CN103521062A - Desulphurization synergist - Google Patents

Desulphurization synergist Download PDF

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Publication number
CN103521062A
CN103521062A CN201210232907.1A CN201210232907A CN103521062A CN 103521062 A CN103521062 A CN 103521062A CN 201210232907 A CN201210232907 A CN 201210232907A CN 103521062 A CN103521062 A CN 103521062A
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synergistic agent
sulfate
synergist
component
calcium
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CN201210232907.1A
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CN103521062B (en
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聂冰晶
刘超莲
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Abstract

The invention discloses a wet flue-gas desulphurization synergist. The desulphurization synergist comprises the following compositions in percentage by weight: 20-70% of adipic acid, 10-40% of DBA, 1-5% of calcium sulphate, 2-7% of magnesium sulfate, 1-5% of manganese sulfate, 1-5% of copper sulfate, 5-10% of magnesium hydroxide, and 5-10% of calcium oxide. The wet flue-gas desulphurization synergist provided by the invention belongs to a compound desulphurization synergist, and can be used for improving the desulfurization efficiency of a desulfurization system on the premise of not carrying out capacity expansion reformation on the desulfurization system, and the desulfurization efficiency is above 93%; the desulphurization synergist provided by the invention is simple and easily available in formulation and raw materials, low in cost, less in application amount, and high in utilization rate of limestone.

Description

A kind of desulfurization synergistic agent
Technical field
The present invention relates to a kind of wet desulfurizing process, particularly a kind of wet desulfurization of flue gas by limestone-gypsum method synergist.
Background technology
In conventional wet sulfur removal technology, mainly adopt limestone-gypsum sulfur removal technology, its operation principle is to utilize lime stone as absorbent, absorbs the SO in flue gas 2, generating calcium sulfite, the airborne oxygen forced oxidation that calcium sulfite is blasted in absorption tower becomes calcium sulfate, i.e. gypsum.In traditional limestone-gypsum sulfur method, low as the lime stone cost of absorbent, and desulfuration byproduct can fully utilize, so this sulfur method application is wider.
Can be used at present Limestone-gypsum Wet Flue Gas Desulfurization Process technique synergist mainly contain inorganic synergist, organic synergistic agent and compound synergist, the advantage of inorganic desulfurization synergistic agent is that reaction speed is fast, can improve rapidly desulfuration efficiency, shortcoming is that the duration is short, is expendable synergist; The advantage of organic desulfurization synergistic agent is that acting duration is long, does not directly consume synergist, and consumption is few, and shortcoming is that onset time is slower, is generally 1～2 hour; Although compound synergist has overcome the shortcoming of inorganic synergist and organic synergistic agent, formula is complicated, and expensive, consumption is large.
Summary of the invention
The object of the invention is to overcome above shortcoming, provide a kind of and can improve smoke desulfurization efficiency, the wet process of FGD synergist that formula is simple, cost is low, consumption is few.
Technical scheme of the present invention is:
A synergist, the component of described desulfurization synergistic agent and the percentage by weight of each component are: adipic acid: 20～70%; DBA:10～40%; Calcium sulfate: 1～5%; Magnesium sulfate: 2～7%; Manganese sulfate: 1～5%; Copper sulphate: 1～5%; Magnesium hydroxide: 5～10%; Calcium oxide: 5～10%.
Further, the component of described desulfurization synergistic agent and the percentage by weight of each component are: adipic acid: 30～70%; DBA:15～40%; Calcium sulfate: 2～5%; Magnesium sulfate: 3～7%; Manganese sulfate: 2～5%; Copper sulphate: 2～5%; Magnesium hydroxide: 7～10%; Calcium oxide: 7～10%.
Further, the component of described desulfurization synergistic agent and the percentage by weight of each component are: adipic acid: 30～60%; DBA:15～35%; Calcium sulfate: 2～4%; Magnesium sulfate: 3～5%; Manganese sulfate: 2～4%; Copper sulphate: 2～4%; Magnesium hydroxide: 7～9%; Calcium oxide: 7～9%.
Desulfurization synergistic agent provided by the invention, tool has the following advantages:
1, desulfuration efficiency is high.Wet process of FGD synergist provided by the invention, belongs to compound desulfurization synergistic agent, and organic compound is mixed with inorganic compound, improves the desulfuration efficiency of absorbent lime stone.In desulfurization synergistic agent provided by the invention, inorganic compound can change the ionic equilibrium of desulfurizing tower slurries, reinforcing desulfuration process, and metal ion has catalytic action to desulphurization reaction simultaneously, for example:
MgSO 4→Mg 2++SO 4 2-
SO 4 2-+Ca 2+→CaSO 4
CaCO 3→Ca 2++CO 3 2-
Mg 2++SO 3 2-→MgSO 3
MgSO 3+O 2→MgSO 4
MgSO 4solubility be greater than calcium carbonate, MgSO 4add, sulfate ion concentration in desulfurization slurry is increased, sulfate ion becomes calcium sulfate precipitation with calcium binding, thereby promotes the dissolving of lime stone, raising desulfuration efficiency.Magnesium sulfate plays catalytic action, regulates slurries intermediate ion balance, promotes the dissolving of calcium carbonate;
Manganese sulfate in inorganic compound and copper sulphate, as catalyst, improve the utilization ratio of oxidation air, promote the oxidation of calcium sulfite in reaction; Calcium sulfate can provide crystalline seed, promotes the crystallization of calcium sulfate in slurries, improves dewatering efficiency.Alkaline matter magnesium hydroxide and calcium oxide can regulate the pH value of desulfurization slurry, make it to be in optimal operating condition.
In desulfurization synergistic agent provided by the invention, adipic acid is organic dibasic acid, and DBA is acid esters, in slightly acidic solution, can decompose and generate organic multicomponent acid and alcohols material, the pH value of available buffer desulfurizing tower slurries, makes pH be in optimum condition condition, promotes dissolving and the SO of calcium carbonate 2absorption, improve utilization rate and the SO of absorbent lime stone 2removal efficiency.
In gas phase surface and liquid film, the SO of dissolving 2react dissociation with water and go out H +, liquid film and liquid phase main body border, R (COO -) and H +reaction generates R (COOH), makes H +be passed to liquid phase main body, H in liquid film +concentration reduces can promote SO 2dissolving, simultaneous buffering pH value decrease speed; In solid phase surface and liquid film, the CO of dissolving 3 2-h with dissociation +reaction generates HCO 3 -, in liquid phase main body, H +with HCO 3 -reaction generates CO 2and H 2o, liquid phase main body HCO 3 -the reduction of concentration, thus the dissolving of calcium carbonate promoted, guarantee that desulphurization system is stable, efficiently operation, improve desulfuration efficiency.Chemical equation is as follows:
Organic carboxyl acid ionization generates H +
R(COOH) n→R(COOH) (n-1)(COO -)+H +→C 4H 8(COO -) (n-2)+2H +…
Flue gas SO 2dissolve hydration ionization and generate H +
SO 2+H 2O→H 2SO 3
H 2SO 3→H ++HSO 3 -→2H ++SO 3 -
H +again be combined with acylate
C 4H 8(COO -) 2+2H +→C 4H 8(COOH) 2
The dissolving of calcium carbonate
CaCO 3→Ca 2++CO 3 2-
CO 3 2-+2H +→HCO 3 -+H +→CO 2+H 2O
Use wet desulphurization synergist provided by the invention, under the prerequisite of not carrying out desulphurization system capacity-increasing transformation, improve the desulfuration efficiency of desulphurization system, at absorption tower entrance SO 2when concentration exceeds design load 40%, the SO of absorption tower outlet 2concentration can realize qualified discharge, and desulfuration efficiency reaches more than 93%.
2, synergist addition is few, and cost is low.Desulfurization synergistic agent selects common several organic matters and inorganic matter to be used in combination, and formula is simple, and after tested, the first use amount of desulfurization synergistic agent is 0.4 of absorption tower slurry weight～0.7 ‰, and later addition is according to SO 2densimeter synergist waste is calculated and is supplemented, and consumption is few, and desulfurization synergistic agent cost is low; And the utilization rate of lime stone is high, in use can greatly reduce the use amount of lime stone, the use cost of desulfurizing agent is low.
The specific embodiment:
Below in conjunction with embodiment, technical solution of the present invention is done to further detailed description, but embodiments of the present invention are not limited to this.
Wet process of FGD synergist provided by the invention is applied in the supporting wet desulfurization of flue gas by limestone-gypsum method system of 600MW station boiler to the design entry flue gas SO of this desulphurization system 2concentration is 2000mg/Nm 3, through test, embodiment is as follows:
Embodiment 1:
The component of desulfurization synergistic agent and the percentage by weight of each component are:
(gross weight is 100kg)
Component DBA Adipic acid Calcium sulfate Magnesium sulfate Copper sulphate Manganese sulfate Calcium oxide Magnesium hydroxide
Weight (kg) 10 70 1 2 4 4 5 5
The using method of desulfurization synergistic agent is as follows:
A, by above-mentioned raw materials composite rear one-tenth finished product in proportion.
B, above-mentioned desulfurization synergistic agent is joined in absorption tower, initial addition is 0.6 ‰ of lime stone slurry weight.
C, desulphurization system, after operation a period of time, are supplemented according to synergist loss situation.
Above-mentioned desulfurization synergistic agent is applied to inlet flue gas SO 2concentration design load is 2000mg/Nm 3desulphurization system in, desulphurization system inlet flue gas SO 2concentration actual value be 2800mg/Nm 3time, SO in outlet flue gas 2concentration be 100mg/Nm 3, liquid-gas ratio is 10.0, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 96.4%.
Embodiment 2:
The component of desulfurization synergistic agent and the percentage by weight of each component are:
(gross weight is 100kg)
Component DBA Adipic acid Calcium sulfate Magnesium sulfate Copper sulphate Manganese sulfate Calcium oxide Magnesium hydroxide
Weight (kg) 20 55 2 3 2 2 10 6
The using method of desulfurization synergistic agent is as follows:
A, by above-mentioned raw materials composite rear one-tenth finished product in proportion.
B, above-mentioned desulfurization synergistic agent is joined in absorption tower, initial addition is 0.5 ‰ of lime stone slurry weight.
C, desulphurization system, after operation a period of time, are supplemented according to synergist loss situation.
Above-mentioned desulfurization synergistic agent is applied to inlet flue gas SO 2concentration design load is 2000mg/Nm 3desulphurization system in, desulphurization system inlet flue gas SO 2concentration actual value be 3000mg/Nm 3time, SO in outlet flue gas 2concentration be 130mg/Nm 3, liquid-gas ratio is 10.0, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 95.6%.
Embodiment 3:
The component of desulfurization synergistic agent and the percentage by weight of each component are:
(gross weight is 100kg)
Component DBA Adipic acid Calcium sulfate Magnesium sulfate Copper sulphate Manganese sulfate Calcium oxide Magnesium hydroxide
Weight (kg) 30 50 3 5 1 1 5 5
The using method of desulfurization synergistic agent is as follows:
A, by above-mentioned raw materials composite rear one-tenth finished product in proportion.
B, above-mentioned desulfurization synergistic agent is joined in absorption tower, initial addition is 0.4 ‰ of lime stone slurry weight.
C, desulphurization system, after operation a period of time, are supplemented according to synergist loss situation.
Above-mentioned desulfurization synergistic agent is applied to inlet flue gas SO 2concentration design load is 2000mg/Nm 3desulphurization system in, desulphurization system inlet flue gas SO 2concentration actual value be 2800mg/Nm 3time, SO in outlet flue gas 2concentration be 130mg/Nm 3, liquid-gas ratio is 10.0, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 95.3%.
Embodiment 4:
The component of desulfurization synergistic agent and the percentage by weight of each component are:
(gross weight is 100kg)
Component DBA Adipic acid Calcium sulfate Magnesium sulfate Copper sulphate Manganese sulfate Calcium oxide Magnesium hydroxide
Weight (kg) 40 40 4 3 1 1 6 5
The using method of desulfurization synergistic agent is as follows:
A, by above-mentioned raw materials composite rear one-tenth finished product in proportion.
B, above-mentioned desulfurization synergistic agent is joined in absorption tower, initial addition is 0.7 ‰ of lime stone slurry weight.
C, desulphurization system, after operation a period of time, are supplemented according to synergist loss situation.
Above-mentioned desulfurization synergistic agent is applied to inlet flue gas SO 2concentration design load is 2000mg/Nm 3desulphurization system in, desulphurization system inlet flue gas SO 2concentration actual value be 3300mg/Nm 3time, SO in outlet flue gas 2concentration be 200mg/Nm 3, liquid-gas ratio is 10.0, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 93.9%.
Embodiment 5:
The component of desulfurization synergistic agent and the percentage by weight of each component are:
(gross weight is 100kg)
Component DBA Adipic acid Calcium sulfate Magnesium sulfate Copper sulphate Manganese sulfate Calcium oxide Magnesium hydroxide
Weight (kg) 24 45 3 2 4 4 10 8
The using method of desulfurization synergistic agent is as follows:
A, by above-mentioned raw materials composite rear one-tenth finished product in proportion.
B, above-mentioned desulfurization synergistic agent is joined in absorption tower, initial addition is 0.7 ‰ of lime stone slurry weight.
C, desulphurization system, after operation a period of time, are supplemented according to synergist loss situation.
Above-mentioned desulfurization synergistic agent is applied to inlet flue gas SO 2concentration design load is 2000mg/Nm 3desulphurization system in, desulphurization system inlet flue gas SO 2concentration actual value be 3100mg/Nm 3time, SO in outlet flue gas 2concentration be 160mg/Nm 3, liquid-gas ratio is 10.0, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 94.8%.
Embodiment 6:
The component of desulfurization synergistic agent and the percentage by weight of each component are:
(gross weight is 100kg)
Component DBA Adipic acid Calcium sulfate Magnesium sulfate Copper sulphate Manganese sulfate Calcium oxide Magnesium hydroxide
Weight (kg) 34 35 1 2 5 5 8 10
The using method of desulfurization synergistic agent is as follows:
A, by above-mentioned raw materials composite rear one-tenth finished product in proportion.
B, above-mentioned desulfurization synergistic agent is joined in absorption tower, initial addition is 0.7 ‰ of lime stone slurry weight.
C, desulphurization system, after operation a period of time, are supplemented according to synergist loss situation.
Above-mentioned desulfurization synergistic agent is applied to inlet flue gas SO 2concentration design load is 2000mg/Nm 3desulphurization system in, the concentration actual value of desulphurization system inlet flue gas SO2 is 2900mg/Nm 3time, SO in outlet flue gas 2concentration be 90mg/Nm 3, liquid-gas ratio is 10.0, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 96.9%.
Embodiment 7:
The component of desulfurization synergistic agent and the percentage by weight of each component are:
(gross weight is 100kg)
Component DBA Adipic acid Calcium sulfate Magnesium sulfate Copper sulphate Manganese sulfate Calcium oxide Magnesium hydroxide
Weight (kg) 40 20 5 7 3 5 10 10
The using method of desulfurization synergistic agent is as follows:
A, by above-mentioned raw materials composite rear one-tenth finished product in proportion.
B, above-mentioned desulfurization synergistic agent is joined in absorption tower, initial addition is 0.5 ‰ of lime stone slurry weight.
C, desulphurization system, after operation a period of time, are supplemented according to synergist loss situation.
Above-mentioned desulfurization synergistic agent is applied to inlet flue gas SO 2concentration design load is 2000mg/Nm 3desulphurization system in, desulphurization system inlet flue gas SO 2concentration actual value be 2900mg/Nm 3time, SO in outlet flue gas 2concentration be 120mg/Nm 3, liquid-gas ratio is 10.0, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 95.9%.
Embodiment 8:
The component of desulfurization synergistic agent and the percentage by weight of each component are:
(gross weight is 100kg)
Component DBA Adipic acid Calcium sulfate Magnesium sulfate Copper sulphate Manganese sulfate Calcium oxide Magnesium hydroxide
Weight (kg) 35 30 5 6 4 4 9 7
The using method of desulfurization synergistic agent is as follows:
A, by above-mentioned raw materials composite rear one-tenth finished product in proportion.
B, above-mentioned desulfurization synergistic agent is joined in absorption tower, initial addition is 0.6 ‰ of lime stone slurry weight.
C, desulphurization system, after operation a period of time, are supplemented according to synergist loss situation.
Above-mentioned desulfurization synergistic agent is applied to inlet flue gas SO 2concentration design load is 2000mg/Nm 3desulphurization system in, desulphurization system inlet flue gas SO 2concentration actual value be 2800mg/Nm 3time, SO in outlet flue gas 2concentration be 90mg/Nm 3, liquid-gas ratio is 10.0, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 93.4%.

Claims (3)

1. a wet process of FGD synergist, is characterized in that, the component of described desulfurization synergistic agent and the percentage by weight of each component are: adipic acid: 20～70%; DBA:10～40%; Calcium sulfate: 1～5%; Magnesium sulfate: 2～7%; Manganese sulfate: 1～5%; Copper sulphate: 1～5%; Magnesium hydroxide: 5～10%; Calcium oxide: 5～10%.
2. wet process of FGD synergist according to claim 1, is characterized in that, the component of described desulfurization synergistic agent and the percentage by weight of each component are: adipic acid: 30～70%; DBA:15～40%; Calcium sulfate: 2～5%; Magnesium sulfate: 3～7%; Manganese sulfate: 2～5%; Copper sulphate: 2～5%; Magnesium hydroxide: 7～10%; Calcium oxide: 7～10%.
3. wet process of FGD synergist according to claim 2, is characterized in that, the component of described desulfurization synergistic agent and the percentage by weight of each component are: adipic acid: 30～60%; DBA:15～35%; Calcium sulfate: 2～4%; Magnesium sulfate: 3～5%; Manganese sulfate: 2～4%; Copper sulphate: 2～4%; Magnesium hydroxide: 7～9%; Calcium oxide: 7～9%.
CN201210232907.1A 2012-07-06 2012-07-06 A kind of Desulfurization synergist Expired - Fee Related CN103521062B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103949287A (en) * 2014-02-11 2014-07-30 党晓军 Magnesium base flue gas wet desulfurization catalyst
CN105854511A (en) * 2016-05-24 2016-08-17 南京华电节能环保设备有限公司 Exhaust gas sulphur removal agent
CN106268293A (en) * 2015-05-14 2017-01-04 王立群 A kind of wet desulphurization denitration synergist for coal-burning boiler
CN107441902A (en) * 2016-05-31 2017-12-08 天津渤海环保工程有限公司 A kind of flue gas desulfurization and denitrification synergist
CN116808814A (en) * 2023-06-13 2023-09-29 北京联发迈通科技有限公司 Efficient composite desulfurization synergist and preparation process thereof

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Publication number Priority date Publication date Assignee Title
US3904742A (en) * 1972-03-18 1975-09-09 Ken Akimoto Method for directly preparing a sulfate or sulfates from exhaust gases containing SO{HD 2 {B gas
CN101396634A (en) * 2007-09-24 2009-04-01 宝山钢铁股份有限公司 Use of magnesium used refractory, preparation and use method of composite scale inhibitor
CN101642674A (en) * 2009-09-03 2010-02-10 浙江天蓝环保技术有限公司 Wet flue gas desulphurization process for carbide slag slurry pretreatment
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904742A (en) * 1972-03-18 1975-09-09 Ken Akimoto Method for directly preparing a sulfate or sulfates from exhaust gases containing SO{HD 2 {B gas
CN101396634A (en) * 2007-09-24 2009-04-01 宝山钢铁股份有限公司 Use of magnesium used refractory, preparation and use method of composite scale inhibitor
CN101642674A (en) * 2009-09-03 2010-02-10 浙江天蓝环保技术有限公司 Wet flue gas desulphurization process for carbide slag slurry pretreatment
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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103949287A (en) * 2014-02-11 2014-07-30 党晓军 Magnesium base flue gas wet desulfurization catalyst
CN106268293A (en) * 2015-05-14 2017-01-04 王立群 A kind of wet desulphurization denitration synergist for coal-burning boiler
CN105854511A (en) * 2016-05-24 2016-08-17 南京华电节能环保设备有限公司 Exhaust gas sulphur removal agent
CN107441902A (en) * 2016-05-31 2017-12-08 天津渤海环保工程有限公司 A kind of flue gas desulfurization and denitrification synergist
CN116808814A (en) * 2023-06-13 2023-09-29 北京联发迈通科技有限公司 Efficient composite desulfurization synergist and preparation process thereof

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