CN103386248A - Additive for limestone-gypsum wet method flue gas desulphurization - Google Patents
Additive for limestone-gypsum wet method flue gas desulphurization Download PDFInfo
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- CN103386248A CN103386248A CN2012101375265A CN201210137526A CN103386248A CN 103386248 A CN103386248 A CN 103386248A CN 2012101375265 A CN2012101375265 A CN 2012101375265A CN 201210137526 A CN201210137526 A CN 201210137526A CN 103386248 A CN103386248 A CN 103386248A
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Abstract
The invention discloses an additive for limestone-gypsum wet method flue gas desulphurization. The desulphurization additive is characterized by comprising the following components by weight: 30-60% of adipic acid, 30-50% of carboxymethylcellulose sodium, 2-20% of sodium carbonate, 1-15% of pearl alum and 2-15% of a catalysis oxidizing agent; and the catalysis oxidizing agent is at least one selected from ferric sulfate, copper sulfate and manganese sulfate. Belonging to compound desulphurization additive, the flue gas desulphurization additive provided by the invention has simple formula and high desulphurization efficiency.
Description
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 additive.
Background technology
In the conventional wet sulfur removal technology, mainly adopt the limestone-gypsum doctor treatment, its operation principle is to use lime stone as absorbent, absorbs the SO in flue gas
2, generating calcium sulfite, calcium sulfite is oxidised with air to calcium sulfate, i.e. gypsum in oxidizing tower.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.
A large amount of exploitations and use along with coal resources, coal quality reduces gradually, makes the amount of sulfur contenting in smoke of generating plant pulverized coal boiler raise gradually, far surpasses the design load of desulphurization system amount of sulfur contenting in smoke, make desulfurization facility overload operation, cause system can not be continuously, stable operation.In prior art, under the prerequisite of not transforming original desulphurization plant, the desulfuration efficiency that the application sulfur-removing additives improves equipment is effective method comparatively.
The additive that can be used at present Limestone-gypsum Wet Flue Gas Desulfurization Process mainly contains inorganic additive, organic additive and composite additive, the advantage of inorganic sulfur-removing additives is that reaction speed is fast, can improve rapidly desulfuration efficiency, shortcoming is that the duration is short, is consumable additive; The advantage of organic sulfur-removing additives is that acting duration is long, not direct consumption of additives, and consumption is few, and shortcoming is that onset time is slower, is generally 2-5h; Although composite additive has overcome the shortcoming of inorganic additive and organic additive, 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 desulfuration efficiency high, and the simple wet desulfurization of flue gas by limestone-gypsum method additive of filling a prescription.
Technical scheme of the present invention is:
A kind of wet desulfurization of flue gas by limestone-gypsum method additive, the component of described sulfur-removing additives and the weight percentage of each component are: adipic acid: 30-60%; Sodium carboxymethylcellulose: 30-50%; Sodium carbonate: 2-20%; Aluminum sulfate: 1-15%; Catalytic oxidant: 2-15%; Described catalytic oxidant is at least a in ferric sulfate, copper sulphate, manganese sulfate.
Further, the weight percentage of described ferric sulfate is: 3-5%.
Further, the weight percentage of described copper sulphate is: 1-3%.
Further, the weight percentage of described manganese sulfate is: 2-4%.
Further, the percentage composition of the component of described sulfur-removing additives and each component is: adipic acid: 40-50%; Sodium carboxymethylcellulose: 30-40%; Sodium carbonate: 5-15%; Aluminum sulfate: 4-10%; Catalytic oxidant: 5-12%.
Sulfur-removing additives provided by the invention has following advantage:
1, effectively improve the desulphurization system desulfuration efficiency.Flue gas desulfurization additive provided by the invention, belong to the compound sulfur-removing additives of organic and inorganic compound, has the dissolving of the lime stone of promotion, SO
2The effect of solution absorption, raising desulfuration efficiency.Reaction equation is as follows:
Organic carboxyl acid ionization generates H
+
R(COOH)
n→R(COO
-)
(n-1)+H
+→R(COO
-)
(n-2)+2H
+→…
SO in flue gas
2Dissolve, hydration ionization generates H
+
SO
2+H
2O→H
2SO
3
H
2SO
3→2H
++HSO
3
H
+Again be combined with the organic carboxyl acid radical ion, generate organic carboxyl acid
R(COO
-)
n+nH
+→R(COO-)
(n-1)(COOH)+(n-1)H
+→…R(COOH)n
The dissolving of calcium carbonate
In gas phase surface and liquid film, the SO of dissolving
2React from solving H with water
+, liquid film and liquid phase main body border, organic carboxyl acid radical ion and H
+Reaction generates organic carboxyl acid, makes H
+Be passed to the liquid phase main body, H in liquid film
+Concentration reduces, and has promoted SO
2Dissolving, alleviate simultaneously pH value decrease speed; In solid phase surface and liquid film, the CO of dissolving
3 -With the H from separating
+Reaction generates HCO
3-, in the liquid phase main body, H
+With HCO
3 -Reaction generates CO
2And H
2O, liquid phase main body HCO
3 -The reduction of concentration, promoted the dissolving of calcium carbonate, reduced to a certain extent the calcium sulfur ratio that the desulphurization system actual motion needs, thereby guarantee stable, the efficient operation of desulphurization system, improves desulfuration efficiency.
In compound sulfur-removing additives, adipic acid is organic dibasic acid, has stronger stability, and ionization produces H in water
+, H
+Be combined with carboxylic acid ion and generate organic carboxyl acid, make organic carboxyl acid composition in additive as catalyst, improve desulfuration efficiency.Sodium carboxymethylcellulose in additive belongs to organic acid polymer salt material,, as the pH value buffer of desulfurizing tower slurries, makes the pH value of desulfurizing tower slurries be stabilized in the optimum response scope in design sulphur content scope situation, promotes SO
2Absorption and the dissolving of calcium carbonate, thereby improve desulfuration efficiency, sodium carboxymethylcellulose can effectively promote the crystallization of calcium sulfate and the growth of calcium sulphate crystal simultaneously, thereby promotes that dewatering system is normal, stable operation.
Sodium carbonate solubility in compound additive, higher than calcium carbonate, can change the ionic equilibrium of desulfurizer slurry, accelerates SO
2Dissolving, thereby the reinforcing desulfuration effect, chemical equation is as follows:
SO
2+H
2O→H
2SO
3
H
2SO
3→2H
++HSO
3
Na
2CO
3→2Na
++CO
3 2
CO
3 2-+H
+→HCO
3 -
HCO
3-+H
+→CO
2(aq)+H
2O
Aluminum sulfate in additive is inorganic compound, can improve the crystal property of calcium sulfate, promotes the crystal grain of calcium sulfate to generate, and solves the problem of calcium sulfate dehydration; Aluminium ion is trivalent metal ion simultaneously, can form chelate with the organic carboxyl acid radical ion, plays the effect of stable organic carboxyl acid, organic carboxyl acid radical ion, thereby reduces the loss of organic carboxyl acid, organic carboxyl acid radical ion, reduces use cost.
Ferric sulfate, manganese sulfate, copper sulphate are as catalytic oxidant, the calcium sulfite that catalytic oxidation generates is oxidized to rapidly calcium sulfate, improve the utilization ratio of oxidation air, even in desulphurization system, surpass under design load ruuning situation, oxidation fan does not need to carry out capacity-increasing transformation.
Use flue gas desulfurization additive provided by the invention, improve the desulfuration efficiency of desulphurization system under the prerequisite of not carrying out the desulphurization system capacity-increasing transformation, at absorption tower entrance SO
2When concentration exceeds design load 50%, the SO of absorption tower outlet
2Concentration can realize qualified discharge, and desulfuration efficiency reaches more than 93%.
2, the additive use amount is few, cost is low, and raw material is simple and easy to.Through pilot scale and field trial, the first use amount of sulfur-removing additives is the 0.4-0.6 ‰ of absorption tower slurry weight; The use of additive can improve the utilization rate of lime stone, in use can greatly reduce the use amount of lime stone, thereby reduces desulphurization cost.
The specific embodiment
Below in conjunction with embodiment, technical solution of the present invention is done further detailed description, but embodiments of the present invention are not limited to this.
Wet FGD with Additives provided by the invention is applied to inlet flue gas SO
2Design concentration is 1584mg/Nm
3Desulphurization system in, specific embodiment is as follows:
Embodiment 1
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Ferric sulfate | Copper sulphate | Manganese sulfate |
| Weight (kg) | 60 | 30 | 2 | 1 | 3 | 2 | 2 |
| Percentage by weight (%) | 60 | 30 | 2 | 1 | 3 | 2 | 2 |
The using method of sulfur-removing additives is as follows:
A, with above-mentioned raw materials composite rear one-tenth finished product in proportion, join in absorption tower, initial addition is 0.6 ‰ of lime stone slurry weight;
B, desulphurization system after operation a period of time, are supplemented according to the additive losses situation.
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2700mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 155mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 94.3%.
Embodiment 2
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Ferric sulfate | Manganese sulfate |
| Weight (kg) | 30 | 50 | 10 | 5 | 2 | 3 |
| Percentage by weight (%) | 30 | 50 | 10 | 5 | 2 | 3 |
The using method of sulfur-removing additives is as follows:
A, with above-mentioned raw materials composite rear one-tenth finished product in proportion, join in absorption tower, initial addition is 0.4 ‰ of lime stone slurry weight;
B, desulphurization system after operation a period of time, are supplemented according to the additive losses situation.
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2500mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 135mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.02, and desulfuration efficiency is 94.6%.
Embodiment 3
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Ferric sulfate |
| Weight (kg) | 40 | 35 | 12 | 10 | 3 |
| Percentage by weight (%) | 40 | 35 | 12 | 10 | 3 |
The using method of sulfur-removing additives is as follows:
A, with above-mentioned raw materials composite rear one-tenth finished product in proportion, join in absorption tower, initial addition is 0.5 ‰ of lime stone slurry weight;
B, desulphurization system after operation a period of time, are supplemented according to the additive losses situation.
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2600mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 143mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.03, and desulfuration efficiency is 94.5%.
Embodiment 4
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Ferric sulfate | Copper sulphate |
| Weight (kg) | 32 | 32 | 20 | 6 | 5 | 5 |
| Percentage by weight (%) | 32 | 32 | 20 | 6 | 5 | 5 |
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 3000mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 189mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 93.7%.
Embodiment 5
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Manganese sulfate |
| Weight (kg) | 31 | 38 | 8 | 15 | 8 |
| Percentage by weight (%) | 31 | 38 | 8 | 15 | 8 |
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2800mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 180mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.02, and desulfuration efficiency is 93.6%.
Embodiment 6
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Copper sulphate | Manganese sulfate |
| Weight (kg) | 38 | 30 | 5 | 12 | 5 | 10 |
| Percentage by weight (%) | 38 | 30 | 5 | 12 | 5 | 10 |
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2900mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 185mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.03, and desulfuration efficiency is 93.6%.
Embodiment 7
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Copper sulphate |
| Weight (kg) | 30 | 40 | 15 | 13 | 2 |
| Percentage by weight (%) | 30 | 40 | 15 | 13 | 2 |
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2600mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 140mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 94.6%.
Embodiment 8
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Ferric sulfate | Copper sulphate | Manganese sulfate |
| Weight (kg) | 50 | 30 | 5 | 4 | 5 | 2 | 4 |
| Percentage by weight (%) | 50 | 30 | 5 | 4 | 5 | 2 | 4 |
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2850mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 178mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 93.7%.
Embodiment 9
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Ferric sulfate | Manganese sulfate |
| Weight (kg) | 44 | 30 | 7 | 7 | 6 | 6 |
| Percentage by weight (%) | 44 | 30 | 7 | 7 | 6 | 6 |
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2950mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 186mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.03, and desulfuration efficiency is 93.6%.
Embodiment 10
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2500mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 100mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.02, and desulfuration efficiency is 95.2%.
Embodiment 11
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Ferric sulfate | Copper sulphate | Manganese sulfate |
| Weight (kg) | 55 | 30 | 3 | 3 | 2 | 5 | 2 |
| Percentage by weight (%) | 55 | 30 | 3 | 3 | 2 | 5 | 2 |
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2800mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 176mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 93.7%.
Embodiment 12
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Sodium carboxymethylcellulose | Sodium carbonate | Aluminum sulfate | Ferric sulfate | Copper sulphate |
| Weight (kg) | 33 | 45 | 16 | 2 | 1 | 3 |
| Percentage by weight (%) | 33 | 45 | 16 | 2 | 1 | 3 |
Above-mentioned sulfur-removing additives is applied to inlet flue gas SO
2The concentration design load be 1584mg/Nm
3Desulphurization system in, the inlet flue gas SO of desulphurization system
2The concentration actual value be 2900mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 187mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.03, and desulfuration efficiency is 93.5%.
Claims (5)
1. a wet desulfurization of flue gas by limestone-gypsum method additive, is characterized in that, the component of described sulfur-removing additives and the weight percentage of each component are:
Adipic acid: 30-60%; Sodium carboxymethylcellulose: 30-50%; Sodium carbonate: 2-20%; Aluminum sulfate: 1-15%;
Catalytic oxidant: 2-15%; Described catalytic oxidant is at least a in ferric sulfate, copper sulphate, manganese sulfate.
2. wet desulfurization of flue gas by limestone-gypsum method additive according to claim 1, is characterized in that, the weight percentage of described ferric sulfate is: 3-5%.
3. wet desulfurization of flue gas by limestone-gypsum method additive according to claim 1, is characterized in that, the weight percentage of described copper sulphate is: 1-3%.
4. wet desulfurization of flue gas by limestone-gypsum method additive according to claim 1, is characterized in that, the weight percentage of described manganese sulfate is: 2-4%.
5. wet desulfurization of flue gas by limestone-gypsum method additive according to claim 1, is characterized in that, the component of described sulfur-removing additives and the percentage composition of each component are:
Adipic acid: 40-50%; Sodium carboxymethylcellulose: 30-40%; Sodium carbonate: 5-15%; Aluminum sulfate: 4-10%;
Catalytic oxidant: 5-12%.
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|---|---|---|---|
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|---|---|---|---|
| CN2012101375265A CN103386248A (en) | 2012-05-07 | 2012-05-07 | Additive for limestone-gypsum wet method flue gas desulphurization |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106039977A (en) * | 2016-07-25 | 2016-10-26 | 合肥天翔环境工程有限公司 | Limestone-gypsum wet flue gas desulfurization additive and preparation method thereof |
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|---|---|---|---|---|
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| 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 |
| CN102114385A (en) * | 2011-01-21 | 2011-07-06 | 洛阳万山高新技术应用工程有限公司 | Flue gas desulfurization additive |
| CN102380301A (en) * | 2011-08-15 | 2012-03-21 | 西安热工研究院有限公司 | Limestone-plaster wet method flue gas desulfurization composite synergistic agent |
-
2012
- 2012-05-07 CN CN2012101375265A patent/CN103386248A/en active Pending
Patent Citations (6)
| 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 |
| US5733517A (en) * | 1995-03-06 | 1998-03-31 | Electric Power Research Institute | Byproduct solids crystal modification with organic acids in wet flue gas desulfurization systems |
| WO2009043108A1 (en) * | 2007-10-04 | 2009-04-09 | Indigo Technologies Group Pty Ltd | Removal of pollutants from a gas flow |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106039977A (en) * | 2016-07-25 | 2016-10-26 | 合肥天翔环境工程有限公司 | Limestone-gypsum wet flue gas desulfurization additive and preparation method thereof |
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Application publication date: 20131113 |