CN102049167B - High-SO2 concentration pressure smoke desulfuration method and device - Google Patents
High-SO2 concentration pressure smoke desulfuration method and device Download PDFInfo
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- CN102049167B CN102049167B CN 200910188117 CN200910188117A CN102049167B CN 102049167 B CN102049167 B CN 102049167B CN 200910188117 CN200910188117 CN 200910188117 CN 200910188117 A CN200910188117 A CN 200910188117A CN 102049167 B CN102049167 B CN 102049167B
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Abstract
The invention discloses a high-concentration smoke desulfuration method and a high-concentration smoke desulfuration device. High-sulfur dioxide concentration smoke passes through a water spray cooler, a Venturi prewasher, a bubbling contact area, a spray packed tower and a desulfuration separation tower in turn, absorbent circulating tanks in two stages are provided, the absorbent in the absorbent circulating tank in the first stage is delivered to the Venturi prewasher and the spray packed tower; the liquid phase materials discharged from the Venturi prewasher and the spray packed tower are returned to the absorbent circulating tank in the first stage, and the bubbling contact area is arranged in the absorbent circulating tank in the first stage; and the absorbent in the absorbent circulating tank in the second stage is delivered to a dynamic wave washing tower and a spray separation tower, and the liquid phase materials discharged from the dynamic wave washing tower and the spray separation tower are discharged into the absorbent circulating tank in the second stage. The high-concentration smoke desulfuration method can greatly increase desulfuration rate by optimizing a desulfuration process and the desulfuration device, and can meet the desulfuration and purification requirements of high-sulfur dioxide concentration smoke even if low-solubility alkaline reagents such as calcium and magnesium are adopted.
Description
Technical field
The present invention relates to a kind of high concentration has pressure fume desulphurization method and device, belongs to environmental improvement method field.
Background technology
SO
2Be a kind of global atmosphere pollution, its harm is mainly formation acid rain.In addition, the SO in the environment
2Can cause immunization programs for children power function reduction, common people's respiratory tract, the increase of eye illness rate etc.At oil plant, the catalytic gasoline adsorpting desulfurization device is a kind of novel process units, produces flue gas in its adsorbent reactivation process, and wherein sulfur dioxide concentration is generally 10000～100000mg/m
3, oxygen content is generally 2000～10000mg/m
3, must carry out flue gas desulfurization and process.
At present, the technique that flue gas desulfurization is mainly adopted has dry method and wet method two large classes, and wherein wet fuel gas desulfurizing technology has: limestone-gypsum method, seawater method, wet-type ammonia, two alkaline process and magnesium method flue gas desulphurization technique etc.; The dry type flue gas desulfurizing technology mainly contains: spray drying process, in-furnace calcium spraying method, circulating fluidized bed dry and charged dry sorbent injection desulfur technology etc.Above-mentioned technique all needs the links such as alkaline agent preparation, slurrying, conveying, product mummification, wastewater treatment and product accumulating, the shortcoming such as have that technological process is long, table of equipment (cover) quantity is many, occupation of land is large, investment is large, operating cost is high and the product quantity of slag is large.Take limestone-gypsum method as example, its flow process comprises: the links such as lime stone storage, fragmentation, abrasive dust, screening, slurrying, spray-absorption, Separation of gypsum, mummification, accumulating and wastewater treatment, it is a lot of to relate to number of devices, and equipment scale is very large, and its equipment investment expense and running expense are all very high.Flue gas desulfur device generally comprises spray column, dynamic wave scrubbing tower, venturi scrubber etc., but these independent flue gas desulfur devices or the simple combination of these flue gas desulfur devices can't be satisfied the demand of high sulfur dioxide FGD.For the higher flue gas of some sulfur dioxide concentrations, existing sulfur method and device are not enough to fully effectively desulfurization.In the catalytic gasoline process for adsorption desulfuration, catalyst regeneration sulfur dioxide in flue gas content can reach 50000mg/m
3More than, existing method and apparatus is purified treatment effectively.
CN200510010119.8 discloses a kind of internal circulating multistaged spray fluidized flue gas desulfurization tower, and tower body is the reverse taper shape that bottom-up cross section ladder increases; The lower surface of the one-level reverse taper in the tower body is fixedly connected with the upper surface of venturi accelerating tube, the upper surface of one-level reverse taper is fixedly connected with the lower surface of the spouted chamber of one-level, the upper surface of the spouted chamber of one-level is fixedly connected with the lower surface of secondary reverse taper, and the upper surface of secondary reverse taper is fixedly connected with the lower surface of the spouted chamber of secondary.Although this device can improve desulfurized effect to a certain extent, still can not reach required desulfurized effect for high-concentration fume.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of high SO
2Concentration has pressure fume desulphurization method and device, by optimizing sulfur removal technology and device, can greatly improve desulfurization degree, even adopt water-soluble relatively poor calcium, magnesium alkaline reagent, also can satisfy the desulfurization requirement of high concentration sulfur dioxide flue gas.
The high SO of the present invention
2Concentration has the pressure fume desulphurization method to comprise following content: high sulfur dioxide concentration has the pressure flue gas successively by venturi pre-wash device, bubbling contact zone, spray packed tower and spray knockout tower, two-stage absorbent circulating storage groove is set, first order absorbent circulating storage groove inner absorbent is delivered to venturi pre-wash device and spray packed tower, the liquid phase material that venturi pre-wash device and spray packed tower are discharged returns first order absorbent circulating storage groove, and the bubbling contact zone is arranged in the first order absorbent circulating storage groove; Second level absorbent circulating storage groove inner absorbent is delivered to the spray knockout tower, and the liquid phase material that the spray knockout tower is discharged returns second level absorbent circulating storage groove.
The high SO of the present invention
2Concentration has in the pressure fume desulphurization method, comprises following content: high sulfur dioxide concentration has the pressure flue gas to derive from the discharging gas of the adsorbent reactivation process of gasoline absorbing desulfurization technique, in general sulfur dioxide concentration 10000～100000mg/m
3, the pressure of flue gas is generally 50～100KPa (gauge pressure).Flue gas can be lowered the temperature first by the spray cooling device first before entering venturi pre-wash device when temperature is very high, and the water that sprays in the spray cooling device can be fresh water (FW), also can be the liquid phase material in the first order absorbent circulating storage groove.
In order further to improve desulfurized effect, before entering the spray knockout tower, flue gas can increase the dynamic wave scrubbing tower, flue gas is through entering the spray knockout tower again after the dynamic wave scrubbing tower, the absorption liquid that sprays in the dynamic wave scrubbing tower is the liquid phase material in the absorbent circulating storage groove of the second level.
In the method for desulfurizing high-concentration flue gas of the present invention, can adopt the alkali lye such as magnesium hydroxide, calcium hydroxide, sodium hydroxide solution (or slurries) to regulate the basicity of material in first order absorbent circulating storage groove and the second level absorbent circulating storage groove, alkali lye can also partly directly enter the top of spray packed tower.The pH value of material is generally 6.0～7.0 in the first order absorbent circulating storage groove, effluxes material and discharges after peroxidating.The pH value of material is generally greater than 10 in the absorbent circulating storage groove of the second level.Second level absorbent circulating storage groove inner absorbent enters in the first order absorbent circulating storage groove by overflow mechanism.First order absorbent circulating storage groove and second level absorbent circulating storage groove can replenish an amount of fresh water (FW), keep normally operation.Spray knockout tower top arranges the demist Disengagement zone, and the demist Disengagement zone arranges the fresh water (FW) spray equipment.Fresh water (FW) is the water that can be used for any source of process of the present invention, such as the recycle-water behind running water, industry water, the dirty water decontamination handles etc.
In this forwarding method, each unit can use the device of this area conventional structure, and concrete apparatus structure and operating condition are that the ability those skilled in the art know, and specifically can specifically determine according to the character of flue gas and the requirement of desulfurization.
High-concentration fume desulfurizer of the present invention comprises venturi pre-wash device, bubbling contact zone member, spray packed tower, spray knockout tower and the absorbent circulatory system successively along the flow of flue gas direction, the absorbent circulatory system comprises the first order absorbent circulatory system and the second level absorbent circulatory system, venturi pre-wash device, bubbling contact zone member and spray packed tower are arranged in the first order absorbent circulatory system, and the spray knockout tower is arranged in the absorbent circulatory system of the second level.Before venturi pre-wash device, the washing cooler can be set, before the spray knockout tower, the dynamic wave scrubbing tower can be set.
In apparatus of the present invention, the first order absorbent circulatory system comprises first order absorbent circulating storage groove and first order absorbent conveying device, bubbling contact zone member is immersed in the first order absorbent circulating storage groove, and first order absorbent conveying device is transported to absorbent in Venturi scrubber and the spray packed tower.The second level absorbent circulatory system comprises second level absorbent circulating storage groove and second level absorbent conveying device, and second level absorbent conveying device is transported to absorbent in dynamic wave scrubbing tower and the spray knockout tower.First order absorbent circulating storage groove and second level absorbent circulating storage groove make up line with fresh alkali lye and are connected, second level absorbent circulating storage groove communicates by flow structure with first order absorbent circulating storage groove, first order absorbent circulating storage groove arranges exhaust system, and exhaust system is connected with oxidation unit.
In apparatus of the present invention, spray knockout tower top arranges the demist Disengagement zone, and the demist Disengagement zone arranges the fresh water (FW) spray equipment.First order absorbent circulating storage groove can make up line with fresh water (FW) with second level absorbent circulating storage groove and communicate.The washing cooler can make up line with fresh water (FW) and communicate or communicate with the first order absorbent circulatory system.
The inventive method and device can be used for various high-concentration fume desulphurization systems, and optimum is used for the sweetening process of catalytic gasoline adsorption-desulfurization sorbent regenerated flue gas.The each several part structure and parameters that Multistage fume gas desulfurization device of the present invention relates to can be determined by this area specific knowledge according to character and the processing requirements of smoke treatment by those skilled in the art.Fresh alkali lye can be solution or the slurries of various alkaline matters, preferred sodium hydroxide solution or magnesium hydroxide slurry.
The inventive method and device have been determined suitable desulfurizer structure and flow process according to the desulfurization requirement of high-concentration fume, can satisfy the requirement of high-concentration fume high-efficiency desulfurization.
Description of drawings
Fig. 1 is high-concentration fume desulfurizer apparatus structure schematic diagram of the present invention.
Wherein: the 1-flue gas, 2-washs cooler, 3-Venturi scrubber, the 4-spray packed tower, 5-bubbling contact zone member, 6-dynamic wave scrubbing tower, 7-sprays knockout tower, 8-demist Disengagement zone, 9-first order absorbent circulating storage groove, 10-second level absorbent circulating storage groove, the 11-oxidation unit, the fresh alkaline absorbent of 12-makes up line, and 13-replenishes the fresh water (FW) pipeline, flue gas after 14-purifies.
The specific embodiment
Further specify high-concentration fume purifier structure of the present invention and technological effect below in conjunction with accompanying drawing.
As shown in Figure 1, high concentration of the present invention has pressure smoke eliminator device to comprise washing cooler 2, venturi pre-wash device 3, spray packed tower 4, bubbling contact zone member 5, dynamic wave scrubbing tower 6 and spray knockout tower 7.The circulation absorbent of first order absorbent circulating storage groove 9 is circulated to venturi pre-wash device 3 and spray packed tower 4, and the circulation absorbent of second level absorbent circulating storage groove 10 is circulated to dynamic wave scrubbing tower 6 and spray knockout tower 7.The top of spray knockout tower 7 arranges demist Disengagement zone 8, purifying smoke 14 dischargings after demist.Second level absorbent circulating storage groove 10 inner absorbents enter first order absorbent circulating storage groove 9 by overflow mechanism, and the absorbent partial discharge of first order absorbent circulating storage groove 9 is to oxidation unit 11, are to discharge behind the sulfate with wherein sulfite oxidation.First order absorbent circulating storage groove 9 and second level absorbent circulating storage groove 10 arrange fresh alkaline absorbent and make up line 12.First order absorbent circulating storage groove 9 and second level absorbent circulating storage groove 10 all arrange and replenish fresh water (FW) pipeline 13.
When the multistage smoke eliminator of the present invention used, flue gas 1 utilized self pressure of flue gas successively by washing cooler 2, venturi pre-wash device 3, spray packed tower 4, bubbling contact zone member 5, dynamic wave scrubbing tower 6 and spray knockout tower 7.Wherein venturi pre-wash device 3 major functions are flue gas cool-down and pre-partial desulfurization, and general liquid-gas ratio is 0.5～5L/m
3, flue-gas temperature can be down to below 60 ℃, at device during operation exception, can adopt the operation of lowering the temperature of washing cooler 2.Bubbling contact zone member 5 is arranged in the first order absorbent circulating storage groove 9, can obtain the desulfurization degree greater than 10% in this bubbling zone.Spray packed tower 4 is main desulphurization plants, and the operation liquid-gas ratio is generally 1～10L/m
3, the flue gas air speed is 300～1500h
-1, the sulfur dioxide removal rate can reach (with spray packed tower inlet flue gas densimeter) more than 95%.Spray knockout tower 7 is further desulphurization plant, and the operation liquid-gas ratio is generally 1～10L/m
3, the sulfur dioxide removal rate can reach (with spray knockout tower inlet flue gas densimeter) more than 95%.If need to further increase desulfurization degree, can before the spray knockout tower, dynamic wave scrubbing tower 6 be set.By above-mentioned multistep desulfurization operations, can with the effective desulfurizing and purifying of high concentration sulfur dioxide flue gas, reach discharge standard.
Embodiment
(main character: 205 ℃ of temperature, pressure 80KPa (gauge pressure), sulfur dioxide concentration are 50000～75000mg/m to certain catalytic gasoline adsorption-desulfurization sorbent high concentration regenerated flue gas
3), adopt the inventive method to process, concrete operations condition and the results are shown in Table 1.
Table 1 high-concentration fume desulfurization operations condition and result
| Operating condition and result | Operating condition 1 | Operating condition 2 |
| Venturi is washed device liquid gas volume ratio, L/m 3 | ?2 | ?4 |
| Venturi is washed the device outlet temperature, ℃ | ?55 | ?51 |
| Spray packed tower liquid gas volume ratio, L/m 3 | ?5 | ?8 |
| The spray packed tower air speed, h -1 | ?500 | ?750 |
| Spray knockout tower liquid gas volume ratio, L/m 3 | ?4 | ?7 |
| Replenish absorbent | 30wt%NaOH solution | ?20wt％Mg(OH) 2Slurries |
| First order absorbent circulating storage groove pH value | ?6.5～6.8 | ?6.0～6.5 |
| Second level absorbent circulating storage groove pH value | Greater than 10 | Greater than 8 |
| Outlet SO 2 from fume content, mg/m 3 | ?＜120 | ?＜135 |
| Total desulfurization degree, % | ?＞99.5 | ?＞99.5 |
Claims (9)
1. high SO
2Concentration has the pressure fume desulphurization method, it is characterized in that: high sulfur dioxide concentration has the pressure flue gas successively by venturi pre-wash device, bubbling contact zone, spray packed tower and spray knockout tower, two-stage absorbent circulating storage groove is set, first order absorbent circulating storage groove inner absorbent is delivered to venturi pre-wash device and spray packed tower, the liquid phase material that venturi pre-wash device and spray packed tower are discharged returns first order absorbent circulating storage groove, and the bubbling contact zone is arranged in the first order absorbent circulating storage groove; Second level absorbent circulating storage groove inner absorbent is delivered to the spray knockout tower, and the liquid phase material that the spray knockout tower is discharged returns second level absorbent circulating storage groove; It is 10000～100000mg/m that high sulfur dioxide concentration has the sulfur dioxide concentration of pressure flue gas
3, pressure is 50～100KPa, force value is gauge pressure.
2. in accordance with the method for claim 1, it is characterized in that: flue gas was lowered the temperature first by the spray cooling device first before entering venturi pre-wash device, the water that sprays in the spray cooling device is fresh water (FW), or the liquid phase material in the first order absorbent circulating storage groove.
3. in accordance with the method for claim 1, it is characterized in that: before flue gas enters the spray knockout tower, increase the dynamic wave scrubbing tower, flue gas is through entering the spray knockout tower again after the dynamic wave scrubbing tower, the absorption liquid that sprays in the dynamic wave scrubbing tower is the liquid phase material in the absorbent circulating storage groove of the second level.
4. in accordance with the method for claim 1, it is characterized in that: adopt alkali lye to regulate the basicity of material in first order absorbent circulating storage groove and the second level absorbent circulating storage groove, the pH value of material is 6.0～7.0 in the first order absorbent circulating storage groove, effluxes material and discharges after peroxidating; The pH value of material is greater than 10 in the absorbent circulating storage groove of the second level, and second level absorbent circulating storage groove inner absorbent enters in the first order absorbent circulating storage groove by overflow mechanism.
5. it is characterized in that in accordance with the method for claim 4: the alkali lye part directly enters the top of spray packed tower.
6. it is characterized in that in accordance with the method for claim 1: venturi pre-wash device liquid-gas ratio is 0.5～5L/m
3, the spray packed tower liquid-gas ratio is 1～10L/m
3, the flue gas air speed is 300～1500h
-1, spray knockout tower operation liquid-gas ratio is 1～10L/m
3
7. high SO
2Concentration has the pressure flue gas desulfur device, it is characterized in that: comprise successively venturi pre-wash device, bubbling contact zone member, spray packed tower, spray knockout tower and the absorbent circulatory system along the flow of flue gas direction, the absorbent circulatory system comprises the first order absorbent circulatory system and the second level absorbent circulatory system, venturi pre-wash device, bubbling contact zone member and spray packed tower are arranged in the first order absorbent circulatory system, and the spray knockout tower is arranged in the absorbent circulatory system of the second level; High SO
2It is 10000～100000mg/m that concentration has the sulfur dioxide concentration of pressure flue gas
3, pressure is 50～100KPa, force value is gauge pressure.
8. according to device claimed in claim 7, it is characterized in that: the first order absorbent circulatory system comprises first order absorbent circulating storage groove and first order absorbent conveying device, bubbling contact zone member is immersed in the first order absorbent circulating storage groove, and first order absorbent conveying device is transported to absorbent in Venturi scrubber and the spray packed tower; The second level absorbent circulatory system comprises second level absorbent circulating storage groove and second level absorbent conveying device, and second level absorbent conveying device is transported to absorbent in the spray knockout tower; First order absorbent circulating storage groove and second level absorbent circulating storage groove make up line with fresh alkali lye and are connected, second level absorbent circulating storage groove communicates by flow structure with first order absorbent circulating storage groove, first order absorbent circulating storage groove arranges exhaust system, and exhaust system is connected with oxidation unit.
9. according to claim 7 or 8 described devices, it is characterized in that: before venturi pre-wash device, the washing cooler is set, before the spray knockout tower, the dynamic wave scrubbing tower is set.
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| CN102389704A (en) * | 2011-10-21 | 2012-03-28 | 宜宾天原集团股份有限公司 | Smoke wet desulphurization technology |
| CN102527214A (en) * | 2011-12-23 | 2012-07-04 | 中国石油化工股份有限公司 | Method for removing hydrogen sulfide from gas |
| CN102814102A (en) * | 2012-07-27 | 2012-12-12 | 中国铝业股份有限公司 | Method for desulfurizing flue gas from aluminum electrolysis |
| CN104607012B (en) * | 2013-11-05 | 2017-01-04 | 中国石油化工股份有限公司大连石油化工研究院 | A kind of flue gas desulfurization and waste liquid oxidization combination device |
| CN103961988A (en) * | 2014-05-19 | 2014-08-06 | 张继惟 | Technical method of purification of flue gas with high water content and major fluctuations |
| CN104560223B (en) * | 2014-12-11 | 2017-01-04 | 南京中电环保科技有限公司 | A kind of gas desulfurizer and method thereof |
| CN107281920A (en) * | 2017-06-12 | 2017-10-24 | 太仓运权化工防腐设备有限公司 | A kind of flue gas desulfurization device |
| CN113509831A (en) * | 2021-06-16 | 2021-10-19 | 宁波新福钛白粉有限公司 | Sulfuric acid method titanium dioxide acidolysis tail gas treatment system and treatment method |
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| CN2277296Y (en) * | 1997-01-30 | 1998-04-01 | 北京市市政工程机械公司 | High-efficiency wet-desulfurizing dust remover |
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