dedusting cooling, send into absorption tower 2.Enter into washing pump 7 from water scrubber 1 washings out by water diversion tank 10 and carry out cleaning supercharging, again deliver to water scrubber top, be reused for cooled flue gas.Through the flue gas of dedusting cooling, enter absorption tower 2 from bottom, absorb temperature and be preferably 40 ~ 90 DEG C, pressure is preferably 0.05 ~ 0.2MPa.SO now in flue gas
2absorb by absorbent, the flue gas after sulphur removal can through sending flue direct emptying.Absorb SO
2after rich solution enter poor rich liquid heat exchanger 11 by the bottom of tower through rich solution pump 4, reclaim after heat and enter to be sent to regenerator 3, desorption temperature is preferably 110 ~ 140 DEG C, and pressure is preferably 0.05 ~ 0.2MPa.Be absorbed with SO
2rich solution enter regenerator 3 from top, by stripping desorption part SO
2after, enter reboiler 6, make SO wherein
2further desorb.Desorb SO
2after lean solution flowed out by the bottom of regenerator 3, through lean pump 5, poor rich liquid heat exchanger 11, lean solution cooler 12 heat exchange cooling after, enter the top on absorption tower 2, reuptake SO
2; The SO that regenerator 3 parses
2, concentration can reach more than 95%, this SO
2gas-liquid separator 9 is entered, the SO after separation and purification after being cooled by condenser 8
2send into sulfuric acid apparatus and produce sulfuric acid, also by pressurization cooling, liquid SO can be produced
2product, economic worth is higher.
In above-mentioned sulfur removal technology, the replacement cycle of absorbent is relevant with the composition in flue gas.
In above-mentioned sulfur removal technology, SO in desulfurized effect and flue gas
2concentration, ionic liquid kind, absorbs temperature and pressure, desorption temperature and pressure and flue gas relevant with the ratio of the volume flow of absorbent.
Compared with prior art, beneficial effect of the present invention is as follows:
1, compared with traditional sulfur removal technology, provided by the present invention based on ionic liquid selective absorbing SO
2technique tool have the following advantages: select this technique, have that stable performance, vapour pressure are extremely low, Selective absorber sulfur dioxide ability is strong, energy consumption is low, desulfuration efficiency is high, the advantages such as easy desorption and regeneration.
2, use in this technique based on the ionic liquid absorption agent of organic cation and organic anion to SO
2assimilation effect better, selective higher, desulfuration efficiency can more than 99%.
3, relative to adopting inorganic anion to be the ionic liquid absorption agent of main body in prior art, in the present invention, the ionic liquid of absorbent adopts organic anion, and the corrosivity of absorbent to equipment can be made lower, also more friendly to environment.
Accompanying drawing explanation
Fig. 1 is the process chart that absorbent in the present invention carries out flue gas desulfurization.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
Certain large-scale coal chemical industry enterprises, SO in its boiler smoke
2content be 5000 ~ 12000mg/Nm
3, temperature is 140 DEG C, adopts technological process as shown in Figure 1 to carry out flue gas desulfurization; Wherein, 1. water scrubber; 2. absorption tower; 3. regenerator; 4. rich solution pump; 5. lean pump; 6. reboiler; 7. washing pump; 8. condenser; 9. gas-liquid separator; 10. water diversion tank; 11. poor rich liquid heat exchangers; 12. lean solution coolers.
First flue gas is after booster fan boosting, enters bottom water scrubber 1.60 DEG C are cooled to, from feeding absorption tower, bottom 2 through the dedusting of washing cooling tower 1.Enter into washing pump 7 from water scrubber 1 washings out by water diversion tank 10 and carry out cleaning supercharging, after cooler cooling, again deliver to water scrubber top, be reused for cooled flue gas.Through the flue gas of dedusting cooling, enter absorption tower 2 from bottom, absorbing temperature is 60 ~ 70 DEG C, and pressure is preferably 0.1MPa.SO now in flue gas
2absorb by absorbent, the flue gas after sulphur removal can through sending flue direct emptying.Absorb SO
2after rich solution enter poor rich liquid heat exchanger 11 by the bottom of tower through rich solution pump 4, reclaim after heat and enter to be sent to regenerator 3, desorption temperature is 120 ~ 130 DEG C, and pressure is 0.1MPa.Be absorbed with SO
2rich solution enter regenerator 3 from top, by stripping desorption part SO
2after, enter reboiler 6, make SO wherein
2further desorb.Desorb SO
2after lean solution gone out by regenerator underflow, through lean pump 5, poor rich liquid heat exchanger 11, lean solution cooler 12 heat exchange cooling after, enter the top on absorption tower 2, reuptake SO
2.Absorbent continuous circulation, forms continuous absorption and desorb SO
2technical process.The SO that regenerator parses
2, concentration can reach more than 95%, by this SO
2gas-liquid separator 9 is entered, the SO after separation and purification after being cooled by condenser 8
2send into back segment program, such as, send into sulfuric acid apparatus and produce sulfuric acid, also by pressurization cooling, liquid SO can be produced
2product.SO in purified gas
2concentration be reduced to 48mg/Nm
3, desulfuration efficiency is more than 99%.
The absorbent that above-mentioned technological process adopts consists of (each proportion of composing is mass fraction): TMG tartrate 45%, n-butanol 0.3%, hydroquinones 0.15%, basic copper carbonate 0.2%, all the other are water.
This process operation result shows, the absorbent that to utilize based on ionic liquid be main body, effectively can absorb the SO in flue gas
2, absorption efficiency is high, selective good, and system can steady in a long-termly be run.
Embodiment 2
Certain large-scale coal chemical industry enterprises, SO in its boiler smoke
2content be 5000 ~ 12000mg/Nm
3, temperature is 140 DEG C, and adopt technological process as shown in Figure 1 to carry out flue gas desulfurization, concrete sweetening process is with embodiment 1.The absorbent adopted consists of (each proportion of composing is mass fraction): melbine lactate 30%, n-butanol 0.3%, hydroquinones 0.15%, basic copper carbonate 0.2%, all the other are water.After this absorbent desulfurization, SO in purified gas
2concentration be reduced to 50mg/Nm
3, desulfuration efficiency is more than 99%.
Embodiment 3
Certain large-scale coal chemical industry enterprises, SO in its boiler smoke
2content be 5000 ~ 12000mg/Nm
3, temperature is 140 DEG C, and adopt technological process as shown in Figure 1 to carry out flue gas desulfurization, concrete sweetening process is with embodiment 1.The absorbent adopted consists of (each proportion of composing is mass fraction): monoethanolamine tartrate 70%, n-butanol 0.3%, hydroquinones 0.15%, basic copper carbonate 0.2%, all the other are water.After this absorbent desulfurization, SO in purified gas
2concentration be reduced to 70mg/Nm
3, desulfuration efficiency is more than 99%.
Above are only part preferred embodiment of the present invention, the present invention is not limited in the content of embodiment.To those skilled in the art, can have various change and change in the concept of technical solution of the present invention, any change done and change, all within scope.
Claims (10)
1. a selective absorbing SO
2absorbent, the composition of this absorbent comprises: the ionic liquid of 30% ~ 70% mass fraction; The activator of 0.1% ~ 4.0% mass fraction; The antioxidant of 0.1% ~ 0.5% mass fraction; The corrosion inhibiter of 0.1% ~ 0.5% mass fraction; Surplus is water.
2. a kind of selective absorbing SO as claimed in claim 1
2absorbent, it is characterized in that: described ionic liquid is cation by nitrogenous type organic matter, organic acid is formed by anion.
3. a kind of selective absorbing SO as claimed in claim 2
2absorbent, it is characterized in that: the cation of described ionic liquid be selected from guanidine salt, alcamines, imidazoles, pyridines, four azoles, quaternary ammonium salt, thiazoles, dicyandiamide class material one or more; Described anion be selected from lactic acid, tartaric acid, citric acid, pyrovinic acid, malic acid, oxalic acid, acetic acid one or more.
4. a kind of selective absorbing SO as claimed in claim 1
2absorbent, it is characterized in that: consisting of of described absorbent, TMG tartrate 45%, n-butanol 0.3%, hydroquinones 0.15%, basic copper carbonate 0.2%, all the other are water.
5. a kind of selective absorbing SO as described in any one of claim 1-3
2absorbent, it is characterized in that: described activator is one or both in organic alcohols material.
6. a kind of selective absorbing SO as described in any one of claim 1-3
2absorbent, it is characterized in that: described antioxidant is have one or both compositions in the phenols of week reduction or quinones substance.
7. a kind of selective absorbing SO as described in any one of claim 1-3
2absorbent, it is characterized in that: described corrosion inhibiter be selected from basic copper carbonate, potassium metavanadate, arsenic trioxide, trichloride antimony one or both.
8. one kind absorbs SO
2process, the method is: the flue gas after washing is passed into absorption tower from bottom, adopts the absorbent described in any one of claim 1-4 to absorb SO
2; Then SO will be absorbed with
2rich solution enter regenerator from top again, to SO
2carry out desorb.
9. a kind of absorption SO as claimed in claim 8
2process, it is characterized in that: in described process, absorption tower temperature is 40 ~ 90 DEG C, pressure is 0.01 ~ 0.2MPa; Described regenerator temperature is 100 ~ 150 DEG C, and pressure is 0.01 ~ 0.2MPa.
10. one absorbs SO as claimed in claim 8 or 9
2process, it is characterized in that: the SO of described solution sucking-off
2send into lower workshop section, directly synthesize H
2sO
4.
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Cited By (4)
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| CN109513329A (en) * | 2018-12-26 | 2019-03-26 | 科洋环境工程（上海）有限公司 | Absorption system and absorption technique containing sulfur dioxide flue gas |
| CN110002994A (en) * | 2019-05-05 | 2019-07-12 | 河北科技大学 | A kind of eutectic ionic liquid and its preparation method and application |
| CN110585860A (en) * | 2019-08-22 | 2019-12-20 | 太原师范学院 | Low-energy-consumption regenerated absorbent and method for absorbing sulfur dioxide in flue gas by using same |
| CN111249860A (en) * | 2020-02-26 | 2020-06-09 | 中国天辰工程有限公司 | Anhydrous ionic liquid and application thereof in flue gas desulfurization |
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