CN103357256A - Limestone-gypsum wet-process desulphurization additive - Google Patents
Limestone-gypsum wet-process desulphurization additive Download PDFInfo
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- CN103357256A CN103357256A CN2012101012079A CN201210101207A CN103357256A CN 103357256 A CN103357256 A CN 103357256A CN 2012101012079 A CN2012101012079 A CN 2012101012079A CN 201210101207 A CN201210101207 A CN 201210101207A CN 103357256 A CN103357256 A CN 103357256A
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Abstract
The invention discloses a limestone-gypsum wet-process desulphurization additive. The desulphurization additive comprises the following components in percentage by weight: 60-90% of adipic acid, 2-10% of magnesium sulfate, 4-20% of sodium carbonate, 1-8% of copper sulfate and 1-8% of manganese sulfate. The desulphurization additive is simple in formula, low in cost, less in amount, quick in response, high in desulphurization efficiency and the like.
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
The limestone-gypsum method flue gas desulfurization technology is that technology is the most ripe in the world at present, is fit to China's national situation and the maximum high-efficiency desulfurization technique of domestic application, accounts for 80% of heat-engine plant desulfurized total amount.This technique has the advantages such as desulfuration efficiency height, technology maturation, putting equipment in service rate height, unit strong adaptability, desulfuration byproduct can fully utilize, the lime stone absorbent is cheap and easy to get.
A large amount of exploitations and use along with coal resources, coal quality reduces gradually, a large amount of low heat values, high-sulphur raw coal are used for generating by thermal power plant, so that the amount of sulfur contenting in smoke of generating plant pulverized coal boiler raises gradually, the design load that surpasses the desulphurization system amount of sulfur contenting in smoke far away makes desulfurization facility overload operation, and the desulphurizing ability of desulfurizer can not satisfy actual needs, aggravated some problems that desulphurization system itself exists, cause system can not be continuously, stable operation.
In order to overcome the above problems, the main employing added the desulfuration efficiency that sulfur-removing additives improves equipment in the prior art.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, prescription 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, and the compound Limestone-gypsum Wet Flue Gas Desulfurization Process additive that prescription is simple, cost is low, consumption is few, rapid-action.
Technical scheme of the present invention is:
A kind of Limestone-gypsum Wet Flue Gas Desulfurization Process additive, the component of described sulfur-removing additives and the percentage by weight of each component are: adipic acid: 60-90%, magnesium sulfate: 2-10%, sodium carbonate: 4-20%, copper sulphate: 1-8%, manganese sulfate: 1-8%.
Further, the component of described sulfur-removing additives and the percentage by weight of each component are: adipic acid: 70-90%, magnesium sulfate: 3-7%, sodium carbonate: 4-16%, copper sulphate: 1-5%, manganese sulfate: 1-5%.
Further, the component of described sulfur-removing additives and the percentage by weight of each component are: adipic acid: 75-85%, magnesium sulfate: 4-6%, sodium carbonate: 9-15%, copper sulphate: 1-3%, manganese sulfate: 1-4%.
Sulfur-removing additives provided by the invention has following advantage:
1, desulfuration efficiency is high.Wet FGD with Additives provided by the invention belongs to compound sulfur-removing additives, and organic compound is mixed with inorganic compound, strengthens the reactivity of lime stone, thereby improves the desulfuration efficiency of lime stone.In the sulfur-removing additives provided by the invention, inorganic compound can change the ionic equilibrium of desulfurizing tower slurries, the reinforcing desulfuration process, and reaction equation is as follows:
MgSO
4Solubility greater than calcium carbonate, MgSO
4Adding so that the sulfate ion concentration in the slurries increases, sulfate ion becomes calcium sulfate precipitation with calcium binding, thereby promotes the dissolving of lime stone, the raising desulfuration efficiency.Magnesium sulfate plays catalytic action, regulates slurries intermediate ion balance, promotes the dissolving of calcium carbonate; Sodium carbonate mainly rises and accelerates SO
2The effect of dissolving improves desulfuration efficiency.
Manganese sulfate in the inorganic compound and copper sulphate promote the oxidation of calcium sulfite in the reaction as catalyst, improve the utilization ratio of oxidation air.
In the sulfur-removing additives provided by the invention, adipic acid is organic dibasic acid, and the pH value of buffering desulfurizing tower slurries makes pH be in the optimum condition condition, promotes dissolving and the SO of calcium carbonate
2Absorption, improve utilization rate and the SO of absorbent
2Removal efficiency.
In gas phase surface and liquid film, the SO of dissolving
2React the H that dissociates out with water
+, liquid film and liquid phase main body border, C
4H
8(COO
-)
2With H
+Reaction generates C
4H
8(COOH)
2, so that H
+Be passed to the liquid phase main body, H in the 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 -H with disassociation
+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 -Concentration reduces, thereby has promoted the dissolving of calcium carbonate, and reaction equation is as follows:
Organic carboxyl acid ionization generates H
+
Flue gas SO
2Dissolving hydration ionization generates H
+
SO
2+H
2O→H
2SO
3
H
2SO
3→2H
++HSO
3
H
+Again be combined with adipate
The dissolving of calcium carbonate
Use Wet FGD with Additives provided by the invention, under the prerequisite of not carrying out the desulphurization system capacity-increasing transformation, improve the desulfuration efficiency of desulphurization system, 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 addition is few, and cost is low.Sulfur-removing additives selects common several organic matters and inorganic matter to be used in combination, and prescription is simple, and after tested, the first use amount of sulfur-removing additives is the 0.3-0.6 ‰ of absorption tower slurry weight, and later addition is according to SO
2The waste of concentration and additive is calculated and is replenished, and consumption is few, and the sulfur-removing additives cost is low; And the utilization rate of lime stone is high, in use can greatly reduce the use amount of lime stone, and the use cost of desulfurizing agent is low.
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 in the supporting wet desulfurization of flue gas by limestone-gypsum method system of 300MW station boiler the design entry flue gas SO of this desulphurization system
2Concentration is 1584mg/Nm
3, through test, 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 | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 60 | 10 | 20 | 5 | 5 |
| Percentage by weight (%) | 60 | 10 | 20 | 5 | 5 |
The using method of sulfur-removing additives is as follows:
A, with above-mentioned raw materials composite rear one-tenth finished product in proportion;
B, above-mentioned sulfur-removing additives is joined in the absorption tower, initial addition is 0.6 ‰ of lime stone slurry weight;
C, desulphurization system were replenished according to the additive losses situation after operation a period of time.
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 162mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 94%.
Embodiment 2
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 90 | 2 | 4 | 1 | 3 |
| Percentage by weight (%) | 90 | 2 | 4 | 1 | 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;
B, above-mentioned sulfur-removing additives is joined in the absorption tower, initial addition is 0.3 ‰ of lime stone slurry weight;
C, desulphurization system were replenished according to the additive losses situation after operation a period of time.
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 162mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.02, and desulfuration efficiency is 94.2%.
Embodiment 3
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 68 | 6 | 17 | 8 | 1 |
| Percentage by weight (%) | 68 | 6 | 17 | 8 | 1 |
The using method of sulfur-removing additives is as follows:
A, with above-mentioned raw materials composite rear one-tenth finished product in proportion;
B, above-mentioned sulfur-removing additives is joined in the absorption tower, initial addition is 0.5 ‰ of lime stone slurry weight;
C, desulphurization system were replenished according to the additive losses situation after operation a period of time.
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 171mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.02, and desulfuration efficiency is 94.1%.
Embodiment 4
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 64 | 8 | 18 | 2 | 8 |
| Percentage by weight (%) | 64 | 8 | 18 | 2 | 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 3000mg/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 1.02, and desulfuration efficiency is 93.8%, and the initial addition of sulfur-removing additives is 0.4 ‰.
Embodiment 5
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 70 | 7 | 16 | 5 | 2 |
| Percentage by weight (%) | 70 | 7 | 16 | 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 2750mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 151mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 94.5%, and the initial addition of sulfur-removing additives is 0.6 ‰.
Embodiment 6
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 90 | 3 | 4 | 2 | 1 |
| Percentage by weight (%) | 90 | 3 | 4 | 2 | 1 |
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 185mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 93.5%, and the initial addition of sulfur-removing additives is 0.4 ‰.
Embodiment 7
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 78 | 5 | 8 | 4 | 5 |
| Percentage by weight (%) | 78 | 5 | 8 | 4 | 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 2780mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 152mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 94.5%, and the initial addition of sulfur-removing additives is 0.5 ‰.
Embodiment 8
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 2950mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 169mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.03, and desulfuration efficiency is 94.6%, and the initial addition of sulfur-removing additives is 0.6 ‰.
Embodiment 9
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 85 | 4 | 9 | 1 | 1 |
| Percentage by weight (%) | 85 | 4 | 9 | 1 | 1 |
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 2830mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 150mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 94.7%, and the initial addition of sulfur-removing additives is 0.4 ‰.
Embodiment 10
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 80 | 5 | 10 | 3 | 2 |
| Percentage by weight (%) | 80 | 5 | 10 | 3 | 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 2880mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 129mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.01, and desulfuration efficiency is 95.5%, and the initial addition of sulfur-removing additives is 0.5 ‰.
Embodiment 11
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 77 | 5 | 12 | 2 | 4 |
| Percentage by weight (%) | 77 | 5 | 12 | 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 2780mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 133mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.02, and desulfuration efficiency is 95.2%, and the initial addition of sulfur-removing additives is 0.5 ‰.
Embodiment 12
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 75 | 5 | 14 | 3 | 3 |
| Percentage by weight (%) | 75 | 5 | 14 | 3 | 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 2800mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 145mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.03, and desulfuration efficiency is 94.8%, and the initial addition of sulfur-removing additives is 0.6 ‰.
Embodiment 13
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 82 | 4 | 11 | 1 | 2 |
| Percentage by weight (%) | 82 | 4 | 11 | 1 | 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 2700mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 137mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.04, and desulfuration efficiency is 94.9%, and the initial addition of sulfur-removing additives is 0.4 ‰.
Embodiment 14
The component of sulfur-removing additives and the percentage by weight of each component are:
(gross weight is 100Kg)
| Component | Adipic acid | Magnesium sulfate | Sodium carbonate | Copper sulphate | Manganese sulfate |
| Weight (Kg) | 88 | 3 | 6 | 1 | 2 |
| Percentage by weight (%) | 88 | 3 | 6 | 1 | 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 2900mg/Nm
3The time, SO in the outlet flue gas
2Concentration be 165mg/Nm
3, liquid-gas ratio is 10.2, and calcium sulfur ratio is 1.03, and desulfuration efficiency is 94.3%, and the initial addition of sulfur-removing additives is 0.5 ‰.
Claims (3)
1. a Limestone-gypsum Wet Flue Gas Desulfurization Process additive is characterized in that, the component of described sulfur-removing additives and the percentage by weight of each component are:
Adipic acid: 60-90%, magnesium sulfate: 2-10%, sodium carbonate: 4-20%, copper sulphate: 1-8%, manganese sulfate: 1-8%.
2. Limestone-gypsum Wet Flue Gas Desulfurization Process additive according to claim 1 is characterized in that, the component of described sulfur-removing additives and the percentage by weight of each component are:
Adipic acid: 70-90%, magnesium sulfate: 3-7%, sodium carbonate: 4-16%, copper sulphate: 1-5%, manganese sulfate: 1-5%.
3. Limestone-gypsum Wet Flue Gas Desulfurization Process additive according to claim 1 is characterized in that, the component of described sulfur-removing additives and the percentage by weight of each component are:
Adipic acid: 75-85%, magnesium sulfate: 4-6%, sodium carbonate: 9-15%, copper sulphate: 1-3%, manganese sulfate: 1-4%.
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|---|---|---|---|
| CN2012101012079A CN103357256A (en) | 2012-03-31 | 2012-03-31 | Limestone-gypsum wet-process desulphurization additive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101012079A CN103357256A (en) | 2012-03-31 | 2012-03-31 | Limestone-gypsum wet-process desulphurization additive |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512679A (en) * | 2016-12-09 | 2017-03-22 | 上海豹豹新材料科技有限公司 | Wet flue gas desulfurization synergist and application method thereof |
| CN110237668A (en) * | 2019-05-28 | 2019-09-17 | 浙江省地质矿产研究所 | Method for improving desulfurization efficiency of limestone desulfurizer |
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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 |
| 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 |
| 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 |
| CN102091510A (en) * | 2010-12-17 | 2011-06-15 | 马鞍山市鸿伟环化有限公司 | Flue gas desulfurization synergist and using method thereof |
-
2012
- 2012-03-31 CN CN2012101012079A patent/CN103357256A/en active Pending
Patent Citations (4)
| 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 |
| 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 |
| CN102091510A (en) * | 2010-12-17 | 2011-06-15 | 马鞍山市鸿伟环化有限公司 | Flue gas desulfurization synergist and using method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512679A (en) * | 2016-12-09 | 2017-03-22 | 上海豹豹新材料科技有限公司 | Wet flue gas desulfurization synergist and application method thereof |
| CN110237668A (en) * | 2019-05-28 | 2019-09-17 | 浙江省地质矿产研究所 | Method for improving desulfurization efficiency of limestone desulfurizer |
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Address after: Sheng Tong Industrial Park No. 109 Venus Road 410200 in Hunan province Changsha District of Wangcheng City Applicant after: Suntown Technology Group Corporation Address before: Sheng Tong Industrial Park No. 109 Venus Road 410200 in Hunan province Changsha District of Wangcheng City Applicant before: Hunan Shengtong Technology Group Co., Ltd. |
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20131023 |