CN1531991A - Sulfur dioxide removing agent - Google Patents
Sulfur dioxide removing agent Download PDFInfo
- Publication number
- CN1531991A CN1531991A CNA031112161A CN03111216A CN1531991A CN 1531991 A CN1531991 A CN 1531991A CN A031112161 A CNA031112161 A CN A031112161A CN 03111216 A CN03111216 A CN 03111216A CN 1531991 A CN1531991 A CN 1531991A
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- Prior art keywords
- sulfur dioxide
- dioxide removal
- removal agent
- amine
- dispersant
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Abstract
The SO2 removing agent is water solution containing cyclohexane and/or diethanol amine, ethylene diamine and hexanediamine as heavy component and dispersant and water as solvent. It contains preferably also alkyl amine and/or potassium carbonate, and at least one of oxide of Fe, Zn and Mg. The amino nitroxide has powerful desulfurizing effect, and its nitrogen is easy to react with sulfide in gas phase; the ethylene diamine and the hexanediamine as heavy components increase the content of amine and raise alkality to convert the absorbed acid into salt timely; and the existence of amine retards the corrosion to apparatus. The SO2 removing agent has effective component content as low as below 1%, low cost and desulfurizing rate as high as 90%.
Description
Technical field: the gas that the sulfur dioxide removal agent is with fire coal produces mixes, and the sulfur dioxide in the gas is separated and absorbs and the circulating fluid of discharging.
Background technology: now industrial fire coal is produced sulfur dioxide removal in the gas, all adopts two alkaline process, at gas-flow, react absorption sulfur dioxide thereby mixes with flue gas with the liquid spraying of milk of lime, soda ash.But liquid is bigger to the sulphur removal equipment corrosion, and milk of lime, soda ash are subjected to the heat deposition fouling in desulphurization plant, causes the obstruction of equipment and pipeline easily, causes equipment to run well.The useful methyl diethanolamine aqueous solution removes the method for the sour gas in the coke-stove gas, but its methyl diethanolamine weight content is up to 23-40%, and also the alkali compounds that will add weight 1-2% forms the mixed aqueous solution absorbent as activator.Desulfurization operation cost height also will have bigger corrosiveness to equipment.
Summary of the invention:
Purpose of the present invention is exactly to solve the technical problem that effectively removes coal fire discharged sulfur in smoke, provides a kind of corrosivity little, less scaling, the sulfur dioxide removal agent that cost is low.
A kind of sulfur dioxide removal agent of the present invention has cyclohexane (C
6H
3N), diethanol amine (HOCH
2CH
2)
2One or both compositions of NH is characterized in that: also have hexamethylene diamine (C
6H
16N
2) and hexamethylene diamine heavy component H
2N (CH
2N)
6NH
2Reach dispersant, and be the liquid that solvent constitutes with water.Since one or both compositions of cyclohexane, diethanol amine are arranged, more intense with the amido nitrogen oxide to desulfidation, easy and sulfide in gas phase (sour gas) reaction of nitrogen; Also have hexamethylene diamine and hexamethylene diamine heavy component, not only increased the content (amine value) of amine and improved alkalescence, the acid that absorbs in time can also be replaced as ammonium salt, in the dehydrogenation simultaneously and dilute sulfuric acid, reduce greatly acid, the corrosion that minimizing moves.Though the pH value of this sulfur dioxide removal agent is alkalescence at 10-12,, slowed down corrosion greatly to equipment because the existence of amine is arranged.Such aqueous solution sulfur dioxide removal agent, the content of above-mentioned composition has only below 1%, and content is quite low, and the aqueous solution sulfur dioxide removal agent cost of formation reduces greatly, and desulfurization degree can reach more than 90%.Soluble in water for the appeal composition is disperseed more equably, then to adopt corresponding dispersant (or emulsifying agent), can adopt multiple corresponding emulsifying agent, preferably adopt polyvinyl chloride ether methyl-monosilane or fatty amine polyvinyl chloride ether.In order to increase the water-soluble of amine compound, increase absorption simultaneously to the sulfur dioxide sour gas, preferably add alkylamine (C
2H
6NO), one or both of potash.Can further improve desulfurization degree like this, desulfurization degree can reach more than 95%.In order in time to absorb and to react and get off to form the sulfuric acid neutralization, in time removing hydrogen ion reduces acid, add at least a in iron oxide, zinc oxide, the magnesia, with the organic component of above-mentioned multiple mode form the desulfurizing agent that mixes and with the agent of water formation aqueous solution sulfur dioxide removal.The organic component of multiple mode that can certainly be above-mentioned forms the agent of aqueous solution sulfur dioxide removal separately, at these aqueous solution sulfur dioxide removal agent utilization and operation one ends after the time, adds at least a in iron oxide, zinc oxide, the magnesia again.But such iron oxide, zinc oxide, magnesia desulfurization unit use amount increase greatly than together mixing formation aqueous solution sulfur dioxide removal agent use amount with the Main Ingredients and Appearance organic component.So preferably at least a mixing in potash and iron oxide, zinc oxide, the magnesia, and with one or both compositions of cyclohexane, diethanol amine, hexamethylene diamine and hexamethylene diamine heavy component and dispersant are that solvent together constitutes the agent of liquid aqueous solution sulfur dioxide removal with water.Can significantly reduce the unit desulfurization use amount of raw material like this, reduce the cost of desulfurization.The combination of these multiple components can be in different ratio proportionings, preferably by weight one or both compositions of 8-10 part cyclohexane, 6-8 part diethanol amine, and 22-23 part hexamethylene diamine and 22-23 part hexamethylene diamine heavy component and dispersant 5-8; Can also add one or both of 10-18 part alkylamine, 10-15 part potash, add at least a in 10-15 part iron oxide, zinc oxide, the magnesia.
The present invention compared with the prior art, have solved desulphurization circulating substantially liquid to equipment corrosion and system jams and sulphur secondary pollution problem, desulfurization degree reaches as high as 99.6%, sulfur-fixing rate also can reach 99.5%.
Specific embodiment:
Embodiment one, a kind of sulfur dioxide removal agent of the present invention have 1 part of cyclohexane, also have 1 part of each 2 parts of hexamethylene diamine and hexamethylene diamine heavy components and dispersant, and are the liquid solution that solvent constitutes with 500 parts in water.With the also reflux cycle use in the coal-fired flue-gas road of this liquid spraying, desulfurization degree reaches 90.1% after testing.
Embodiment two, a kind of sulfur dioxide removal agent of the present invention have 1 part of diethanol amine, also have 1 part of each 2.5 parts of hexamethylene diamine and hexamethylene diamine heavy components and dispersant, and are the liquid solution that solvent constitutes with 550 parts in water.This sulfur dioxide liquid remove the agent pH value be 10.5 with this liquid spraying in the coal-fired flue-gas road and reflux cycle use, desulfurization degree reaches 90.4% after testing.
Embodiment three, a kind of sulfur dioxide removal agent of the present invention, 1 kilogram of cyclohexane, 1 kilogram of diethanol amine are arranged, also have 1 kilogram of 1 kilogram of hexamethylene diamine and 1 kilogram of hexamethylene diamine heavy component and dispersant polyvinyl chloride ether methyl-monosilane, and be the liquid solution of solvent formation with 1000 kilograms in water.This sulfur dioxide liquid remove the agent pH value be 11 with this liquid spraying in the coal-fired flue-gas road and reflux cycle use, desulfurization degree reaches 91.4% after testing.Desulfurization degree can reach more than 95%.
Embodiment four, a kind of sulfur dioxide removal agent of the present invention, 8 kilograms of cyclohexanes, 7 kilograms of diethanol amine are arranged, also have 6 kilograms of 22 kilograms of hexamethylene diamines and 23 kilograms of hexamethylene diamine heavy components and dispersant polyvinyl chloride ether methyl-monosilanes, add 16 kilograms of alkylamines, and be the liquid solution of solvent formation with 10 tons in water.This sulfur dioxide liquid remove the agent pH value be 11.5 with this liquid spraying in the coal-fired flue-gas road and reflux cycle use, desulfurization degree reaches 95.1% after testing.With 60 kilograms of 1: 1 the aqueous solution of at least a formation in iron oxide, zinc oxide, the magnesia, be added in the solution of circulation after half an hour at desulfurization operation, just the pH value that constantly descends can be gone up can about 5, and can make the sulphur composition in the solution non-volatile, sulfur-fixing rate can reach 95%, has avoided secondary pollution effectively.If 1: 1 the aqueous solution of at least a formation in iron oxide, zinc oxide, the magnesia is just added desulfurizing agent before use to be mixed, only need to add 30 kilograms, just can reach desulfurization degree and reach 95.2%, pH value keeps about 4-5, and sulfur-fixing rate can reach 95.1% effect.
Embodiment five, a kind of sulfur dioxide removal agent of the present invention, 10 kilograms of cyclohexanes, 6 kilograms of diethanol amine are arranged, also have 8 kilograms of 12 kilograms of hexamethylene diamines and 18 kilograms of hexamethylene diamine heavy components and dispersant polyvinyl chloride ether methyl-monosilanes, add 18 kilograms of alkylamines, and be the liquid solution of solvent formation with 20 tons in water.This sulfur dioxide liquid remove the agent pH value be 12 with this liquid spraying in the coal-fired flue-gas road and reflux cycle use, desulfurization degree reaches 95.1% after testing.A kind of in potash and iron oxide, zinc oxide, the magnesia formed 1: 1 100 kilograms of the aqueous solution, be added in the solution of circulation after half an hour at desulfurization operation, just the pH value that constantly descends can be gone up can about 4, and can make the sulphur composition in the solution non-volatile, sulfur-fixing rate can reach 95.4%, has avoided secondary pollution effectively.If a kind of in potash and iron oxide, zinc oxide, the magnesia formed 1: 1 the aqueous solution just to add desulfurizing agent before use and mixes, only need to add 35 kilograms, just can reach desulfurization degree and reach 95.2%, pH value keeps about 4-5, and sulfur-fixing rate can reach 95.6% effect.
Embodiment six, a kind of sulfur dioxide removal agent of the present invention, 10 kilograms of cyclohexanes, 16 kilograms of diethanol amine are arranged, also has 6 kilograms in 10 kilograms of hexamethylene diamines and 8 kilograms of hexamethylene diamine heavy components and dispersant fatty amine polyvinyl chloride ether, add 18 kilograms in potash, and be the liquid solution of solvent formation with 20 tons in water.This sulfur dioxide liquid remove the agent pH value be 11.6 with this liquid spraying in the coal-fired flue-gas road and reflux cycle use, desulfurization degree reaches 95.1% after testing.With 50 kilograms of iron oxide, 1: 1 the aqueous solution of magnesia formation, be added in the solution of circulation after half an hour at desulfurization operation, just the pH value that constantly descends can be gone up can about 6, and can make the sulphur composition in the solution non-volatile, sulfur-fixing rate can reach 95.8%, has avoided secondary pollution effectively.If potash and iron oxide, 1: 1 the aqueous solution of magnesia formation are just added desulfurizing agent before use and mix, only need to add 10 kilograms, just can reach desulfurization degree and reach 95.2%, about pH value maintenance 6-7, sulfur-fixing rate can reach 95.8% effect.
Claims (9)
1, a kind of sulfur dioxide removal agent has one or both compositions of cyclohexane, diethanol amine, it is characterized in that: also have hexamethylene diamine and hexamethylene diamine heavy component and dispersant, and be the liquid that solvent constitutes with water.
2, as the said sulfur dioxide removal agent of claim 1, it is characterized in that: add one or both of alkylamine, potash.
3, as claim 1 or 2 said sulfur dioxide removal agent, it is characterized in that: add at least a in iron oxide, zinc oxide, the magnesia.
4, as the said sulfur dioxide removal agent of claim 1, it is characterized in that: by weight one or both compositions of 8-10 part cyclohexane, diethanol amine, 22-23 part hexamethylene diamine and 22-23 part hexamethylene diamine heavy component and dispersant 5-8 part.
5, as the said sulfur dioxide removal agent of claim 4, it is characterized in that: one or both of 10-18 part alkylamine, potash.
6, as claim 4 or 5 said sulfur dioxide removal agent, it is characterized in that: add at least a in 4-15 part iron oxide, zinc oxide, the magnesia.
7, as claim 1 or 2 or 4 or 5 said sulfur dioxide removal agent, it is characterized in that: dispersant is polyvinyl chloride ether methyl-monosilane or fatty amine polyvinyl chloride ether.
8, as the said sulfur dioxide removal agent of claim 3, it is characterized in that: dispersant is polyvinyl chloride ether methyl-monosilane or fatty amine polyvinyl chloride ether.
9, as the said sulfur dioxide removal agent of claim 6, it is characterized in that: dispersant is polyvinyl chloride ether methyl-monosilane or fatty amine polyvinyl chloride ether.
Priority Applications (1)
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---|---|---|---|
CNB031112161A CN1331567C (en) | 2003-03-18 | 2003-03-18 | Sulfur dioxide removing agent |
Applications Claiming Priority (1)
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---|---|---|---|
CNB031112161A CN1331567C (en) | 2003-03-18 | 2003-03-18 | Sulfur dioxide removing agent |
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CN1531991A true CN1531991A (en) | 2004-09-29 |
CN1331567C CN1331567C (en) | 2007-08-15 |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103908885A (en) * | 2014-04-04 | 2014-07-09 | 泰兴电除尘设备厂有限公司 | Preparation method and application of zinc oxide slurry for flue gas desulfurization |
CN103908884A (en) * | 2014-04-04 | 2014-07-09 | 泰兴电除尘设备厂有限公司 | Zinc oxide slurry for flue gas desulfurization |
CN103908886A (en) * | 2014-04-04 | 2014-07-09 | 泰兴电除尘设备厂有限公司 | Method for desulphurizing by zinc oxide slurry containing novel additive |
CN103908887A (en) * | 2014-04-04 | 2014-07-09 | 泰兴电除尘设备厂有限公司 | Additive for zinc oxide slurry for flue gas desulfurization |
CN105797783A (en) * | 2016-04-06 | 2016-07-27 | 山东成泰化工有限公司 | Low-temperature crude oil catalyst and preparation method thereof |
CN109107375A (en) * | 2017-06-22 | 2019-01-01 | 江苏瑞丰科技实业有限公司 | A kind of high-efficiency titanium dioxide sulfur catalysis remover and its application method |
CN113318586A (en) * | 2021-06-09 | 2021-08-31 | 华东理工大学 | Application of amine compound in improvement of organic sulfur dissolution and absorption removal |
CN115634713A (en) * | 2022-10-26 | 2023-01-24 | 浙江誉衡环保科技有限公司 | Desulfurization synergist for flue gas desulfurization and preparation method thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1037068C (en) * | 1994-03-12 | 1998-01-21 | 湖北省化学研究所 | Absorptive sweetening agent for room temp. conversion of hydrogen sulfide, carbonyl sulfide, carbon disulfide and preparation thereof |
CN1085103C (en) * | 1998-11-13 | 2002-05-22 | 中国石油化工集团公司 | Desulfurizer for refining gas and its preparation method |
CN1101717C (en) * | 2000-10-16 | 2003-02-19 | 中国石油化工集团公司 | Wet process for removing SO2 from fume |
CN1139422C (en) * | 2001-12-30 | 2004-02-25 | 国家环境保护总局华南环境科学研究所 | Wet urea additive process for simultanously desulfurizing and denitrification |
-
2003
- 2003-03-18 CN CNB031112161A patent/CN1331567C/en not_active Expired - Fee Related
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103908885A (en) * | 2014-04-04 | 2014-07-09 | 泰兴电除尘设备厂有限公司 | Preparation method and application of zinc oxide slurry for flue gas desulfurization |
CN103908884A (en) * | 2014-04-04 | 2014-07-09 | 泰兴电除尘设备厂有限公司 | Zinc oxide slurry for flue gas desulfurization |
CN103908886A (en) * | 2014-04-04 | 2014-07-09 | 泰兴电除尘设备厂有限公司 | Method for desulphurizing by zinc oxide slurry containing novel additive |
CN103908887A (en) * | 2014-04-04 | 2014-07-09 | 泰兴电除尘设备厂有限公司 | Additive for zinc oxide slurry for flue gas desulfurization |
CN103908886B (en) * | 2014-04-04 | 2016-08-31 | 江苏蓝电环保股份有限公司 | A kind of employing zinc oxide paste liquid sulfur method containing additive |
CN105797783A (en) * | 2016-04-06 | 2016-07-27 | 山东成泰化工有限公司 | Low-temperature crude oil catalyst and preparation method thereof |
CN109107375A (en) * | 2017-06-22 | 2019-01-01 | 江苏瑞丰科技实业有限公司 | A kind of high-efficiency titanium dioxide sulfur catalysis remover and its application method |
CN113318586A (en) * | 2021-06-09 | 2021-08-31 | 华东理工大学 | Application of amine compound in improvement of organic sulfur dissolution and absorption removal |
CN115634713A (en) * | 2022-10-26 | 2023-01-24 | 浙江誉衡环保科技有限公司 | Desulfurization synergist for flue gas desulfurization and preparation method thereof |
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CN1331567C (en) | 2007-08-15 |
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