CN102049176A - Flue gas desulfurization process adopting high-gravity solvent cycle absorption method - Google Patents
Flue gas desulfurization process adopting high-gravity solvent cycle absorption method Download PDFInfo
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Abstract
The invention is characterized in that a high-gravity rotating packed bed is applied to flue gas desulfurization process and desulphurization solvent regeneration process of ionic liquid, organic amine and other desulphurization solvents, nitrogen, air and the like are taken as stripping gas to take part in desorption of SO2 in desulphurization solvent and regeneration of desulphurization solvent, and the technologies of filter purification, adsorption purification and desalination purification of desulphurization solvent are combined, so that the flue gas desulfurization process adopting the high-gravity solvent cycle absorption method is formed, which has the characteristics of low equipment investment, low energy consumption and high desulphurization stability and has the functions of both flue gas desulfurization control and sulfurous pollutant resource utilization. The technology provided by the invention can be widely applied to the field of flue gas desulfurization in the industries of iron steel, nonferrous metallurgy, thermoelectricity, chemical engineering, building material and the like.
Description
Technical field
The present invention relates to a kind of technological process of adopting high-gravity technology to carry out flue gas desulfurization, mainly be applicable to the flue gas desulfurization of industries such as iron and steel, nonferrous metallurgy, thermoelectricity, chemical industry, building materials, be particularly useful for the occasion that adopts the solvent absorption cycle to carry out flue gas desulfurization in the above-mentioned field.
Background technology
At present, the fume desulphurization method of domestic employing is a lot, as lime stone---gypsum method, two alkaline process, magnesium oxide method etc., but also there is following shortcoming simultaneously in varying degrees in above-mentioned sulfur method: (1) complex process, equipment investment height, operating cost height, floor space are big, and the wide and discarded object of desulfurizing byproduct purposes is difficult to dispose; (2) desulfurizing agent can not be regenerated mostly, thereby can not reuse; (3) external some flue gases purifications of introducing are not suitable for China's national situation, though device equipment advanced persons that some countries introduce from the U.S., Japan and West Europe for example, automatic control degree height, but its equipment investment and operating cost are very expensive, national power of China and national conditions can't allow us to take external existing method, this makes over nearly 20 years, the very difficult popularization of technology and equipment that China spends huge sums and introduces.
And along with the development of technology, the solvent absorption cycle flue gas desulfurization technique of Chu Xianing has been subjected to paying attention to widely both at home and abroad and developing because its technological process is brief, desulfurization solvent can be recycled, desulfurizing byproduct has higher economic value in recent years.The desulfurization solvent that can be used for the flue gas desulfurization of solvent absorption cycle at present mainly is organic amine and ionic liquid.Wherein, the organic amine desulfurizing agent is mainly formed with liquid monoamine, diamine or its mixture, as the SO of Cansolv company
2Remove solvent and be the organic amine desulfurization solvent that a kind of main component is a diamine.And ionic liquid be by anion and cation composition in room temperature or near the material that is in a liquid state under the room temperature, it does not generally have vapour pressure, ionic liquid has only by after the specific molecule design and just possesses splendid SO
2Absorb selectivity, SO
2Absorptive capacity and easily desorb regeneration at high temperature can be used as desulfurization solvent.Patent of invention " removes and reclaim the absorbent of sulfur dioxide " from gaseous mixture (application number 200710048743.6) " sulfur dioxide absorbent " of having proposed, its essence is a kind of ionic liquid that can be used as desulfurizing agent.During as desulfurizing agent, it can absorb SO when normal temperature with ionic liquid or organic amine
2And under high-temperature condition, separate sucking-off SO
2, and can utilize desulfurizing byproduct SO
2Prepare sulfuration chemical products such as sulfuric acid, sulphur for base stock, this has the double meaning that flue gas desulfurization improvement and changing waste into resources utilize under the situation of China's ubiquity sulphur resource shortage.
But at present, the existing solvent absorption cycle flue gas desulfurization technique that matches with desulfurization solvents such as ionic liquid or organic amines, its essence mainly still is tradition " absorption---regeneration cycle " technology in the chemical process, and promptly desulfurization solvent adopts the absorption tower to absorb SO in the flue gas at normal temperatures
2, thereafter again in regenerator with external heat source heating desulfurization solvent and be aided with water vapour gas and carry, make it at high temperature separate sucking-off SO
2And make and self regenerated and recycle.Patent of invention " removes and reclaim the absorbent of sulfur dioxide " from gaseous mixture (application number 200710048743.6) also explains to some extent to this sulfur removal technology.But there are three important shortcomings in this technology, at first, with the absorption tower as SO
2Absorption equipment and with regenerator as the desulfurization solvent reclaim equiment, under the bigger situation of exhaust gas volumn and desulfurization solvent internal circulating load, absorption tower and regenerator (especially absorption tower) are bulky, housing structure is complicated, equipment investment is huge.Secondly, in regenerator,, employing is aided with the mode desorb SO that water vapour gas is carried because heating
2, the regenerative sulfur binding solvent, so desulfurization solvent regeneration energy consumption is high.In addition, usually the component in the flue gas is very complicated, wherein can cause the impurity of adverse effect to mainly contain three classes to desulfurization solvent, promptly the component cation forms the anion of thermal-stable salt (as SO in solid impurity (as dust), the organic matter that is soluble in desulfurization solvent and easily a small amount of and the desulfurization solvent
4 2-, F
-, Cl
-Deng).Though the water washing dedust heat sink can be removed most of above-mentioned impurity in the flue gas, but after small amount of impurities enters desulfurization solvent, its continuous accumulation in system will make the component of desulfurization solvent change, desulfuration efficiency and regeneration effect to desulfurization solvent cause great reduction effect, and threaten the normal operation of desulfurizer.
Therefore, from reducing the angle of flue gas desulfur device investment, reduction plant energy consumption, enhancing desulfurizer long period stability, and bring into play the application advantage of desulfurization solvents such as ionic liquid, organic amine to greatest extent in the flue gas desulfurization field, be necessary to set up the new process for fume desulfurization that adapts with the solvent method desulfurization.
Summary of the invention
Hypergravity solvent absorption cycle flue gas desulfurization technique flow process provided by the present invention, it is specially adapted to adopt desulfurization solvent to carry out the occasion of flue gas desulfurization.The purpose of invention is to form with desulfurization solvent and adapts, and possesses the new process for fume desulfurization of low equipment investment, low operation energy consumption, high desulfurization stability characteristics.
Hypergravity solvent absorption cycle flue gas desulfurization technique flow process provided by the present invention, its main contents comprise: desulfurization solvent adopts SO in the rotary packed bed absorption flue gas of hypergravity at normal temperatures
2, at high temperature adopt the rotary packed bed sucking-off SO that separates of hypergravity again
2And make desulfurization solvent be able to the regeneration cycle use; Be provided with desulfurization solvent filtration, purification, adsorption cleaning and desalination cleaning system, with stability and the desulfurization performance of keeping desulfurization solvent.
Among the present invention, utilize desulfurization solvent to absorb SO in the flue gas
2Desulfurizing and purifying process and desulfurization solvent separate sucking-off SO
2The desulfurization solvent regenerative process, it is rotary packed bed that absorption that it adopted or reclaim equiment are hypergravity.As a kind of hypergravity equipment, hypergravity is rotary packed bed to be rotated formed centrifugal force with filling batch and simulates and realize the hypergravity environment.Because under the hypergravity environment, gas---liquid two-phase produces the contact of flowing in porous media such as structured packing or dumped packing or duct, great shear forces is torn into liquid the liquid film of micron to nano grade, brin and drop, produce the boundary of huge and quick renewal, make 1～3 order of magnitude of raising in the interphase mass transfer speed ratio tradition tower, microcosmic mixes and mass transport process is greatly strengthened, therefore, in the desulfurizing and purifying stage of flue gas, adopt rotary packed bed greatly reinforcing desulfuration solvent---mass transport process between the gas-liquid two-phase of flue gas, significantly improve desulfurization solvent SO in the flue gas
2Absorption rate and the utilization rate of desulfurization solvent, and can reduce desulfurization solvent internal circulating load in the desulfurizer thus; Equally, separate sucking-off SO at desulfurization solvent
2The desulfurization solvent regeneration stage, adopt rotary packed bed also very big reinforcing desulfuration solvent---mass transport process between the gas-liquid two-phase of gas stripping gas, significantly improve gas stripping gas such as nitrogen, air to SO in the desulfurization solvent
2Gas stripping efficiency.Because rotary packed bed employing, absorption and reclaim equiment have been realized brand-new hypergravity reinforcement mass transfer pattern in the desulfurizer when gas-liquid mass transfer, thereby its equipment volume and equipment investment are sharply reduced, usually under the situation of identical flue gas treating capacity, rotary packed bed volume only is 1/5～1/20 of traditional absorption tower (or regenerator) volume, and equipment investment reduces more than 40% than the latter, and technology has clear superiority.
Simultaneously, among the present invention, separate sucking-off SO at desulfurization solvent
2The desulfurization solvent regeneration stage, except with the rotary packed bed replacement regenerator of hypergravity as the reclaim equiment, on regeneration, the gas stripping gas when also replacing water vapour as regeneration with nitrogen heating or normal temperature, air or other gas.Owing to compare with water vapour, gas such as nitrogen, air possesses lower thermal capacitance, when heating up, need then are easier to heat temperature raising, and the heat of vaporization in the time of needn't providing water vapour to form, during therefore as gas stripping gas, the use of gas such as nitrogen, air has the considerable energy saving advantage, and it is compared with the mode that traditional heating and water vapour gas are carried, and the energy consumption of desulfurization solvent can being regenerated reduces more than 25%.In addition, as previously mentioned, owing to adopt the rotary packed bed desulfurization solvent internal circulating load that can reduce desulfurizer during as absorption equipment of hypergravity, this has also directly reduced the desulfurization solvent amount and the regeneration energy consumption of required regeneration.Therefore, the employing that hypergravity is rotary packed bed, and the gas stripping gas when gases such as nitrogen, air are replaced water vapour as regeneration can promote the remarkable reduction of desulfurizer energy consumption.
Among the present invention, adopt SO in the rotary packed bed absorption flue gas of hypergravity
2The time, for satisfying desulfurization solvent to SO
2Good absorption capacity and absorption efficiency, suitable flue-gas temperature is 10～75 ℃.
Among the present invention, adopt the rotary packed bed sucking-off SO that separates of hypergravity
2And when desulfurization solvent is regenerated, by improving desulfurization solvent to being absorbed SO
2The desorb degree and the regeneration efficiency of desulfurization solvent, suitable desulfurization solvent regeneration temperature is 80～150 ℃.
In addition, as previously mentioned, contained solid impurity (as dust) in the flue gas, be soluble in the organic matter of desulfurization solvent and easily with desulfurization solvent in the anion of component cation formation thermal-stable salt, all will cause great negative effect to the desulfuration efficiency and the regeneration effect of desulfurization solvent.Be stability and the desulfurization performance of keeping the desulfurization solvent component, so the present invention is provided with desulfurization solvent filtration, purification system, removes the middle solid impurity that desolvates in the mode of mechanical filter; Be provided with desulfurization solvent adsorption cleaning system, to remove organic impurities in the solvent as adsorbents adsorb such as active carbons; Be provided with desulfurization solvent desalination cleaning system, to remove the heat endurance salt impurity of the middle accumulation of desolvating.
Desulfurization solvent desalination cleaning system described in the present invention, for enter easy formation thermal-stable salt in the desulfurization solvent as SO
4 2-Deng anion, can utilize ion-exchange, adopt anion exchange resin to remove; Also can utilize chemical precipitation method, adopt precipitating reagents such as for example adding milk of lime, form calcium precipitation, the mode with Separation of Solid and Liquid such as centrifugations removes again; Also can utilize electroosmose process, adopt electrodialysis cell, outside under the effect of electric field, migrate by the orientation of ion and anion to be enriched in anode to remove.Desulfurization solvent desalination cleaning system described in the present invention can adopt single desalination technology or its technical combinations such as above-mentioned ion-exchange, chemical precipitation method, electroosmose process.
Favourable part of the present invention is, by the rotary packed bed application in desulfurization solvent flue gas desulfurization course and desulfurization solvent regenerative process of hypergravity, and adopts gases such as nitrogen, air to participate in SO in the desulfurization solvent as gas stripping gas
2Desorb and the regeneration of desulfurization solvent, and in conjunction with filtration, purification, adsorption cleaning and the desalination purification techniques of desulfurization solvent, formed possess low equipment investment, low operation energy consumption, high desulfurization stability hypergravity solvent absorption cycle flue gas desulfurization technique characteristics, that take into account flue gas desulfurization improvement and amounts of sulphur contaminants recycling.
Description of drawings
Fig. 1 is the schematic diagram of the hypergravity solvent absorption cycle flue gas desulfurization technique flow process that content is implemented according to the present invention.
The specific embodiment
Embodiment 1
Hypergravity solvent absorption cycle flue gas desulfurization with the steel works sintering flue gas is example, and the present invention will be described in conjunction with Fig. 1.
About about the 140 ℃ sinter fume that comes out from main exhauster, enter booster fan, after booster fan boosts, enter water scrubber, with from washing cat head spray and under washing cold water counter current contacting, washings such as the most dust in the flue gas, organic impurities are got off, after flue-gas temperature is reduced to about 50 ℃, enter the rotary packed bed absorber of hypergravity, in the rotary packed bed absorber of hypergravity, strengthen mass transfer, the SO in the flue gas with desulfurization solvent lean solution adverse current
2Being desulfurized solvent absorbs.Unabsorbed purified gas is drawn emptying from absorbing cat head.Deliver to cooling tower from the hot washings that water scrubber comes out, go into the sedimentation basin precipitation through spray cooling is laggard, remove mud after, add again and be sent to water scrubber top cooled flue gas again.Washings are because of the accumulation of absorption portion sour gas, and it is acid that water quality is, and should extract part acid water continuously out from sedimentation basin, send Sewage Disposal to handle, and replenish the part fresh water simultaneously, to keep the stable of washings pH value.Absorb SO
2After desulfurization solvent be called rich solution, rich solution flows out from the rotary packed bed absorber bottom of hypergravity goes forward side by side into poor rich liquid heat exchanger, with enter the rich solution heater after the hot lean solution heat exchange and be heated to about 80～120 ℃, enter the rotary packed bed regenerator of hypergravity again and its counter current contacting gas is carried, thereby separate the rich SO of sucking-off with hot nitrogen or hot-air
2Gaseous mixture, and desulfurization solvent is regenerated as contain SO
2Lower lean solution.Lean solution is delivered to the poor rich liquid heat exchanger heat exchange, rich SO
2Gas is sent to relieving haperacidity or system sulphur after condensation, gas-liquid separation.The condensate liquid that forms in the condenser, the liquid of gas-liquid separator IT merge with the lean solution that flows out from poor rich liquid heat exchanger, after the cooling of lean solution cooler, purification after filtration again, adsorption cleaning and desalination purify, to remove solid impurity, organic impurities and thermal-stable salt, thereby form clean desulfurization solvent lean solution, enter the rotary packed bed absorber of hypergravity again the SO in the flue gas
2Absorb.
Claims (5)
1. hypergravity solvent absorption cycle flue gas desulfurization technique flow process is characterized in that: (1) desulfurization solvent at normal temperatures adopts SO in the rotary packed bed absorption flue gas of hypergravity
2, at high temperature adopt the rotary packed bed desulfurization solvent that makes of hypergravity to separate sucking-off SO again
2And make desulfurization solvent be able to the regeneration cycle use; (2) be provided with desulfurization solvent filtration, purification, adsorption cleaning and desalination cleaning system, with stability and the desulfurization performance of keeping desulfurization solvent.
2. according to the described hypergravity solvent of claim 1 absorption cycle flue gas desulfurization technique flow process, it is characterized in that the rotary packed bed desulfurization solvent that makes of utilization hypergravity is separated sucking-off SO under the high temperature
2And making desulfurization solvent when regeneration, adopting heating or normal temperature nitrogen, air or other gas during hypergravity is rotary packed bed is that gas stripping gas is to SO in the desulfurization solvent
2Carrying out gas carries.
3. according to the described hypergravity solvent of claim 1 absorption cycle flue gas desulfurization technique flow process, it is characterized in that desulfurization solvent adopts SO in the rotary packed bed absorption flue gas of hypergravity
2The time, suitable flue-gas temperature is 10～75 ℃.
4. according to the described hypergravity solvent of claim 1 absorption cycle flue gas desulfurization technique flow process, it is characterized in that adopting the rotary packed bed desulfurization solvent that makes of hypergravity to separate sucking-off SO
2And making desulfurization solvent when regeneration, suitable desulfurization solvent regeneration temperature is 80～150 ℃.
5. according to the described hypergravity solvent of claim 1 absorption cycle flue gas desulfurization technique flow process, it is characterized in that desulfurization solvent desalination cleaning system can adopt single desalination technology or its technical combinations such as ion-exchange, chemical precipitation method, electroosmose process.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019137A (en) * | 2010-12-01 | 2011-04-20 | 中北大学 | Method and device for removing low-concentration sulfur dioxide in flue gas |
| CN103285728A (en) * | 2013-06-14 | 2013-09-11 | 中石化南京工程有限公司 | Method and device for treating sulfur dioxide in sulfuric acid tail gas |
| CN103482583A (en) * | 2013-09-10 | 2014-01-01 | 山东三维石化工程股份有限公司青岛分公司 | SWSR (SunWay Sulfur recovery)-1 device and technique |
| CN105935540A (en) * | 2016-05-31 | 2016-09-14 | 衢州巨化锦纶有限责任公司 | Apparatus and method for removing and recovering sulfur dioxide in mixed gas |
| CN106422667A (en) * | 2015-08-04 | 2017-02-22 | 北京思践通科技发展有限公司 | Method for removing acidic components and water from gas in one step |
| CN106853322A (en) * | 2015-12-08 | 2017-06-16 | 谈骏嵩 | Device for absorbing a component in a gas |
| CN107583431A (en) * | 2016-07-07 | 2018-01-16 | 北京化工大学苏州（相城）研究院 | High gravity desulfurization method based on sacrificial desulfurizing agent and put into skid |
| CN108744932A (en) * | 2018-06-20 | 2018-11-06 | 北京化工大学 | One kind removing from industrial smoke or tail gas and recycle SO2Device and technique |
| US10413862B2 (en) | 2015-12-08 | 2019-09-17 | National Tsing Hua University | Apparatus and method for absorbing a component from a gas mixture using rotating packed bed unit |
| CN110732238A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | sulfur-containing tail gas treatment method and system |
| CN112246071A (en) * | 2020-09-29 | 2021-01-22 | 中国船舶重工集团公司第七一一研究所 | Flare gas compression and desulfurization integrated process and system |
| CN114191942A (en) * | 2021-09-28 | 2022-03-18 | 广东捷玛节能科技股份有限公司 | Flue gas CO2Hypergravity regeneration energy-saving process for trapping system |
| CN114367169A (en) * | 2020-10-15 | 2022-04-19 | 北京荣华康都环境技术有限公司 | Flue gas renewable desulfurization device and method |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019137B (en) * | 2010-12-01 | 2013-02-06 | 中北大学 | A method and device for removing low-concentration sulfur dioxide in flue gas |
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| CN103285728A (en) * | 2013-06-14 | 2013-09-11 | 中石化南京工程有限公司 | Method and device for treating sulfur dioxide in sulfuric acid tail gas |
| CN103285728B (en) * | 2013-06-14 | 2015-02-11 | 中石化南京工程有限公司 | Method and device for treating sulfur dioxide in sulfuric acid tail gas |
| CN103482583A (en) * | 2013-09-10 | 2014-01-01 | 山东三维石化工程股份有限公司青岛分公司 | SWSR (SunWay Sulfur recovery)-1 device and technique |
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| CN106422667A (en) * | 2015-08-04 | 2017-02-22 | 北京思践通科技发展有限公司 | Method for removing acidic components and water from gas in one step |
| CN106853322A (en) * | 2015-12-08 | 2017-06-16 | 谈骏嵩 | Device for absorbing a component in a gas |
| US10413862B2 (en) | 2015-12-08 | 2019-09-17 | National Tsing Hua University | Apparatus and method for absorbing a component from a gas mixture using rotating packed bed unit |
| CN105935540A (en) * | 2016-05-31 | 2016-09-14 | 衢州巨化锦纶有限责任公司 | Apparatus and method for removing and recovering sulfur dioxide in mixed gas |
| CN107583431A (en) * | 2016-07-07 | 2018-01-16 | 北京化工大学苏州（相城）研究院 | High gravity desulfurization method based on sacrificial desulfurizing agent and put into skid |
| CN108744932A (en) * | 2018-06-20 | 2018-11-06 | 北京化工大学 | One kind removing from industrial smoke or tail gas and recycle SO2Device and technique |
| CN110732238A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | sulfur-containing tail gas treatment method and system |
| CN112246071A (en) * | 2020-09-29 | 2021-01-22 | 中国船舶重工集团公司第七一一研究所 | Flare gas compression and desulfurization integrated process and system |
| CN114367169A (en) * | 2020-10-15 | 2022-04-19 | 北京荣华康都环境技术有限公司 | Flue gas renewable desulfurization device and method |
| CN114191942A (en) * | 2021-09-28 | 2022-03-18 | 广东捷玛节能科技股份有限公司 | Flue gas CO2Hypergravity regeneration energy-saving process for trapping system |
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Application publication date: 20110511 |