CN1923339A - Fume desulfurizing process with enhancement lime method - Google Patents
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Abstract
The invention relates to a method for desulfurising smoke, especially a strengthen limestone smoke desulfurising method. Wherein, it comprises adding limestone and additive into reactor, to be mixed and reacted with water to generate adsorption slurry; inputting slurry into adsorption tower; the sulfur smoke enters into tower to react with slurry; the purified smoke is discharge outside the tower; the slurry with sulfur dioxide will be discharged at the bottom of tower to be recycled. The invention can improve desulfurising efficiency at 5-10% and improve the absorber utilization at 1-10%.
Description
Technical Field
The invention relates to a flue gas desulfurization process, in particular to an enhanced lime method flue gas desulfurization process which is mainly applied to the technical field of atmospheric pollution treatment and prevention.
Background
The history of flue gas desulfurization has been long and studies have been made by people as early as over a hundred years ago. Currently, desulfurization techniques can be classified into three major categories: (1) desulfurization before combustion, such as coal washing and microbial desulfurization; (2) desulfurizing during combustion, such as industrial briquette sulfur fixation and in-furnace calcium injection; (3) post-combustion desulfurization, i.e., Flue Gas Desulfurization (FGD). The FGD process is the only large-scale commercial desulfurization technology in the world. FGD technology, mainly uses absorbent or adsorbent to remove SO in flue gas2And converting it to a more stable sulfur compound. FGD technology is widely varied, but the wet limestone/lime process is dominant in today's technology.
The wet limestone/lime fume desulfurizing technology is to utilize low cost lime and limestone as absorbent to absorb SO in fume2To produce calcium sulfite hemihydrate or gypsum. The technology influences the application of the technology in thermal power plants in the 70 s due to the problems of large investment, high operating cost, corrosion, scaling, blockage and the like. After years of practice and improvement, the working performance and reliability are greatly improved,the investment and operating cost are obviously reduced, and the method is a main method for flue gas desulfurization in devices introduced in China at present. The method has the main advantages that: a. the desulfurization efficiency is high (when the Ca/S of some devices is 1, the desulfurization efficiency is more than 95%); b. the utilization rate of the absorbent is high and can be more than 95 percent; c. the equipment running rate is high (can reach more than 95 percent). The flue gas desulfurization technology and equipment of 2 sets of wet limestone/gypsum method matched with 2 x 360MW unit introduced into the Chongqing Lopa sulfur plant during the seven five period, namely Mitsubishi heavy industry, firstly establishes the flue gas desulfurization demonstration project of a large-scale power plant boiler, and is put into commercial operation in 1992 and 1993, the desulfurization rate of the system reaches more than 95%, and the purity of the byproduct gypsum is higher than 90%.
However, the existing wet limestone/lime flue gas desulfurization technology has the main disadvantages of high investment, and the need of carrying out oxidation control (forced oxidation or inhibition oxidation) on sulfite generated in the desulfurization process to ensure the reliable operation of the system, which results in higher operation cost.
Disclosure of Invention
The invention provides an enhanced lime method flue gas desulfurization process which can improve the utilization rate of a desulfurizer, reduce the desulfurization cost and avoid system scaling without oxidation control.
A flue gas desulfurization process by an enhanced lime method comprises the steps of respectively inputting lime and an additive into a digestion reactor, mixing the lime and the additive in the digestion reactor, andreacting with water to generate absorption slurry; inputting the absorption slurry into an absorption tower, and discharging purified flue gas out of the absorption tower after the sulfur-containing flue gas enters the absorption tower and reacts with the absorption slurry; the absorption slurry absorbing the sulfur dioxide is discharged from the bottom of the absorption tower and recycled or subjected to post-treatment.
The post-treatment process comprises the following steps: discharging the absorption slurry absorbing sulfur dioxide from the bottom of the absorption tower, then feeding the absorption slurry into a hydrocyclone for solid-liquid separation, returning the top flow of the hydrocyclone into the absorption tower or mechanically applying the top flow to a digestion reactor, feeding the bottom flow of the hydrocyclone into a vacuum belt filter for further dehydration to prepare low-moisture-content desulfurized slag, discharging the desulfurized slag, and discharging the filtrate or mechanically applying the desulfurized slag to the digestion reactor.
The additive is organic acid and/or inorganic additive, and the organic acid is: at least one of adipic acid, citric acid, humic acid, benzoic acid, and acetic acid; the inorganic additive is: at least one of magnesium oxide, sodium sulfate and sodium nitrate.
The absorption tower is a packed tower, a sieve plate tower, a rotational flow plate tower or a Venturi. The bottom of the absorption tower is provided with a lateral stirring device to prevent the absorption slurry from precipitating.
The desulfurization process conditions are as follows: the pH value of absorption slurry entering the tower is 5.0-9.0, and the liquid-gas ratio is 2.0-20.0L/m3The concentration of the inorganic additive is 0-100000mg/L, the concentration of the organic acid is 0-3000mg/L, and the concentrations of the inorganic additive and the organic acid are not 0mg/L at the same time. The calcium ion concentration is 600-2000mg/L, the absorption slurry mass percentage concentration is 1-35%, and the desulfurization efficiency can be more than 95%.
The process of the invention comprises the following steps:
the absorbent lime and the additive enter the digestion reactor through respective feeding and metering devices. The calcium oxide and additive react with water in the digestion reactor to form an absorbent slurry (the additive is exemplified by magnesium oxide).
The absorption slurry after the digestion reaction enters an absorption tower through an absorption slurry conveying pump, the sulfur-containing flue gas enters the absorption tower, and the sulfur-containing flue gas and the absorption slurry are subjected to desulfurization reaction inside the absorption tower:
if the additive is an organic acid, the reaction is as follows:
in the desulfurization tower, the organic acid reacts with lime to obtain regeneration:
the purified flue gas is discharged from the upper part of the absorption tower, and the absorption slurry absorbing the sulfur dioxide is recycled through a main circulating pump or subjected to aftertreatment after reaching the bottom of the absorption tower.
After-treatment is required when the absorption slurry reaches a certain concentration and cannot be recycled.
And (3) discharging a part of slurry from the bottom of the absorption tower, passing the part of slurry through a desulfurization residue delivery pump, entering a hydrocyclone, separating in the hydrocyclone, returning the top flow of the hydrocyclone to the absorption tower, or mechanically using a digestion reactor as make-up water, and further removing water from the bottom flow by a vacuum belt filter to obtain desulfurization residues.
The enhanced lime method flue gas desulfurization process adopts lime and a certain proportion of additives for desulfurization together, improves the pH buffer capacity of the desulfurization absorption slurry and the concentration of sulfite ions in the desulfurization absorption slurry, effectively reduces the concentration of calcium ions, avoids the scaling of calcium sulfite and calcium sulfate, improves the utilization rate of the lime and reduces the desulfurization cost. Compared with the traditional lime method, the desulfurization efficiency can be improved by about 5-10% under the condition of the same liquid-gas ratio, and the utilization rate of the absorbent is improved by 1-10%.
Drawings
FIG. 1 is a process flow diagram of an enhanced lime process, wherein:
1. absorption tower 2, sulfur-containing flue gas 3 and process flushing water
4. Purified flue gas 5, lime bin 6 and additive bin
7. Screw conveyer 8, digestion reactor 9, absorption slurry delivery pump
10. Cyclone 11, vacuum belt filter 12, filtrate pump
13. Filtrate tank 14, desulfurized slag delivery pump 15 and main circulating pump
16. Process make-up water 17, discharged part filtrate 18 and drum-type ash melting device
Detailed Description
Example 1
Referring to fig. 1, the absorbent lime and the additive are stored in a lime bin 5, an additive bin 6, respectively, and enter a digestion reactor 8 through respective screw conveyors 7 and metering devices. If a liquid additive, the additive may be delivered directly to the digestion reactor 8 via a liquid delivery line. If the lime blocks are lump lime blocks, the lump lime blocks are firstly crushed by the roller type lime slaker 18.
The lime and additives react with water (which may be process make-up water 16 or filtrate from filtrate tank 13 or the overhead stream of cyclone 10) in the digestion reactor 8 to produce an absorption slurry.
The absorption slurry after the digestion reaction is conveyed to an output pipeline of a main circulating pump 15 through an absorption slurry conveying pump 9 or directly enters the absorption tower 1.
The sulfur-containing flue gas 2 enters the absorption tower 1 and reacts with the absorption slurry in the absorption tower 1, the purified flue gas 4 is discharged from the upper part of the absorption tower 1, and the absorption slurry which absorbs sulfur dioxide enters the main circulating pump 15 through an output pipeline for recycling or post-treatment after reaching the bottom of the absorption tower 1. The bottom of the absorption tower is provided with a lateral stirring device to prevent the absorption slurry from precipitating.
When the absorbed slurry needs post-treatment after reaching a certain concentration, the slurry enters a hydrocyclone 10 through a desulphurization residue delivery pump 14 for solid-liquid separation, the bottom flow of the hydrocyclone 10 enters a vacuum belt filter 11 for further dehydration, and the desulphurization residue with low water content is prepared and discharged. The top of the cyclone 10 flows back into the absorption tower 1 and can also be used as make-up water for the digestion reactor 8. The filtrate of the vacuum belt filter 11 is conveyed to the digestion reactor 8 for reuse through a filtrate pump 12, and the filtrate 17 is discharged out of the digestion reactor 12 after the ion concentration in the absorbed slurry is accumulated to a certain degree.
The process rinse water 3 can clean the equipment when needed.
The flue gas desulfurization process matched with the boiler at 410t/h is carried out according to the process, and the SO is arranged at the flue gas inlet of the boiler2The concentration is 2037mg/m3The flue gas temperature is 155 ℃, the pH value of the flue gas entering the tower is 7.0, and the liquid-gas ratio is 3.0L/m3The concentration of magnesium ions is 100000mg/L, the concentration of calcium ions is 668mg/L, the mass ratio of the concentration of absorption slurry is 18.0 percent, and the desulfurization efficiency reaches 95.0 percent.
Example 2
The 220t/h boiler matching flue gas desulfurization is carried out according to the technical process described in the embodiment 1. Boiler flue gas inlet SO2The concentration is 9690mg/m3The temperature is 160 ℃, the pH value of the mixture entering the tower is 5.0, and the liquid-gas ratio is 20.0L/m3The concentration of sodium sulfate ion is 28520mg/L, the concentration of calcium ion is 620mg/L, and the absorption serous fluid is concentratedThe mass ratio of the components is 11.7 percent, and the desulfurization efficiency reaches 97.0 percent.
Example 3
The 130t/h boiler matched flue gas desulfurization process is carried out according to the technical process described in the embodiment 1, and the SO is arranged at the flue gas inlet of the boiler2The concentration is 2050mg/m3The temperature is 155 ℃, the pH value of the mixture entering the tower is 6.5, and the liquid-gas ratio is 5.0L/m3The concentration of sodium nitrate is 50960mg/L, the concentration of calcium ions is 600mg/L, the mass ratio of the absorption slurry concentration is 13.0 percent, and the desulfurization efficiency is 96.1 percent.
Example 4
The process described in example 1 was followed for 170t/h boiler matched flue gas desulfurization. Boiler flue gas inlet SO2The concentration is 1800mg/m3The temperature is 152 ℃, the pH value of the mixture entering the tower is 6.0, and the liquid-gas ratio is 4.0L/m3The concentration of adipic acid is 3000mg/L, the concentration of calcium ions is 600mg/L, the mass ratio of the concentration of the absorption serosity is 11.0 percent, and the desulfurization efficiency is 95.8 percent.
Example 5
The 75t/h boiler matched flue gas desulfurization was carried out according to the process described in example 1. Boiler flue gas inlet SO2The concentration is 2060mg/m3The temperature is 155 ℃, the pH value of the mixture entering the tower is 6.0, and the liquid-gas ratio is 5.0L/m3The concentration of citric acid is 1960mg/L, the concentration of calcium ions is 940mg/L, the mass ratio of the concentration of the absorption serosity is 12.0 percent, and the desulfurization efficiency is 96.0 percent.
Example 6
The process described in example 1 was followed for 170t/h boiler matched flue gas desulfurization. Boiler flue gas inlet SO2The concentration is 1050mg/m3The temperature is 160 ℃, the pH value of the mixture entering the tower is 6.5, and the liquid-gas ratio is 2.0L/m3The concentration of humic acid is 100mg/L, the concentration of calcium ions is 2000mg/L, the concentration-mass ratio of absorption serosity is 15.0 percent, and the desulfurization efficiency is 95.1 percent.
Example 7
The 220t/h boiler matching flue gas desulfurization is carried out according to the technical process described in the embodiment 1. Boiler flue gas inlet SO2The concentration is 2590mg/m3The temperature is 165 ℃, the pH value of the mixture entering the tower is 7.0, and the liquid-gas ratio is 5.0L/m3The concentration of magnesium ions is 4203mg/LThe concentration of diacid is 500mg/L, the concentration of calcium ions is 600mg/L, the mass ratio of the concentration of the absorption serosity is 13.0 percent, and the desulfurization efficiency is 97.0 percent.
Example 8
The process described in example 1 was followed for 170t/h boiler matched flue gas desulfurization. Boiler flue gas inlet SO2The concentration is 1700mg/m3The temperature is 165 ℃, the pH value of the mixture entering the tower is 5.8, and the liquid-gas ratio is 5.0L/m3The concentration of magnesium ions is 4416mg/L, the concentration of citric acid is 300mg/L, the concentration of calcium ions is 560mg/L, the concentration-mass ratio of absorption serosity is 12.6 percent, and the desulfurization efficiency is 98.4 percent.
Example 9
The 130t/h boiler complete flue gas desulfurization was carried out according to the process described in example 1. Boiler flue gas inlet SO2The concentration is 9900mg/m3The temperature is 168 ℃, the pH value of the mixture entering the tower is 9.0, and the liquid-gas ratio is 20.0L/m3The magnesium ion concentration is 7332mg/L, the humic acid concentration is 1000mg/L, and the calcium ion concentration is600mg/L, the mass ratio of the absorption slurry concentration is 17.0 percent, and the desulfurization efficiency is 98.8 percent.
Example 10
The 410t/h boiler matching flue gas desulfurization is carried out according to the technical process described in the example 1. Boiler flue gas inlet SO2The concentration is 1900mg/m3The temperature is 156 ℃, the pH value of the mixture entering the tower is 7.0, and the liquid-gas ratio is 4.0L/m3The concentration of sodium sulfate is 23680mg/L, the concentration of adipic acid is 100mg/L, the concentration of calcium ions is 1120mg/L, the concentration-mass ratio of absorption serosity is 13.0 percent, and the desulfurization efficiency is 96.0 percent.
Claims (9)
1. An enhanced lime method flue gas desulfurization process comprises the following steps: respectively inputting lime and an additive into a digestion reactor, mixing the lime and the additive in the digestion reactor, and reacting with water to generate absorption slurry; inputting theabsorption slurry into an absorption tower, and discharging purified flue gas out of the absorption tower after the sulfur-containing flue gas enters the absorption tower and reacts with the absorption slurry; the absorption slurry absorbing the sulfur dioxide is discharged from the bottom of the absorption tower and recycled or subjected to post-treatment.
2. The enhanced lime process flue gas desulfurization process of claim 1, characterized in that: the post-treatment comprises the following steps: discharging the absorption slurry absorbing sulfur dioxide from the bottom of the absorption tower, then feeding the absorption slurry into a hydrocyclone for solid-liquid separation, returning the top flow of the hydrocyclone into the absorption tower or mechanically applying the top flow to a digestion reactor, feeding the bottom flow of the hydrocyclone into a vacuum belt filter for further dehydration to prepare low-moisture-content desulfurized slag, discharging the desulfurized slag, and discharging the filtrate or mechanically applying the desulfurized slag to the digestion reactor.
3. The enhanced lime process flue gas desulfurization process of claim 1, characterized in that: the additive is organic acid and/or inorganic additive.
4. The enhanced lime process flue gas desulfurization process of claim 3, characterized in that: the organic acid is at least one of adipic acid, citric acid, humic acid, benzoic acid and acetic acid.
5. The enhanced lime process flue gas desulfurization process of claim 3, characterized in that: the inorganic additive is at least one of magnesium oxide, sodium sulfate and sodium nitrate.
6. The enhanced lime process flue gas desulfurization process of claim 1, characterized in that: the pH value of the absorption slurry entering the absorption tower is 5.0-9.0.
7. The enhanced lime process flue gas desulfurization process of claim 1, characterized in that: the liquid-gas ratio is 2.0-20.0L/m during the absorption reaction in the absorption tower3。
8. The enhanced lime process flue gas desulfurization process of claim 1, characterized in that: the concentration of the inorganic additive is 0-100000mg/L and the concentration of the organic acid is 0-3000mg/L when the absorption reaction is carried out in the absorption tower, and the concentrations of the inorganic additive and the organic acid are not 0mg/L at the same time.
9. The enhanced lime process flue gas desulfurization process of claim 1, characterized in that: the concentration of calcium ions is 600-2000mg/L when the absorption reaction is carried out in the absorption tower.
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| CN100486673C (en) * | 2007-06-06 | 2009-05-13 | 中电投远达环保工程有限公司 | Adsorption tower smoke directly ventilating technology |
| CN102485324A (en) * | 2011-04-15 | 2012-06-06 | 安徽理工大学 | Ammonium sulphate-limestone method for desulphurization of flue gas |
| CN102814118A (en) * | 2012-09-17 | 2012-12-12 | 上海电力学院 | Flue gas desulfurization additive, and preparation method and application thereof |
| CN102847418A (en) * | 2011-07-01 | 2013-01-02 | 湖南晟通科技集团有限公司 | Additive for limestone-gypsum wet flue gas desulfurization and denitration process |
| CN103084055A (en) * | 2011-10-30 | 2013-05-08 | 湖南晟通科技集团有限公司 | Desulphurization additive |
| CN103638790A (en) * | 2013-12-11 | 2014-03-19 | 中国神华能源股份有限公司 | Method for preventing sulfur dioxide absorption tower from scaling inside |
| CN103977698A (en) * | 2014-05-23 | 2014-08-13 | 东南大学 | Method for reducing emission of PM 2.5 and SO2 at outlet of wet desulphurization system |
| CN105384262A (en) * | 2015-10-29 | 2016-03-09 | 华电电力科学研究院 | Special scale inhibitor for wet desulfurization system |
| CN105396449A (en) * | 2015-10-30 | 2016-03-16 | 太仓东能环保设备有限公司 | Limestone-gypsum wet-process flue gas desulfurization process |
| CN106731636A (en) * | 2017-02-09 | 2017-05-31 | 合肥天翔环境工程有限公司 | A kind of boiler flue gas desulfurization system |
| CN106823711A (en) * | 2017-02-09 | 2017-06-13 | 合肥天翔环境工程有限公司 | A kind of boiler smoke dusting and desulfuring system |
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| CN109499342A (en) * | 2018-11-29 | 2019-03-22 | 大余明发矿业有限公司 | A kind of lime desulfurization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100486673C (en) * | 2007-06-06 | 2009-05-13 | 中电投远达环保工程有限公司 | Adsorption tower smoke directly ventilating technology |
| CN102485324A (en) * | 2011-04-15 | 2012-06-06 | 安徽理工大学 | Ammonium sulphate-limestone method for desulphurization of flue gas |
| CN102485324B (en) * | 2011-04-15 | 2015-12-16 | 安徽理工大学 | The method of sulphur ammonium-limestone-based process flue gas desulfurization |
| CN102847418B (en) * | 2011-07-01 | 2016-03-23 | 晟通科技集团有限公司 | A kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive |
| CN102847418A (en) * | 2011-07-01 | 2013-01-02 | 湖南晟通科技集团有限公司 | Additive for limestone-gypsum wet flue gas desulfurization and denitration process |
| CN103084055A (en) * | 2011-10-30 | 2013-05-08 | 湖南晟通科技集团有限公司 | Desulphurization additive |
| CN102814118A (en) * | 2012-09-17 | 2012-12-12 | 上海电力学院 | Flue gas desulfurization additive, and preparation method and application thereof |
| CN103638790A (en) * | 2013-12-11 | 2014-03-19 | 中国神华能源股份有限公司 | Method for preventing sulfur dioxide absorption tower from scaling inside |
| CN103977698A (en) * | 2014-05-23 | 2014-08-13 | 东南大学 | Method for reducing emission of PM 2.5 and SO2 at outlet of wet desulphurization system |
| CN103977698B (en) * | 2014-05-23 | 2016-03-23 | 东南大学 | A kind of wet desulfurization system that reduces exports PM 2.5and SO 2the method of discharge |
| CN105384262A (en) * | 2015-10-29 | 2016-03-09 | 华电电力科学研究院 | Special scale inhibitor for wet desulfurization system |
| CN105396449A (en) * | 2015-10-30 | 2016-03-16 | 太仓东能环保设备有限公司 | Limestone-gypsum wet-process flue gas desulfurization process |
| CN106731636A (en) * | 2017-02-09 | 2017-05-31 | 合肥天翔环境工程有限公司 | A kind of boiler flue gas desulfurization system |
| CN106823711A (en) * | 2017-02-09 | 2017-06-13 | 合肥天翔环境工程有限公司 | A kind of boiler smoke dusting and desulfuring system |
| CN107140668A (en) * | 2017-05-31 | 2017-09-08 | 镇江严彦气体有限公司 | A kind of preparation method of hydrated silica |
| CN109499342A (en) * | 2018-11-29 | 2019-03-22 | 大余明发矿业有限公司 | A kind of lime desulfurization method |
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Effective date of registration: 20110222 Address after: Hangzhou City, Zhejiang province Xiaoshan District 311202 North Street Xingyi Village Patentee after: ZHEJIANG TIANLAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: Hangzhou City, Zhejiang Province, Xihu District Wensanlu Road 310012 building room 1019, No. 369 digital Co-patentee before: Wu Zhongbiao Patentee before: ZHEJIANG TIANLAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
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Address after: Hangzhou City, Zhejiang province Xiaoshan District 311202 North Street Xingyi Village Patentee after: ZHEJIANG TIANLAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: Hangzhou City, Zhejiang province Xiaoshan District 311202 North Street Xingyi Village Patentee before: ZHEJIANG TIANLAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |