CN103721556A - Desulfurization, denitrification and demercuration additive as well as preparation method thereof - Google Patents

Desulfurization, denitrification and demercuration additive as well as preparation method thereof Download PDF

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CN103721556A
CN103721556A CN201410026774.1A CN201410026774A CN103721556A CN 103721556 A CN103721556 A CN 103721556A CN 201410026774 A CN201410026774 A CN 201410026774A CN 103721556 A CN103721556 A CN 103721556A
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additive
desulfurization
demercuration
gypsum
cobalt
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CN201410026774.1A
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高同柱
路艳霞
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高同柱
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Abstract

The invention discloses a desulfurization, denitrification and demercuration additive as well as a preparation method thereof. The additive consists of the following components in percentage by weight: 20-80% of accelerants, 5-20% of limestone activating agents, 0.04-1% of catalytic synergists, 0.2-10% of metal oxide and 0.5-15% of surfactants. The additive disclosed by the invention can improve the desulfurization efficiency of an absorption tower, is adaptive to high-sulfur coal and enables the exit concentration of SO2 to reach the standard, and a serum circulation pump can be stopped at varying degrees so as to reach the aim of saving energy; moreover, the additive is easily soluble in water, and has the characteristics of simplicity and convenience in using, no air bubble in the using process and no corrosion to equipment; the desulfurization method for applying the additive not only can be used for reducing the using quantity of limestone, improving the CaSO3 oxidation efficiency and the gypsum purity and the dehydration efficiency of gypsum, but also can be used for reducing the content of NO and Hg in flue gas, and reaches the effects of desulfurization, denitrification and demercuration and flue gas purification.

Description

A kind of desulfurization denitration demercuration additive and manufacture method thereof
technical field:
The invention belongs to smoke gas treatment and control technology field, concrete is exactly a kind of desulfurization denitration demercuration and preparation method thereof.
background technology:
Coal is occupied an leading position in the production of energy of China and consumption structure always, its output accounts for 70% left and right of national primary energy output, in a foreseeable future, in decades, coal be take as main energy resource structure can not change in China, remains an important component part of energy source in China.The formation of China's primary energy, has determined that power generation energy resource take coal as main general layout.Coal-fired thermal power generation unit is occupied an leading position in China's power industry.The large-scale power station overwhelming majority of China is conventional coal fired power plant, and therefore, it is the greatest contamination source of causing China's environmental destruction that coal must burn.Coal resources in China has difficult choosing, coal is many, height is grey, the heavy feature of sulphur coal.Wherein, coal fire discharged SOx amount is maximum, accounts for 87% of other kinds pollution sources.Although limestone-gypsum desulphurization system has mostly been installed by coal-burning power plant, what power plant moved in recent years uses coal sulfur content far away higher than design load, therefore need to increase spraying layer and improve desulfuration efficiency, makes SO2 exit concentration up to standard.This method can increase investment and the operating cost of power plant undoubtedly.In addition, even if increased spraying layer, temporarily improved desulfuration efficiency, if but oxidation fan is exerted oneself not, also the oxidation efficiency of CaSO3 may be affected, because CaSO3 is little a lot of compared with CaSO4 particle, in follow-up dewatering system, filter cloth can be stopped up, cause gypsum purity to decline, gypsum can not up to standardly be sold.In addition, along with the execution of more and more stricter pollutant emission standard, it is also imperative that the discharge standard of NOx and Hg is controlled.If add a certain amount of sulfur-removing additives in wet desulphurization, can realize the oxidation efficiency that improves desulfuration efficiency and CaSO3, reduction systematic running cost use and the simultaneously object of desulfurization denitration demercuration simultaneously.
summary of the invention:
The object of the invention is to: a kind of desulfurization denitration demercuration additive and preparation method thereof is provided.This additive and sulfur method are mainly used in using coal sulfur content higher than the Limestone-gypsum Wet Flue Gas Desulfurization Process system of design load, to improve SO2 removal efficiency and CaSO3 oxidation efficiency, and can save power consumption, realize the object of desulfurization denitration demercuration simultaneously.
Technical scheme of the present invention: a kind of desulfurization denitration demercuration additive and preparation method thereof, according to percentage by weight, calculate, it is comprised of 20-80% promoter, 5-20% lime stone activator, 0.04-1% catalytic synergist 0.2-10% metal oxide and 0.5-15% surfactant.Aforementioned promoter select oneself diacid, adipic acid sodium, sodium acetate, sodium chlorite, sodium chlorate, potassium permanganate, citric acid, natrium citricum, manganese dioxide one or more.
Aforementioned lime stone activator be sodium sulphate and/or magnesium sulfate, manganese sulfate, cobalt acetate, sodium carbonate, urea one or more.
Aforementioned metal oxide be the weight ratio magnesia that is and cobalt oxide one or more.
Aforementioned catalytic synergist be triethylenediamine cobalt (II), triethylene tetramine close cobalt (II), cobalt nitrate, CoCL2 6H2O, two water cobalt chlorides one or more.
Aforementioned surfaces activator be neopelex, triethanolamine one or more.
Coal-fired power plant wet desulphurization method with the above additive, comprises the following steps:
(a) additive, agstone and water are added in 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 absorption tower, spray and lower slurries directly contact with the upstream flue gas that contains sulfur dioxide, absorbs reflection, the air oxidation that the oxidized blower fan of reacted slurries blasts, discharge after serum density is qualified.Promoter in additive can buffered ph fast reducing promote in flue gas that NO2 and Hg2+ absorb, surfactant can promote the dissolving of lime stone and the absorption of SO2, lime stone activator can increase the utilization rate of lime stone, catalytic synergist promotes that metal oxide is NO2 and Hg2+ soluble in water by the NO in flue gas and Ng catalytic oxidation, metal oxide can improve the oxidation efficiency of CaSO3 on the one hand, can be NO2 and Hg2+ soluble in water by the NO in flue gas and Ng catalytic oxidation on the other hand, reach the effect of out of stock demercuration simultaneously;
(c) slurries of discharging from absorption tower are delivered to gypsum dehydration system and are carried out processed, are separated into gypsum and water, can reduce gypsum water content.
Another kind of wet desulphurization method for coal-fired power plant with the above additive, comprises the following steps:
(a) additive is added in melt pit, with existing slurries in melt pit and/or adding technology water, dissolve, then squeeze in absorption tower with sump pump;
(b) slurries that contain additive in absorption tower, spray and under, the upstream flue gas containing sulfur dioxide is sprayed, is absorbed, the air oxidation that the oxidized blower fan of slurries after absorption blasts, treats the qualified discharge of serum density.Promoter in additive can buffered ph fast reducing promote in flue gas that NO2 and Hg2+ absorb, surfactant can promote the dissolving of lime stone and the absorption of SO2, lime stone activator can increase the utilization rate of lime stone, metal oxide can improve the oxidation efficiency of CaSO3 on the one hand, can be NO2 and Hg2+ soluble in water by the NO in flue gas and Ng catalytic oxidation on the other hand, reach the effect of out of stock demercuration simultaneously;
(c) slurries of discharging from absorption tower are delivered to gypsum dehydration system and are carried out processed, are separated into gypsum and water, can reduce gypsum water content.
Additive of the present invention and sulfur method are compared with existing desulfur technology, have advantages of as follows:
1) the lime stone activator in additive can make the activation of part lime stone, participates in desulphurization reaction, thereby reduces lime stone use amount;
2) in the situation that reducing lime stone use amount, the also corresponding growing amount that reduces gypsum, thus reduced gypsum dehydration workload;
3) in additive, add metal oxide, can increase the oxidation efficiency of CaSO4, CaSO4 crystal seed increases, and particle increases, and gypsum dehydration is effective, has not only improved the purity of gypsum, has also reduced gypsum water content;
4) the present invention can reach the effect of the out of stock demercuration of desulfurization simultaneously;
5) additive ph value of the present invention is neutral, has the foaming of not producing, the feature of etching apparatus not in use procedure.Compared with prior art, additive of the present invention can improve the desulfuration efficiency on absorption tower, adapts to sulphur coal, makes SO2 exit concentration up to standard, and the slurry circulating pump of can also stopping using to some extent, reaches energy-conservation object; And this additive is soluble in water, it is neutral that ph value is, and has and in easy to use and use procedure, do not produce foaming, the feature of etching apparatus not.The sulfur method of applying this additive not only can reduce amount of lime, improves CaSO3 oxidation efficiency and gypsum purity, promotes the dewatering efficiency of gypsum, can also reduce the content of NO and Hg in flue gas simultaneously, reaches the out of stock demercuration purifying smoke of desulfurization simultaneously.
the specific embodiment:
Embodiment 1: the preparation of additive: the raw material of getting following weight proportion: adipic acid sodium 20%,, sodium acetate 20%, sodium chlorite 40%, neopelex 10.8%, sodium carbonate 10%, cobalt oxide 0.2%, magnesia 2%, manganese dioxide 7%, triethylenediamine cobalt (II) 0.05% are mixed, are stirred.
Do not adopt the desulfurization situation of additive
Sulfur method: the lime stone slurry that is 30% by solid content is squeezed into absorption tower, slurries spray upstream flue gas, washing, in stock tank, oxidation by air is CaSO4 subsequently, is finally fed to gypsum dehydration system, is separated into gypsum and water.Desulfurized effect: SO2 entrance concentration 5000ppm, four slurry circulating pumps move simultaneously, and in desulfuration efficiency 93%, absorption tower, ph value is that, CaCO3 content are 3.40% at 5.8 o'clock, CaSO3 content is 1.82%, CaSO4 content is 76.45%, gypsum water content is 10.45%.
Adopt the desulfurization situation after additive:
Add 1.5 tons of aforementioned additive and lime stone, water to mix, additive concentration is that the lime stone slurry that 1500ppm forms sprays in absorption tower, inactive two slurry circulating pumps, desulfuration efficiency increases to 97%, denitration rate and demercuration rate increase to respectively 65% and 40%, ph value is that, CaCO3 content are 1.65% at 5.8 o'clock in absorption tower, CaSO3 content is 0.55%,
CaSO4 content is 89.45%, gypsum water content is 8.25%.
Embodiment 2: the preparation of additive: the raw material of getting following weight proportion: adipic acid 50%, citric acid 10%, neopelex 10.8%, sodium sulphate 6%, sodium carbonate 4%, cobalt oxide 0.2%, magnesia 2%, triethylenediamine cobalt (II) 0.08%, mixed, stir.
Do not adopt the desulfurization situation of additive:
Sulfur method: the lime stone slurry that is 30% by solid content is squeezed into absorption tower, slurries spray upstream flue gas, washing, in stock tank, oxidation by air is CaSO4 subsequently, is finally fed to gypsum dehydration system, is separated into gypsum and water.Desulfurized effect: in desulphurization system, load is 23mw, SO2 entrance concentration 5000ppm, four slurry circulating pumps move simultaneously, and in desulfuration efficiency 92%, absorption tower, ph value is that 5.8 o'clock CaCO3 content is 3.40%, CaSO3 content is 1.85%, CaSO4 content is 75.45%, gypsum water content is 10.59%.
Adopt the desulfurization situation after additive:
Add 1.5 tons of additives that prepared and lime stone, urea, water to mix, additive concentration is 1500ppm, agstone accounts for 30% of slurries gross mass, the lime stone slurry forming sprays in absorption tower, urea accounts for 2% of slurries gross mass, the urea solution forming sprays in absorption tower, inactive two slurry circulating pumps, desulfuration efficiency increases to 97%, and denitration rate and demercuration rate increase to respectively 85% and 40%, ph value is that 5.8 o'clock CaCO3 content is 1.09% in absorption tower, CaSO3 content is 0.45%, CaSO4 content is 89.67%, gypsum water content is 9.44%.
Embodiment 3: the preparation of additive: the raw material of getting following weight proportion: sodium sulfite 55%, sodium acetate 25%, neopelex 5%, sodium carbonate 9.2%, cobalt oxide 0.8%, magnesia 5%, triethylenediamine cobalt (II) 0.05%, mixed, stir.
Do not adopt the desulfurization situation of additive:
Sulfur method: the lime stone slurry that is 30% by solid content is squeezed into absorption tower, slurries spray upstream flue gas, washing, in stock tank, oxidation by air is CaSO4 subsequently, is finally fed to gypsum dehydration system, is separated into gypsum and water.Desulfurized effect SO2 entrance concentration 6000ppm, four slurry circulating pumps move simultaneously, and in desulfuration efficiency 91%, absorption tower, ph value is that 6.0 o'clock CaCO3 content is 3.67%, CaSO3 content is 2.08%, CaSO4 content is 74.88%, gypsum water content is 13.84%.
Adopting the concentration of additive in absorption tower is 600ppm, the slurry circulating pump of stopping using, and desulfuration efficiency increases to 98%, and denitration rate and demercuration rate are 70%.In absorption tower, ph value is that, CaCO3 content are 1.45% at 5.8 o'clock, CaSO3 content is 0.66%, CaSO4 content is 86.43%, gypsum water content is 9.62%.
Embodiment 4: the preparation of additive: the raw material of getting following weight proportion: adipic acid sodium 50%, sodium acetate 20%, neopelex 8.5%, triethanolamine 10%, manganese sulfate 6%, cobalt oxide 1%, magnesia 5%, triethylenediamine cobalt (II) 0.03%, mixed, stir.
Do not adopt the desulfurization situation of additive:
Sulfur method: the lime stone slurry that is 30% by solid content is squeezed into absorption tower, slurries spray upstream flue gas, washing, in stock tank, oxidation by air is CaSO4 subsequently, is finally fed to gypsum dehydration system, is separated into gypsum and water.Desulfurized effect: SO2 entrance concentration 7200ppm, four slurry circulating pumps move simultaneously, desulfuration efficiency 86%, in absorption tower, ph value is that 5.6 o'clock CaCO3 content is 2.85%, CaSO3 content is 1.54%, CaSO4 content is 78.45%, gypsum water content is 12.50%.
Adopt the desulfurization situation after additive:
The additive configuring is joined in melt pit, dissolve, then get in absorption tower with sump pump with existing slurries in melt pit, the concentration of additive in absorption tower is 800ppm.The slurry circulating pump of stopping using, desulfurization degree, denitration rate, demercuration rate increase to respectively 98%, 68%, 56%, ph value is that 5.6 o'clock CaCO3 content is that 1.25%CaSO3 content is 0.64% in absorption tower, CaSO4 content is 89.85%, gypsum water content is 8.95%.
Embodiment 5: the preparation of additive: the raw material of getting following weight proportion: adipic acid 60%, citric acid 18%, neopelex 2%, sodium sulphate 6%, cobalt oxide 1.2%, cobalt nitrate 5.5%, magnesia 8%, mixed, stir.
Do not adopt the desulfurization situation of additive:
Sulfur method: the lime stone slurry that is 30% by solid content is squeezed into absorption tower, slurries spray upstream flue gas, washing, in stock tank, oxidation by air is CaSO4 subsequently, is finally fed to gypsum dehydration system, is separated into gypsum and water.Desulfurized effect: SO2 entrance concentration 9000ppm, four slurry circulating pumps move simultaneously, and in desulfuration efficiency 85%, absorption tower, ph value is that 6.0 o'clock CaCO3 content is 3.66%, CaSO3 content is 2.08%, CaSO4 content is 74.65%, gypsum water content is 16.56%.
Adopt the desulfurization situation after additive
The additive preparing is joined in melt pit, with existing slurries in melt pit, adding technology water dissolves when not enough, with sump pump, get in absorption tower again, the concentration of additive in absorption tower is 1000ppm, inactive slurry circulating pump, desulfurization degree, denitration rate, demercuration rate increase to respectively 95%, 68%, 56%, ph value is 5.6 o'clock in absorption tower, and CaCO3 content is 1.34%, CaSO3 content is 0.24%, CaSO4 content is 86.86%, gypsum water content is 9.45%.

Claims (7)

1. a desulfurization denitration demercuration additive and manufacture method thereof, it is characterized in that: according to percentage by weight, calculate, it is that 20-80% promoter, 5-20% lime stone activator, 0.04-1% catalytic synergist, 0.2-10% metal oxide and 0.5-15% surfactant form.
2. the out of stock demercuration additive of a kind of desulfurization and manufacture method thereof according to claim 1, is characterized in that: described promoter select oneself diacid, adipic acid sodium, sodium acetate, sodium chlorite, sodium chlorate, potassium permanganate, citric acid, natrium citricum, manganese dioxide one or more.
3. the out of stock demercuration additive of a kind of desulfurization and manufacture method thereof according to claim 1, is characterized in that: described lime stone activator be selected from sodium sulphate or magnesium sulfate, manganese sulfate, cobalt acetate, sodium carbonate, urea one or more.
4. a kind of desulfurization denitration demercuration additive and manufacture method thereof according to claim 1, is characterized in that: described metal oxide be selected from magnesia and cobalt oxide one or more.
5. according to the out of stock demercuration additive of claim 1 desulfurization and manufacture method thereof, it is characterized in that: described catalytic synergist be selected from triethylenediamine cobalt (II), triethylene tetramine close cobalt (II), cobalt nitrate, CoCL2 6H2O, two water cobalt chlorides one or more.
6. the out of stock demercuration additive of a kind of desulfurization and manufacture method thereof according to claim 1, is characterized in that: described surfactant be selected from neopelex, triethanolamine one or more.
7. according to the wet desulphurization method for coal-fired power plant of additive described in any one in claim 1-6, it is characterized in that: comprise the following steps,
(a) additive, agstone and water are added in 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 absorption tower, spray and lower slurries directly contact with the upstream flue gas that contains sulfur dioxide, absorbs reflection, the air oxidation that the oxidized blower fan of reacted slurries blasts, discharge after serum density is qualified;
(c) slurries of discharging from absorption tower are delivered to gypsum dehydration system and are carried out processed, are separated into gypsum and water.
CN201410026774.1A 2014-01-20 2014-01-21 Desulfurization, denitrification and demercuration additive as well as preparation method thereof Pending CN103721556A (en)

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CN103964484A (en) * 2014-05-27 2014-08-06 湖南恒光科技股份有限公司 Preparation process of nano anhydrous calcium sulfate
CN106039976A (en) * 2016-07-25 2016-10-26 合肥天翔环境工程有限公司 Wet desulphurization additive for smoke and preparation method of wet desulphurization additive
CN106039948A (en) * 2016-07-25 2016-10-26 合肥天翔环境工程有限公司 Boiler smoke chemical-process desulfurization and denitrification agent and preparation method thereof
CN106582246A (en) * 2016-12-26 2017-04-26 合肥天翔环境工程有限公司 Carbide slag wet-method flue gas simultaneous desulfurization and denitrification process
CN106621783A (en) * 2016-12-22 2017-05-10 贵州大学 Compound desulfurization and demercuration agent and preparation method thereof
CN106823718A (en) * 2017-02-13 2017-06-13 中国石油大学(北京) A kind of solid denitrfying agent and its preparation method and application
CN107998869A (en) * 2017-11-17 2018-05-08 王彦霖 A kind of dry type desulfurizing denitration material and preparation method thereof
CN108686651A (en) * 2018-05-30 2018-10-23 临沂大学 A kind of catalyst and its preparation method and application of flue gas denitration demercuration simultaneously
CN108939801A (en) * 2018-08-13 2018-12-07 长有彬 A kind of desulfurizing agent preparation method
CN111171891A (en) * 2020-02-27 2020-05-19 廊坊中蓝星新材料节能环保有限公司 Synergistic dust suppressant and application thereof

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CN106823718A (en) * 2017-02-13 2017-06-13 中国石油大学(北京) A kind of solid denitrfying agent and its preparation method and application
CN107998869A (en) * 2017-11-17 2018-05-08 王彦霖 A kind of dry type desulfurizing denitration material and preparation method thereof
CN108686651A (en) * 2018-05-30 2018-10-23 临沂大学 A kind of catalyst and its preparation method and application of flue gas denitration demercuration simultaneously
CN108686651B (en) * 2018-05-30 2020-10-23 临沂大学 Catalyst for simultaneously denitrifying and removing mercury from flue gas, and preparation method and application thereof
CN108939801A (en) * 2018-08-13 2018-12-07 长有彬 A kind of desulfurizing agent preparation method
CN111171891A (en) * 2020-02-27 2020-05-19 廊坊中蓝星新材料节能环保有限公司 Synergistic dust suppressant and application thereof

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