CN102380301A - Limestone-plaster wet method flue gas desulfurization composite synergistic agent - Google Patents
Limestone-plaster wet method flue gas desulfurization composite synergistic agent Download PDFInfo
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- CN102380301A CN102380301A CN2011102318424A CN201110231842A CN102380301A CN 102380301 A CN102380301 A CN 102380301A CN 2011102318424 A CN2011102318424 A CN 2011102318424A CN 201110231842 A CN201110231842 A CN 201110231842A CN 102380301 A CN102380301 A CN 102380301A
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Abstract
The invention relates to a limestone-plaster wet method flue gas desulfurization composite synergistic agent, which comprises the following ingredients in percentage by mass: 40 percent to 50 percent of organic acid synergistic agents, 25 percent to 35 percent of organic salt synergistic agents, 15 percent to 20 percent of efficient activating agents, 5 to 10 percent of oxidation catalysts and 1 percent of tracers. The half dissolving time of limestone is shortened by more than 40 percent, and the dissolving speed of the limestone is greatly accelerated, so the activity of the limestone is greatly improved. Under the work condition of the designed surfur content, the circulation intensity of serous fluid can be reduced by one third to one half, the liquid-gas ratio of a system is reduced, the system resistance is reduced, the energy consumption of a desulphurization system is obviously reduced, the utilization rate of limestone and oxidation air is improved, and the scale formation and blockage effects on back-stage equipment are reduced. Under the condition that the coal-fired sulfur exceeds the design value, the utilization rate of the oxidation air can be improved by 50 percent to 60 percent, on the basis without transforming the original oxidative system, the oxidation effect that when the fired-coal surfur content exceeds 20 to 30 percent can be met, and the requirements of the desulfurization efficiency and the clean flue gas SO2 discharge concentration are met.
Description
Technical field
The invention belongs to Coal,steam plant with FGD engineering application, be specifically related to a kind of composite synergist that is applicable to all limestone-gypsum wet flue gas desulfurizers.
Background technology
Characteristics such as the limestone-gypsum wet fuel gas desulfurizing technology is high because of its technology maturation, desulfuration efficiency, and the absorbent source is abundant, cheap, and byproduct is capable of using and extensively being adopted become present coal-fired plant flue gas Desulfurization Application method the most widely.But at present the operation ubiquity energy consumption of Power Plant in China limestone-gypsum wet flue gas desulfurizer is with operating cost is high, poor to the adaptive capacity of coal sulfur, absorption tower follow-up equipment obstruction scale formation is serious; Problems such as equipment attrition is serious; Unstability along with coal in China market; Numerous power plant use for a long time and exceed the fire coal that designs sulfur; Cause desulphurization system normally to move, along with the enforcement of more and more stricter environmental emission standard, a lot of desulfurizers are compelled to carry out the capacity-increasing transformation work of existing apparatus.The capacity-increasing transformation of desulfurizer is expensive tens million of easily, and the construction period that the desulfurization stoppage in transit is transformed has brought unprecedented economy and environmental protection pressure generally at 3～4 months to power plant.If can original desulphurization plant not carried out under the prerequisite of capacity-increasing transformation, the design desulfuration efficiency that desulphurization system is satisfied in the agent of application desulfurization synergistic is the research direction of present desulfurization industry.
Summary of the invention
The object of the present invention is to provide and a kind ofly original desulphurization plant is not being carried out under the prerequisite of capacity-increasing transformation, can reach satisfied energy-saving index and SO
2The limestone-gypsum wet process of FGD composite synergist of CER.
For achieving the above object, synergist of the present invention comprises the organic acid synergist of 40%-50% by mass percentage, the organic salt synergist of 25%-35%, the efficient activator of 15%-20%, 5～10% oxidation catalyst and 1% tracer.
Organic acid synergist of the present invention is one or more in benzoic acid, succinic acid, adipic acid, the citric acid; The organic salt synergist is one or both in sodium succinate, sodium formate, the Sodium Benzoate; High-efficiency activated dose is one or both in formamide, the polyethylene glycol; Oxidation catalyst is one or both in ferric trichloride, manganese sulfate, the vanadium oxide; Tracer is one or both in sodium bromide, the KBr.
Thereby the present invention shortens the time of contact that reaches design desulfuration efficiency flue gas and slurries to improving desulphurization reaction speed on the reaction mechanism of limestone-gypsum wet desulfurizing process; Can shorten the time of dissolving that partly disappears of lime stone more than 40%; Quicken the dissolution velocity of lime stone greatly, thereby significantly improve the activity of lime stone.Thereby this synergist can quicken lime stone dissolving, significantly improve limestone activity, improve oxidation air utilization ratio, improve quality of desulphurization gypsum, the Ca/S that reduces system than the utilization ratio that improves lime stone, prevent equipment scaling and obstruction, alleviate wearing and tearing, the buffering slurry pH value fluctuates; It can be adapted to exceed the coal that designs sulfur about 20%～30%; Reduce the system capacity loss, bring good economic and social benefit to power plant.
The specific embodiment
Embodiment 1: the composite synergist of present embodiment comprises 40% organic acid synergist benzoic acid by mass percentage; 35% organic salt synergist sodium succinate; 15% efficient activator formamide, 9% oxidation catalyst ferric trichloride and 1% tracer sodium bromide.
Embodiment 2: the composite synergist of present embodiment comprises 50% organic acid synergist succinic acid by mass percentage; 25% organic salt synergist sodium formate; 17% efficient activator polyethylene glycol, 7% oxidation catalyst manganese sulfate and 1% tracer KBr.
Embodiment 3: the composite synergist of present embodiment comprises 41% organic acid synergist benzene adipic acid by mass percentage; 28% organic salt synergist Sodium Benzoate; 20% the efficient activator formamide and the mixture of polyethylene glycol, 10% oxidation catalyst oxidizes vanadium and 1% the tracer sodium bromide and the mixture of KBr.
Embodiment 4: the composite synergist of present embodiment comprises 46% the organic acid synergist benzoic acid and the mixture of adipic acid by mass percentage; 30% the organic salt synergist sodium succinate and the mixture of sodium formate; 18% efficient activator formamide, the tracer sodium bromide of 5% oxidation catalyst ferric trichloride and the mixture of manganese sulfate and 1%.
Embodiment 5: the composite synergist of present embodiment comprises 43% the organic acid synergist succinic acid and the mixture of citric acid by mass percentage; 32% the organic salt synergist sodium formate and the mixture of Sodium Benzoate; 16% the efficient activator formamide and the mixture of polyethylene glycol, 8% oxidation catalyst oxidizes vanadium and 1% the tracer sodium bromide and the mixture of KBr.
Embodiment 6: the composite synergist of present embodiment comprises 48% organic acid synergist citric acid by mass percentage; 26% organic salt synergist Sodium Benzoate; 19% efficient activator formamide, 6% oxidation catalyst ferric trichloride and 1% tracer sodium bromide.
Composite multi-component acid of the present invention and organic salt: in the slurry environments of absorption tower, provide buffering right, accelerate the mass transport process between air film and the liquid film, improve reaction speed; Oxidation catalyst: improve the utilization ratio of oxygen in the oxidation air, the accelerating oxidation reaction; Efficient activator: change the solid liquid interface wettability, reduce the liquid-film resistance between solid phase and the liquid phase, improve interfacial mass transfer efficient; Tracer: the concentration that is used for the slurries desulfurization synergistic agent of tracking and monitoring absorption tower;
One of which performance of the present invention is energy-saving and cost-reducing type desulfurization composite synergist; Be mainly used in coal-fired sulfur and designing sulfur with interior desulfurizer; Use desulfurization synergistic agent of the present invention can reduce slurries intensity of circulation 1/3rd to 1/2nd, reduce the liquid-gas ratio of system, reduce the resistance of absorption tower part; Thereby significantly reduce the desulphurization system energy consumption; Improve lime stone utilization ratio, improve the quality of desulfurated plaster, thereby reduce the Ca/S ratio of system, and reduce the absorption tower slurries drop that flue gas takes out of the fouling of back level equipment stopped up.
Its two performance is an enhancement mode desulfurization composite synergist; Be mainly used in coal-fired sulfur and exceeding the desulfurizer that designs sulfur about 20%～30%; Thereby the utilization ratio of using desulfurization synergistic agent of the present invention can significantly improve oxidation air satisfies desulphurization system and normally moves; Can the oxidation air utilization rate be improved about 50%～60%; On the basis that original oxidative system is not transformed, can satisfy the oxidation effectiveness that coal-fired sulfur exceeds design load 20～30% o'clock, reach the desulfuration efficiency and the SO of environmental requirement
2Concentration of emission; But pH value that this prerequisite that will produce a desired effect is the absorption tower slurries and absorption tower serum density must be controlled within the normal range of operation; Exceeding under the operating mode that designs sulfur about 20%～30%; Original confession slurry of desulfurizer and dewatering system can't guarantee the normal operation level of absorption tower slurries; Need carry out necessary capacity-increasing transformation to supplying slurry and gypsum discharge system; This part retrofit work change quantities and improvement expenses are all less, and can under the situation that does not influence the normal operation of desulfurizer, carry out, and have very strong operability.
The present invention has significantly improved the adaptive capacity of existing desulfurizer to the coal sulfur.Can reduce desulfurization plant power consumption rate 0.15%～0.25%, about 1000～1800kW that per hour economizes on electricity has reduced the operating cost of desulfurization significantly, and has significantly improved the operational percentage and the availability of desulfurizer.
Desulfurization synergistic agent of the present invention can add in the optional position of slurries closed circuit, proposes concrete scheme according to power plant's actual conditions.
Add first system from the absorption tower melt pit directly squeezing in the absorption tower through sump pump;
Later stage replenishes and should directly add in the lime stone slurry case when adding, and the synergist concentration of generally keeping in the lime stone slurry is that 600～800ppm gets final product, and also can in melt pit, add, but can increase the loss of synergist like this.
Generally addition is 500～1000ppm first, because each factory's desulphurization system has nothing in common with each other, it is different to use coal sulfur content, and addition needs to adjust accordingly according to actual conditions.
Follow-up addition is only considered loss and the attenuation of self that plaster splint water, desulfurization wastewater discharging, flue gas carries steps such as water and is done to replenish as one feels fit.
Need absorption tower slurries quality be adjusted to normal scope before using the desulfurization synergistic agent, the absorption tower slurry pH value is controlled between 5.2～5.8, and the absorption tower serum density is controlled at 1100～1160kg/m
3Between, exceed design SO because of using the desulfurization synergistic agent to adapt to
2Concentration about 20%～30%; Therefore in order to keep absorption tower slurry pH value and density can maintain in the normal range of operation, need supply slurry and gypsum discharge system to carry out suitable transformation to the absorption tower to satisfy the normal operation needs of absorption tower slurry pH value and absorption tower serum density.
Because of desulfurization synergistic agent meeting has a certain amount of loss because of links such as gypsum tyre water, desulfurization wastewater and flue gas carry, need be according to a certain amount of desulfurization synergistic agent of the ruuning situation regular replenishment of desulfurizer.
If the following situation of desulphurization system emerged in operation:
(1) after the background concentration of setting up the desulfurization synergistic agent, do not replenish the desulfurization synergistic agent as requested every day continuously according to quantity;
(2) there is the slurry of throwing situation to take place, can't confirms to throw how many times of slurry amount;
When (3) desulfurization wastewater effluxes in a large number;
(4) the desulphurization system filtrate water is public and can't distinguish the time;
In the above-mentioned situation of the emerged in operation of desulphurization system, then need adopt the analytical method of tracer in the desulfurization synergistic agent that the synergist concentration in the slurries of absorption tower is carried out analytical test, adjust the desulfurization synergistic agent quantity that should replenish according to test data.
Complicated and contain numerous heavy metals because of the desulfuration absorbing tower slurry content, agent all has influence in various degree to the test desulfurization synergistic for this.The present invention has carried out extensive studies aspect the test of desulfurization synergistic agent.In the desulfurization synergistic agent, add quantitative tracer, can convert out the desulfurization synergistic agent concentration in the slurries of absorption tower, calculate the day magnitude of recruitment of desulfurization synergistic agent according to test concentrations through analyzing tracer concentration.
Claims (6)
1. limestone-gypsum wet process of FGD composite synergist; It is characterized in that: the organic acid synergist that comprises 40%-50% by mass percentage; The organic salt synergist of 25%-35%, the efficient activator of 15%-20%, 5～10% oxidation catalyst and 1% tracer.
2. limestone-gypsum wet process of FGD composite synergist according to claim 1 is characterized in that: described organic acid synergist is one or more in benzoic acid, succinic acid, adipic acid, the citric acid.
3. limestone-gypsum wet process of FGD composite synergist according to claim 1 is characterized in that: described organic salt synergist is one or both in sodium succinate, sodium formate, the Sodium Benzoate.
4. limestone-gypsum wet process of FGD composite synergist according to claim 1 is characterized in that: described high-efficiency activated dose is in the formamide, polyethylene glycol one or both.
5. limestone-gypsum wet process of FGD composite synergist according to claim 1 is characterized in that: described oxidation catalyst is one or both in ferric trichloride, manganese sulfate, the vanadium oxide.
6. limestone-gypsum wet process of FGD composite synergist according to claim 1 is characterized in that: described tracer is one or both in sodium bromide, the KBr.
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Cited By (21)
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| CN102961957A (en) * | 2012-12-20 | 2013-03-13 | 新疆鑫恒发环保科技有限公司 | Synergistic limestone desulfuration absorbent |
| CN103055690A (en) * | 2013-01-11 | 2013-04-24 | 上海申欣环保实业有限公司 | Devulcanizing additive and preparation method thereof |
| CN103143252A (en) * | 2013-02-22 | 2013-06-12 | 广东电网公司电力科学研究院 | Additive capable of simultaneous desulphurization and demercuration and preparation method thereof |
| CN103157370A (en) * | 2013-03-11 | 2013-06-19 | 上海申欣环保实业有限公司 | Desulfuration additive and manufacturing method thereof |
| CN103272472A (en) * | 2013-06-18 | 2013-09-04 | 上海电力学院 | Flue gas desulfurization synergist for wet desulfurization system, and preparation method and application thereof |
| CN103386242A (en) * | 2012-05-07 | 2013-11-13 | 湖南晟通科技集团有限公司 | Flue gas desulphurization synergist |
| CN103386243A (en) * | 2012-05-07 | 2013-11-13 | 湖南晟通科技集团有限公司 | Synergist for wet method flue gas desulphurization |
| CN103386248A (en) * | 2012-05-07 | 2013-11-13 | 湖南晟通科技集团有限公司 | Additive for limestone-gypsum wet method flue gas desulphurization |
| CN103432894A (en) * | 2013-08-30 | 2013-12-11 | 杨子江 | Synergist for assisting wet-process desulphurization of thermal power plant, and application method of synergist |
| CN103505989A (en) * | 2012-06-25 | 2014-01-15 | 上海保纳新材料科技有限公司 | Fluorescent molecule-containing desulfurization synergist and concentration detection method thereof |
| CN104437067A (en) * | 2014-11-03 | 2015-03-25 | 武汉光谷环保科技股份有限公司 | Method for strengthening activity of limestone-gypsum wet-method flue gas desulfurization slurry |
| CN104645816A (en) * | 2015-01-28 | 2015-05-27 | 上海水平衡环境科技发展有限公司 | Wet desulphurization synergist |
| CN105251335A (en) * | 2014-07-16 | 2016-01-20 | 麦适（上海）化工有限公司 | Limestone-gypsum wet flue gas desulfurization synergist and preparation method thereof |
| CN105964131A (en) * | 2016-07-25 | 2016-09-28 | 合肥天翔环境工程有限公司 | Additive for flue gas desulfurization of thermal power plant and preparation method of additive |
| CN106178938A (en) * | 2016-07-25 | 2016-12-07 | 合肥天翔环境工程有限公司 | Coal burning flue gas desulfurization agent and preparation method thereof |
| CN107824039A (en) * | 2017-12-04 | 2018-03-23 | 中晶环境科技股份有限公司 | Composite oxidant and the method for dry desulfurization denitration |
| CN108114587A (en) * | 2017-12-31 | 2018-06-05 | 华电高科环保技术有限公司 | The Desulfurization synergist of wet process of FGD |
| CN108744906A (en) * | 2018-06-14 | 2018-11-06 | 昆明理工大学 | A kind of phosphorus ore slurry wet desulfurization additive |
| CN111569634A (en) * | 2020-05-21 | 2020-08-25 | 河北丰强科技有限公司 | Catalytic synergist for desulfurization, denitrification and foam inhibition of coal-fired flue gas and use method thereof |
| CN114788987A (en) * | 2021-05-26 | 2022-07-26 | 上海未来企业股份有限公司 | Synergist with high desulfurization efficiency and obvious energy-saving effect and preparation method thereof |
| CN115646181A (en) * | 2022-11-03 | 2023-01-31 | 西安新盛环保科技有限公司 | Limestone-gypsum wet flue gas desulfurization composite synergist and desulfurization method thereof |
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| CN103386248A (en) * | 2012-05-07 | 2013-11-13 | 湖南晟通科技集团有限公司 | Additive for limestone-gypsum wet method flue gas desulphurization |
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| CN103386243A (en) * | 2012-05-07 | 2013-11-13 | 湖南晟通科技集团有限公司 | Synergist for wet method flue gas desulphurization |
| CN103505989A (en) * | 2012-06-25 | 2014-01-15 | 上海保纳新材料科技有限公司 | Fluorescent molecule-containing desulfurization synergist and concentration detection method thereof |
| CN102961957A (en) * | 2012-12-20 | 2013-03-13 | 新疆鑫恒发环保科技有限公司 | Synergistic limestone desulfuration absorbent |
| CN103055690A (en) * | 2013-01-11 | 2013-04-24 | 上海申欣环保实业有限公司 | Devulcanizing additive and preparation method thereof |
| CN103055690B (en) * | 2013-01-11 | 2015-08-05 | 上海申欣环保实业有限公司 | Sulfur-removing additives and preparation method thereof |
| CN103143252B (en) * | 2013-02-22 | 2015-06-10 | 广东电网公司电力科学研究院 | Additive capable of simultaneous desulphurization and demercuration and preparation method thereof |
| CN103143252A (en) * | 2013-02-22 | 2013-06-12 | 广东电网公司电力科学研究院 | Additive capable of simultaneous desulphurization and demercuration and preparation method thereof |
| CN103157370A (en) * | 2013-03-11 | 2013-06-19 | 上海申欣环保实业有限公司 | Desulfuration additive and manufacturing method thereof |
| CN103272472A (en) * | 2013-06-18 | 2013-09-04 | 上海电力学院 | Flue gas desulfurization synergist for wet desulfurization system, and preparation method and application thereof |
| CN103272472B (en) * | 2013-06-18 | 2015-06-17 | 上海电力学院 | Flue gas desulfurization synergist for wet desulfurization system, and preparation method and application thereof |
| CN103432894A (en) * | 2013-08-30 | 2013-12-11 | 杨子江 | Synergist for assisting wet-process desulphurization of thermal power plant, and application method of synergist |
| CN105251335A (en) * | 2014-07-16 | 2016-01-20 | 麦适（上海）化工有限公司 | Limestone-gypsum wet flue gas desulfurization synergist and preparation method thereof |
| CN104437067A (en) * | 2014-11-03 | 2015-03-25 | 武汉光谷环保科技股份有限公司 | Method for strengthening activity of limestone-gypsum wet-method flue gas desulfurization slurry |
| CN104645816A (en) * | 2015-01-28 | 2015-05-27 | 上海水平衡环境科技发展有限公司 | Wet desulphurization synergist |
| CN105964131A (en) * | 2016-07-25 | 2016-09-28 | 合肥天翔环境工程有限公司 | Additive for flue gas desulfurization of thermal power plant and preparation method of additive |
| CN106178938A (en) * | 2016-07-25 | 2016-12-07 | 合肥天翔环境工程有限公司 | Coal burning flue gas desulfurization agent and preparation method thereof |
| CN107824039A (en) * | 2017-12-04 | 2018-03-23 | 中晶环境科技股份有限公司 | Composite oxidant and the method for dry desulfurization denitration |
| CN108114587A (en) * | 2017-12-31 | 2018-06-05 | 华电高科环保技术有限公司 | The Desulfurization synergist of wet process of FGD |
| CN108114587B (en) * | 2017-12-31 | 2021-03-16 | 华电高科环保技术有限公司 | Desulfurization synergist for wet flue gas desulfurization |
| CN108744906A (en) * | 2018-06-14 | 2018-11-06 | 昆明理工大学 | A kind of phosphorus ore slurry wet desulfurization additive |
| CN111569634A (en) * | 2020-05-21 | 2020-08-25 | 河北丰强科技有限公司 | Catalytic synergist for desulfurization, denitrification and foam inhibition of coal-fired flue gas and use method thereof |
| CN114788987A (en) * | 2021-05-26 | 2022-07-26 | 上海未来企业股份有限公司 | Synergist with high desulfurization efficiency and obvious energy-saving effect and preparation method thereof |
| CN114788987B (en) * | 2021-05-26 | 2023-11-10 | 上海未来企业股份有限公司 | Synergist with high desulfurization efficiency and obvious energy-saving effect and preparation method thereof |
| CN115646181A (en) * | 2022-11-03 | 2023-01-31 | 西安新盛环保科技有限公司 | Limestone-gypsum wet flue gas desulfurization composite synergist and desulfurization method thereof |
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Application publication date: 20120321 |