CN102101011B - Wet desulphurization method for coal-fired power plant and additive used by same - Google Patents

Wet desulphurization method for coal-fired power plant and additive used by same Download PDF

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CN102101011B
CN102101011B CN 201010606343 CN201010606343A CN102101011B CN 102101011 B CN102101011 B CN 102101011B CN 201010606343 CN201010606343 CN 201010606343 CN 201010606343 A CN201010606343 A CN 201010606343A CN 102101011 B CN102101011 B CN 102101011B
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additive
slurries
gypsum
absorption tower
coal
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CN102101011A (en
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李建浏
陶爱平
苏军划
金颖姗
沈煜晖
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China Huadian Engineering Group Co Ltd
Huadian Environmental Protection Engineering and Technology Co Ltd
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China Huadian Engineering Group Co Ltd
Huadian Environmental Protection Engineering and Technology Co Ltd
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Abstract

The invention discloses a wet desulphurization method for a coal-fired power plant and an additive used by the same. The additive comprises the following components in percentage by weight: 70 to 80 percent of alkyl carboxylates, 5 to 10 percent of limestone active agent, 2 to 10 percent of metallic oxide and 5 to 15 percent of surfactant. The additive of the invention can improve the desulfurization effect of an absorption tower and adapt to high-sulfur coal, so that the outlet concentration of SO2 reaches the standard, and a slurry circulating pump also can be stopped in varying degrees to fulfill the aim of energy conservation; and the additive is dissolved in water easily, and the pH value is neutral, so the additive has the characteristic that the additive is easy and convenient to use, does not have air bubbles in the using process and corrode equipment. By the desulphurization method using the additive, the use amount of limestone can be reduced, the oxidization efficiency and gypsum purity of CaSO3 can be improved, the dehydration efficiency of gypsum can be improved, and NO content and Hg content in smoke also can be reduced to achieve the effects of desulfuration, denitration, demercuration and smoke purifying.

Description

A kind of wet desulphurization method for coal-fired power plant and used additive thereof
Technical field
The present invention relates to the method for a kind of coal-burning power plant wet desulphurization and used additive thereof, belong to the flue gas desulfurization technique field.
Background technology
Coal is occupied an leading position in the production of energy of China and consumption structure always, its output accounts for about 70% of national primary energy output, in a foreseeable future in decades, China remains an important component part of Chinese energy take coal as main energy resource structure can not change.The formation of China's primary energy has determined power generation energy resource take coal as main general layout, and coal-fired thermal power generation unit is occupied an leading position in China's power industry, and the large-scale power station overwhelming majority of China is conventional coal fired power plant.Therefore, burning of coal is the greatest contamination source of causing China's environmental destruction.Coal resources in China has difficult choosing, coal is many, height is grey, the heavy characteristics of sulphur coal.Wherein, coal fire discharged SO xAmount is maximum, accounts for 87% of other kinds pollution sources.Although limestone-gypsum desulphurization system has mostly been installed by the coal-burning power plant, the coal sulfur content that uses of in recent years power plant's operation is higher than design load far away, therefore needs to increase spraying layer and improves desulfuration efficiency, makes SO 2Exit concentration is up to standard.This method can increase investment and the operating cost of power plant undoubtedly.In addition, even increased spraying layer, temporarily improve desulfuration efficiency, if still oxidation fan is exerted oneself not, also may affect CaSO 3Oxidation efficiency, because of CaSO 3Than CaSO 4Particle is little a lot, can stop up filter cloth in follow-up dewatering system, causes gypsum purity to descend, and gypsum can not up to standardly be sold.In addition, along with the execution of more and more stricter pollutant emission standard, to NO xWith the discharge standard of Hg control also imperative.If in wet desulphurization, add a certain amount of sulfur-removing additives, can realize simultaneously improving desulfuration efficiency and CaSO 3Oxidation efficiency, reduce systematic running cost with and the purpose of desulfurization denitration demercuration simultaneously.
US Patent No. 4,869,885 have reported the lipophilic surfactant that be used for wet desulphurization of a class HLB scope at 1-5.The patented technology of Chinese patent CN101574615A report is that list/pair alkyl semi-annular jade pendant base succinate and wetting agent (such as alkyl diol) are mixed, and uses this synergist can improve desulfuration efficiency and reduction gypsum water content.What but these patented technologies added all is simple organic matter, and purpose is to promote SO 2Absorption and CaCO 3Dissolving, and the pH value of buffering slurries still can not realize improving CaSO 3Oxidation effectiveness and the purpose of denitration demercuration simultaneously, and organic matter bubbles easily.The present invention is just for the deficiency of above-mentioned technology, the material of same-action not mixed, to prepare many effects desulfurization synergistic additive.
Summary of the invention
The object of the invention is to: a kind of wet desulphurization method for coal-fired power plant and used additive thereof are provided.This additive and sulfur method are mainly used in using the Limestone-gypsum Wet Flue Gas Desulfurization Process system that the coal sulfur content is higher than design load, to improve SO 2Removal efficiency and CaSO 3Oxidation efficiency, and can save power consumption, realize the simultaneously purpose of desulfurization denitration demercuration.
Technical scheme of the present invention: a kind of additive for coal-burning power plant's wet desulphurization, calculate according to percentage by weight, it is comprised of 70%-80% alkyl carboxylic acid base salt, 5%-10% lime stone activator, 2%-10% metal oxide and 5%-15% surfactant.
Aforesaid alkyl carboxylic acid group salt is selected from least a in the dialkyl carboxylic acid salt of the monoalkyl carboxylate of 2,3,4,5,6,8,10,12 alkyl chain length or 2,3,4,5,6,8,10,12 alkyl chain length.
Aforementioned lime stone activator is Na 2CO 3And/or Na 2SO 4
The aforementioned metal oxide is that weight ratio is 10: 1 MgO and Co 3O 4
Aforementioned surfactants is neopelex.
Wet desulphurization method for coal-fired power plant with the above additive may further comprise the steps:
(a) additive, agstone and water are added in the lime stone slurry case, additive concentration is 500-2000ppm, and agstone accounts for 30% of slurries gross mass, then stirs and evenly mixs;
(b) lime stone slurry is sprayed in the absorption tower, the spray and under slurries directly contact with the upstream flue gas that contains sulfur dioxide, carry out absorption reaction, the air oxidation that the oxidized blower fan of reacted slurries blasts is until the qualified rear discharge of serum density; Alkyl carboxylic acid base salt in the additive can the buffer pH value fast reducing, surfactant can promote dissolving and the SO of lime stone 2Absorption, the lime stone activator can increase the utilization rate of lime stone, metal oxide on the one hand can improve CaSO 3Oxidation efficiency, can be NO soluble in water with the NO in the flue gas and Hg catalytic oxidation on the other hand 2And Hg 2+, reach the simultaneously effect of denitration demercuration;
The slurries of (c) discharging from the absorption tower are delivered to gypsum dehydration system and are carried out processed, are separated into gypsum and water, can reduce the gypsum water content.
Another kind of wet desulphurization method for coal-fired power plant with the above additive may further comprise the steps:
(a) additive is added in the melt pit, dissolve with existing slurries in the melt pit and/or adding technology water, squeeze in the absorption tower with sump pump again;
(b) slurries that contain additive spray in the absorption tower and descend, and the upstream flue gas that contains sulfur dioxide is sprayed, absorbs, and the air oxidation that the oxidized blower fan of the slurries after the absorption blasts is until the qualified rear discharge of serum density; Alkyl carboxylic acid base salt in the additive can the buffer pH value fast reducing, surfactant can promote dissolving and the SO of lime stone 2Absorption, the lime stone activator can increase the utilization rate of lime stone, metal oxide on the one hand can improve CaSO 3Oxidation efficiency, can be NO soluble in water with the NO in the flue gas and Hg catalytic oxidation on the other hand 2And Hg 2+, reach the simultaneously effect of desulfurization denitration demercuration;
The slurries of (c) discharging from the absorption tower are delivered to gypsum dehydration system and are carried out processed, are separated into gypsum and water, can reduce the gypsum water content.
Additive of the present invention and sulfur method are compared with existing desulfur technology, have following advantage:
1) the lime stone activator in the additive can make the activation of part lime stone, participates in desulphurization reaction, thereby reduces the lime stone use amount;
2) reducing in the situation of amount of lime, the also corresponding growing amount that reduces gypsum, thus reduced the gypsum dehydration workload;
3) add metal oxide in the additive, can increase CaSO 3Oxidation efficiency, CaSO 4Crystal seed increases, and particle increases, and gypsum dehydration is effective, has not only improved the purity of gypsum, has also reduced the gypsum water content;
4) the present invention can reach the simultaneously effect of desulfurization denitration demercuration;
5) additive pH value of the present invention is neutral, has in the use procedure not produce bubble, do not corrode equipment characteristic.
Compared with prior art, additive of the present invention can improve the desulfuration efficiency on absorption tower, adapts to sulphur coal, makes SO 2Exit concentration is up to standard, and the slurry circulating pump of can also stopping using to some extent reaches energy-conservation purpose; And this additive is soluble in water, and it is neutral that the pH value is, have easy to use and use procedure in do not produce bubble, do not corrode equipment characteristic; The sulfur method of using this additive not only can reduce amount of lime, improves CaSO 3Oxidation efficiency and gypsum purity promote the dewatering efficiency of gypsum, can also reduce simultaneously the content of NO and Hg in the flue gas, reach the simultaneously effect of desulfurization denitration demercuration, purifying smoke.
The specific embodiment
Embodiment 1: the preparation of additive: the raw material of getting following weight proportion: adipic acid sodium 77%, neopelex 10.8%, Na 2CO 310%, cobalt oxide 0.2%, magnesia 2%, with its mixing, stirring gets final product.
Do not adopt the desulfurization situation of additive:
Sulfur method: be that 30% lime stone slurry is squeezed into the absorption tower with solid content, slurries spray upstream flue gas, washing, and oxidation by air is CaSO in stock tank subsequently 4, be fed at last gypsum dehydration system, be separated into gypsum and water.Desulfurized effect: load is 23MW, SO in the desulphurization system 2Entrance concentration 5000ppm, four slurry circulating pumps move simultaneously, desulfuration efficiency 92%, the denitration rate is 30%, the demercuration rate is 10%.The pH value is 5.8 o'clock in the absorption tower, CaCO 3Content is 3.40%, CaSO 3Content is 1.85%, CaSO 4Content is 75.45%.The gypsum water content is 10.59%.
Desulfurization situation behind the employing additive:
Add 1.5 tons of aforementioned additive and lime stone, water mixing, the lime stone slurry of formation sprays in the absorption tower, two slurry circulating pumps of stopping using, and desulfuration efficiency increases to 96%, and denitration rate and demercuration rate increase to respectively 50% and 40%.The pH value is 5.8 o'clock in the absorption tower, CaCO 3Content is 1.78%, CaSO 3Content is 0.54%, CaSO 4Content is 89.37%.The gypsum water content is 8.44%.
Embodiment 2: the preparation of additive: the raw material of getting following weight proportion: adipic acid sodium 77%, neopelex 10.8%, Na 2SO 46%, Na 2CO 34%, cobalt oxide 0.2%, magnesia 2%, and with its mixing, stirring gets final product.
Do not adopt the desulfurization situation of additive:
Sulfur method: be that 30% lime stone slurry is squeezed into the absorption tower with solid content, slurries spray upstream flue gas, washing, and oxidation by air is CaSO in stock tank subsequently 4, be fed at last gypsum dehydration system, be separated into gypsum and water.Desulfurized effect: load is 23MW, SO in the desulphurization system 2Entrance concentration 5000ppm, four slurry circulating pumps move simultaneously, desulfuration efficiency 92%, the denitration rate is 30%, the demercuration rate is 10%.The pH value is 5.8 o'clock in the absorption tower, CaCO 3Content is 3.40%, CaSO 3Content is 1.85%, CaSO 4Content is 75.45%.The gypsum water content is 10.59%.
Desulfurization situation behind the employing additive:
Add 1.5 tons of additives that prepared and lime stone, water mixing, additive concentration is 1500ppm, agstone accounts for 30% of slurries gross mass, the lime stone slurry that forms sprays in the absorption tower, inactive two slurry circulating pumps, desulfuration efficiency increases to 96%, and denitration rate and demercuration rate increase to respectively 50% and 40%.The pH value is 5.8 o'clock in the absorption tower, CaCO 3Content is 1.08%, CaSO 3Content is 0.34%, CaSO 4Content is 89.37%.The gypsum water content is 9.64%.
Embodiment 3: the preparation of additive: the raw material of getting following weight proportion: sodium succinate 78%, neopelex 9%, Na 2CO 37.5%, cobalt oxide 0.5%, magnesia 5%, with its mixing, stirring gets final product.
Do not adopt the desulfurization situation of additive:
Sulfur method: be that 30% lime stone slurry is squeezed into the absorption tower with solid content, slurries spray upstream flue gas, washing, and oxidation by air is CaSO in stock tank subsequently 4, be fed at last gypsum dehydration system, be separated into gypsum and water.Desulfurized effect: load is 25MW, SO in the desulphurization system 2Entrance concentration 6000ppm, four slurry circulating pumps move simultaneously, desulfuration efficiency 90%, the denitration rate is 30%, the demercuration rate is 10%.The pH value is 6.0 o'clock in the absorption tower, CaCO 3Content is 3.64%, CaSO 3Content is 2.05%, CaSO 4Content is 74.78%.The gypsum water content is 13.86%.
Desulfurization situation behind the employing additive:
The additive for preparing is joined in the melt pit, and adding technology water dissolves, and gets in the absorption tower with sump pump again, the concentration of additive in the absorption tower is 400ppm, inactive slurry circulating pump, desulfuration efficiency increases to 98%, and denitration rate and demercuration rate are 60%.The pH value is 5.8 o'clock in the absorption tower, CaCO 3Content is 1.44%, CaSO 3Content is 0.56%, CaSO 4Content is 85.83%.The gypsum water content is 9.55%.
Embodiment 4: the preparation of additive: the raw material of getting following weight proportion: adipic acid sodium 80%, neopelex 8.5%, Na 2CO 36%, cobalt oxide 0.5%, magnesia 5%, with its mixing, stirring gets final product.
Do not adopt the desulfurization situation of additive:
Sulfur method: be that 30% lime stone slurry is squeezed into the absorption tower with solid content, slurries spray upstream flue gas, washing, and oxidation by air is CaSO in stock tank subsequently 4, be fed at last gypsum dehydration system, be separated into gypsum and water.Desulfurized effect: load is 30MW, SO in the desulphurization system 2Entrance concentration 7000ppm, four slurry circulating pumps move simultaneously, desulfuration efficiency 88%, denitration rate and demercuration rate are 20%.The pH value is 5.6 o'clock in the absorption tower, CaCO 3Content is 2.95%, CaSO 3Content is 1.43%, CaSO 4Content is 78.69%.The gypsum water content is 12.30%.
Desulfurization situation behind the employing additive:
The additive for preparing is joined in the melt pit, dissolve with existing slurries in the melt pit, get in the absorption tower with sump pump, the concentration of additive in the absorption tower is 500ppm, inactive slurry circulating pump, desulfurization degree, denitration rate, demercuration rate increase to respectively 96%, 50%, 40%.The pH value is 5.6 o'clock in the absorption tower, CaCO 3Content is 1.21%, CaSO 3Content is 0.65%, CaSO 4Content is 89.74%.The gypsum water content is 8.89%.
Embodiment 5: the preparation of additive: the raw material of getting following weight proportion: adipic acid sodium 80%, neopelex 5.2%, Na 2CO 36%, cobalt oxide 0.8%, magnesia 8%, with its mixing, stirring gets final product.
Do not adopt the desulfurization situation of additive:
Sulfur method: be that 30% lime stone slurry is squeezed into the absorption tower with solid content, slurries spray upstream flue gas, washing, and oxidation by air is CaSO in stock tank subsequently 4, be fed at last gypsum dehydration system, be separated into gypsum and water.Desulfurized effect: load is 28MW, SO in the desulphurization system 2Entrance concentration 10000ppm, four slurry circulating pumps move simultaneously, desulfuration efficiency 85%, denitration rate and demercuration rate are respectively 10%, 30%.The pH value is 6.0 o'clock in the absorption tower, CaCO 3Content is 3.64%, CaSO 3Content is 2.05%, CaSO 4Content is 74.78%.The gypsum water content is 16.76%.
Desulfurization situation behind the employing additive:
The additive for preparing is joined in the melt pit, with existing slurries in the melt pit, adding technology water dissolves when not enough, get in the absorption tower with sump pump again, the concentration of additive in the absorption tower is 1000ppm, inactive slurry circulating pump, desulfurization degree, denitration rate, demercuration rate increase to respectively 95%, 40%, 50%.The pH value is 5.8 o'clock in the absorption tower, CaCO 3Content is 1.35%, CaSO 3Content is 0.44%, CaSO 4Content is 86.78%.The gypsum water content is 9.79%.
Embodiment 6: the preparation of additive: the raw material of getting following weight proportion: Sodium Caprylate 78%, neopelex 9.8%, Na 2SO 410%, cobalt oxide 0.2%, magnesia 2%, with its mixing, stirring gets final product.
Do not adopt the desulfurization situation of additive:
Sulfur method: be that 30% lime stone slurry is squeezed into the absorption tower with solid content, slurries spray upstream flue gas, washing, and oxidation by air is CaSO in stock tank subsequently 4, be fed at last gypsum dehydration system, be separated into gypsum and water.Desulfurized effect: load is 33MW, SO in the desulphurization system 2Entrance concentration 10000ppm, four slurry circulating pumps move simultaneously, desulfuration efficiency 80%, denitration rate and demercuration rate are respectively 20%, 40%.The pH value is 6.0 o'clock in the absorption tower, CaCO 3Content is 3.64%, CaSO 3Content is 2.05%, CaSO 4Content is 74.78%.The gypsum water content is 16.76%.
Desulfurization situation behind the employing additive:
The additive for preparing is joined in the melt pit, dissolve with existing slurries in the melt pit, get in the absorption tower with sump pump, the concentration of additive in the absorption tower is 1200ppm, inactive slurry circulating pump, desulfurization degree, denitration rate, demercuration rate increase to respectively 95%, 30%, 50%.The pH value is 6.0 o'clock in the absorption tower, CaCO 3Content is 1.47%, CaSO 3Content is 0.23%, CaSO 4Content is 88.96%.The gypsum water content is 8.78%.

Claims (3)

1. additive that is used for coal-burning power plant's wet desulphurization, it is characterized in that: calculate according to percentage by weight, it is comprised of 70-80% alkyl carboxylic acid base salt, 5-10% lime stone activator, 2-10% metal oxide and 5-15% surfactant; Described alkyl carboxylic acid base salt is selected from least a in the dialkyl carboxylic acid salt of the monoalkyl carboxylate of 2,3,4,5,6,8,10,12 alkyl chain length or 2,3,4,5,6,8,10,12 alkyl chain length; Described lime stone activator is Na 2CO 3And/or Na 2SO 4Described metal oxide is that weight ratio is MgO and the Co of 10:1 3O 4Described surfactant is neopelex.
2. with the wet desulphurization method for coal-fired power plant of the described additive of claim 1, it is characterized in that: may further comprise the steps:
(a) additive, agstone and water are added in the lime stone slurry case, additive concentration is 500-2000ppm, and agstone accounts for 30% of slurries gross mass, then stirs and evenly mixs;
(b) lime stone slurry is sprayed in the absorption tower, the spray and under slurries directly contact with the upstream flue gas that contains sulfur dioxide, carry out absorption reaction, the air oxidation that the oxidized blower fan of reacted slurries blasts is until the qualified rear discharge of serum density;
The slurries of (c) discharging from the absorption tower are delivered to gypsum dehydration system and are carried out processed, are separated into gypsum and water.
3. with the wet desulphurization method for coal-fired power plant of the described additive of claim 1, it is characterized in that: may further comprise the steps:
(a) additive is added in the melt pit, dissolve with existing slurries in the melt pit and/or adding technology water, squeeze in the absorption tower with sump pump again;
(b) slurries that contain additive spray in the absorption tower and descend, and the upstream flue gas that contains sulfur dioxide is sprayed, absorbs, and the air oxidation that the oxidized blower fan of the slurries after the absorption blasts is until the qualified rear discharge of serum density;
The slurries of (c) discharging from the absorption tower are delivered to gypsum dehydration system and are carried out processed, are separated into gypsum and water.
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CN102847428B (en) * 2011-07-01 2015-09-30 湖南晟通科技集团有限公司 A kind of Limestone-gypsum Wet Flue Gas Desulfurization Process additive
CN103084055A (en) * 2011-10-30 2013-05-08 湖南晟通科技集团有限公司 Desulphurization additive
CN102489133A (en) 2011-12-06 2012-06-13 江西省电力科学研究院 Desulfurization slurry stabilizing agent for wet limestone flue gas desulfurization, and using method of desulfurization slurry stabilizing agent
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CN103537183B (en) * 2013-10-23 2016-09-21 华北电力大学（保定） A kind of method of preparation and use of the type flue gas circulating fluidized bed desulfurization synergist that is humidified
CN103721556A (en) * 2014-01-20 2014-04-16 高同柱 Desulfurization, denitrification and demercuration additive as well as preparation method thereof
CN104208993A (en) * 2014-07-31 2014-12-17 仙桃市中星电子材料有限公司 Device and method for treatment of calcination tail gas
CN104923001B (en) * 2015-06-05 2016-08-17 北京中晶环境科技股份有限公司 Dedusting composition, desulfurization compositions and purposes
CN105289269B (en) * 2015-12-04 2018-02-16 中海油天津化工研究设计院有限公司 A kind of Desulfurization synergist for thermal power plant wet method fume desulfurizing system
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