CN1923338A - Fume desulfurizing process with enhancement limestone method - Google Patents
Fume desulfurizing process with enhancement limestone method Download PDFInfo
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- CN1923338A CN1923338A CN 200610053076 CN200610053076A CN1923338A CN 1923338 A CN1923338 A CN 1923338A CN 200610053076 CN200610053076 CN 200610053076 CN 200610053076 A CN200610053076 A CN 200610053076A CN 1923338 A CN1923338 A CN 1923338A
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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 limestone 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). 2 sets of wet limestone/gypsum method flue gas desulfurization technology and method introduced into Nissan Mitsubishi heavy industry and matched with 2X 360MW unit in Chongqing Lopa Huang power plant during 'seventy five' periodThe equipment is firstly built into 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 percent, and the purity of the byproduct gypsum is higher than 90 percent.
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 limestone 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 enhanced limestone method flue gas desulfurization process comprises respectively inputting limestone and additive into a digestion reactor, mixing the limestone and additive in the digestion reactor, and reacting 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.
Theabsorption 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 limestone and the additive enter the digestion reactor through respective feeding and metering devices. Limestone and additives react with water in the digestion reactor to form an absorbent slurry (the additives being magnesium oxide for example).
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 limestone 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 limestone method flue gas desulfurization process adopts limestone and a certain proportion of additives to carry out desulfurization together, improves the pH buffer capacity of desulfurization absorption slurry and the concentration of sulfite ions in the desulfurization absorption slurry, effectively reduces the concentration of calcium ions, avoids thescaling of calcium sulfite and calcium sulfate, improves the utilization rate of the limestone and reduces the desulfurization cost. Compared with the traditional limestone method, the desulfurization efficiency can be improved by about 5-10% under the same liquid-gas ratio condition, and the utilization rate of the absorbent is improved by 1-10%.
Drawings
FIG. 1 is a flow diagram of an enhanced limestone process wherein:
1. absorption tower 2, sulfur-containing flue gas 3 and process flushing water
4. Purified flue gas 5, limestone 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 limestone grinder
Detailed Description
Example 1
Referring to fig. 1, the absorbent limestone powder and the additive are stored in a limestone bin 5 and an additive bin 6, respectively, and enter a digestion reactor 8 through respective screw conveyors 7 and metering devices. If the limestone blocks are pulverized by a limestone grinder 18 and then enter the limestone silo 5. If a liquid additive, the additive may be delivered directly to the digestion reactor 8 via a liquid delivery line.
Limestone and additives are reacted with water (which may be process make-up water 16 or filtrate from filtrate tank 13 or the overhead stream of cyclone 10) in 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 ions is 2852mg/L, the concentration of calcium ions is 620mg/L, the mass ratio of the absorption slurry concentration 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 5096mg/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/L, the concentration of adipic acid is 500mg/L, the concentration of calcium ions is 600mg/L, the concentration-mass ratio of 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/m3Sulfuric acid, sulfuric acidThe concentration of sodium is 2368mg/L, the concentration of adipic acid is 100mg/L, the concentration of calcium ions is 1120mg/L, the mass ratio of the absorption slurry concentration is 13.0%, and the desulfurization efficiency is 96.0%.
Claims (9)
1. An enhanced limestone flue gas desulfurization process, which comprises the following steps: respectively inputting limestone and an additive into a digestion reactor, mixing the limestone and the additive in the digestion reactor, and reacting 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.
2. The enhanced limestone method flue gas desulfurization process according to 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 limestone method flue gas desulfurization process according to claim 1, characterized in that: the additive is organic acid and/or inorganic additive.
4. The enhanced limestone method 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 limestone method 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 limestone method flue gas desulfurization process according to claim 1, characterized in that: the pH value of the absorption slurry entering the absorption tower is 5.0-9.0.
7. The enhanced limestone method flue gas desulfurization process according to 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 limestone method flue gas desulfurization process according to 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 limestone method flue gas desulfurization process according to 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947410A (en) * | 2010-09-28 | 2011-01-19 | 浙江天达环保股份有限公司 | Active activator of limestone powder |
| CN102000489A (en) * | 2010-11-24 | 2011-04-06 | 东北电力科学研究院有限公司 | Wet desulfurizer for thermal power plant and desulfurization method thereof |
| CN102019138A (en) * | 2010-11-18 | 2011-04-20 | 华北电力大学（保定） | Multifunctional composite additive for wet-method flue gas desulfuration process and using method thereof |
| CN101342460B (en) * | 2008-08-20 | 2011-08-17 | 浙江天蓝环保技术有限公司 | Automatically controlled desulphurizing agent slurry formulating device |
| CN102183518A (en) * | 2011-01-26 | 2011-09-14 | 中节能六合天融环保科技有限公司 | Method for quickly measuring sulfate radical content in magnesium method desulfurization process |
| CN102485323A (en) * | 2011-04-15 | 2012-06-06 | 安徽理工大学 | Rapid calcium desulphurization method for flue gas |
| CN102000481B (en) * | 2009-08-31 | 2012-10-10 | 宝山钢铁股份有限公司 | Method for treating desulfurization ash |
| CN109126409A (en) * | 2018-10-30 | 2019-01-04 | 中冶焦耐(大连)工程技术有限公司 | It is a kind of that desulfurization and decarburization technique being carried out to biogas with causticization liquid |
| CN111013345A (en) * | 2019-12-05 | 2020-04-17 | 盛尼克能源环保技术(重庆)有限公司 | Wet flue gas desulfurization method by adding magnesium limestone |
| CN114682161A (en) * | 2020-12-26 | 2022-07-01 | 黄华丽 | Solid-liquid different-weight mixed slurry material storage tank and application thereof |
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- 2006-08-18 CN CNB2006100530766A patent/CN100469418C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101342460B (en) * | 2008-08-20 | 2011-08-17 | 浙江天蓝环保技术有限公司 | Automatically controlled desulphurizing agent slurry formulating device |
| CN102000481B (en) * | 2009-08-31 | 2012-10-10 | 宝山钢铁股份有限公司 | Method for treating desulfurization ash |
| CN101947410A (en) * | 2010-09-28 | 2011-01-19 | 浙江天达环保股份有限公司 | Active activator of limestone powder |
| CN102019138A (en) * | 2010-11-18 | 2011-04-20 | 华北电力大学（保定） | Multifunctional composite additive for wet-method flue gas desulfuration process and using method thereof |
| CN102019138B (en) * | 2010-11-18 | 2013-02-13 | 华北电力大学（保定） | Multifunctional composite additive for wet-method flue gas desulfuration process and using method thereof |
| CN102000489A (en) * | 2010-11-24 | 2011-04-06 | 东北电力科学研究院有限公司 | Wet desulfurizer for thermal power plant and desulfurization method thereof |
| CN102183518A (en) * | 2011-01-26 | 2011-09-14 | 中节能六合天融环保科技有限公司 | Method for quickly measuring sulfate radical content in magnesium method desulfurization process |
| CN102485323A (en) * | 2011-04-15 | 2012-06-06 | 安徽理工大学 | Rapid calcium desulphurization method for flue gas |
| CN109126409A (en) * | 2018-10-30 | 2019-01-04 | 中冶焦耐(大连)工程技术有限公司 | It is a kind of that desulfurization and decarburization technique being carried out to biogas with causticization liquid |
| CN111013345A (en) * | 2019-12-05 | 2020-04-17 | 盛尼克能源环保技术(重庆)有限公司 | Wet flue gas desulfurization method by adding magnesium limestone |
| CN114682161A (en) * | 2020-12-26 | 2022-07-01 | 黄华丽 | Solid-liquid different-weight mixed slurry material storage tank and application thereof |
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