CN103113930B - Method and equipment for improving desulfurization efficiency of coke oven gas by vacuum potassium carbonate method - Google Patents
Method and equipment for improving desulfurization efficiency of coke oven gas by vacuum potassium carbonate method Download PDFInfo
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- CN103113930B CN103113930B CN201310062957.4A CN201310062957A CN103113930B CN 103113930 B CN103113930 B CN 103113930B CN 201310062957 A CN201310062957 A CN 201310062957A CN 103113930 B CN103113930 B CN 103113930B
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Abstract
The invention discloses a method for improving desulfurization efficiency of coke oven gas by a vacuum potassium carbonate method. The method comprises the steps of adding KOH solution into regenerated potassium carbonate barren liquor to fully mix, conveying the mixing solution to the lower segment of a desulfurizing tower, reversely contacting airflow of coke oven gas to absorb acid gas, so as to reuse in circulation, wherein the barren liquor outlet at the bottom part of a regeneration tower in the equipment is connected with the input end of a barren liquor tank; a sylvite supply opening is arranged in the barren liquor tank; and the output end of the barren liquor tank is communicated with the barren liquor inlet at the top part of the lower section of the desulfurizing tower. The KOH solution is supplied to the regenerated potassium carbonate barren liquor; the pH value of the potassium carbonate barren liquor is increased because of adding of KOH; adsorption of the acid gas inside the desulfurizing tower is facilitated, so as to improve the desulfurization efficiency; and the pH value of pregnant solution is constant due to the supplement of KOH, so as to optimize the acid gas analysis condition. Therefore, the desulfurization efficiency is further improved.
Description
Technical field
The present invention relates to coke oven gas purification technology, refer to particularly a kind of method and equipment thereof that improves vacuum potassium carbonate method coke oven gas desulfurization efficiency.
Background technology
Vacuum potassium carbonate coal gas desulfurization technique is adopted by numerous domestic coal chemical industry enterprises in recent years.This technique mainly comprises desulfurization and regeneration two parts, uses solution of potassium carbonate directly to absorb the H in coke-oven gas in thionizer
2the sour gas such as S and HCN, solution of potassium carbonate has absorbed a large amount of H
2after S, become sulfur removing pregnant solution; The absorption out of thionizer bottom the rich solution of sour gas after rich solution groove storage buffering, enter regenerator column regeneration, in regenerator column, carry out acid gas parsing, discharge sour gas and become regeneration lean solution, lean solution is returned thionizer again and is recycled.In this system, solution of potassium carbonate is CO in the KOH solution that supplemented by system and coal gas
2reaction generates.Side reaction produces KSCN and K owing to can occur solution of potassium carbonate in absorption-reprocessing cycle
4fe (CN)
6etc. non-renewable salt, generally can adjust by measures such as outer row's lean solution, supplementary KOH amounts the quality of doctor solution.At present, adopt the arbitrary way that KOH is mixed with the rich solution before regenerator column after thionizer, this arbitrary way is simple to operate, but because KOH replenishes before regenerator column, basicity and the pH value of rich solution in regenerator column after supplementary KOH, are improved, according to Analytic Tower Analytic principle, there is disadvantageous effect to the parsing of acid gas in rich solution in the rising of basicity and pH value, and after can causing regenerating, lean solution is containing H
2s concentration is higher, and then after causing lean solution to be back to thionizer, desulfuration efficiency declines.
Summary of the invention
The problem that the object of the invention is to exist for prior art provides a kind of method and equipment thereof that improves vacuum potassium carbonate method coke oven gas desulfurization efficiency, the method is optimized the processing condition in thionizer and regenerator column by the arbitrary way of improving KOH, and then improves the desulfuration efficiency of system.
For achieving the above object, the technical solution used in the present invention is: a kind of method that improves vacuum potassium carbonate method coke oven gas desulfurization efficiency, it comprises the steps:
1) adopt salt of wormwood lean solution to contact with coke-oven gas air-flow is reverse at thionizer hypomere as sweetening agent, salt of wormwood lean solution generates sulfur removing pregnant solution after absorbing the sour gas in coke-oven gas;
2) sulfur removing pregnant solution producing in step 1) is sent into regenerator column regeneration, sour gas is desorbed from rich solution, obtain the salt of wormwood lean solution of regeneration;
3) KOH solution is added by step 2) fully mix in the salt of wormwood lean solution that obtains, then this mixed solution is delivered to thionizer hypomere, contact cyclically utilizing with coke-oven gas air-flow is reverse;
4) adopt NaOH solution or the mixed solution that obtains from step 3) and distribute a part of mixed solution as washing composition, at thionizer epimere, coke-oven gas is carried out to secondary washing with this washing composition.
Further, the mass percent concentration scope of described KOH solution is 10 ~ 50%.
The present invention adopts the mode of adding KOH solution to supplement sylvite, and its reaction is as follows: 2KOH+CO
2→ K
2cO
3+ H
2o
For realizing the equipment of the raising vacuum potassium carbonate method coke oven gas desulfurization efficiency that aforesaid method designs, comprise the thionizer for absorbing coke-oven gas sour gas and the regenerator column for sulfur removing pregnant solution is regenerated, the washings entrance at described thionizer epimere top is connected with the output terminal of alkali groove, the sulfur removing pregnant solution outlet of described thionizer hypomere bottom is connected with the input terminus of rich solution groove, the output terminal of described rich solution groove is communicated with the rich solution entrance at regenerator column top, the lean solution outlet of described regenerator column bottom is connected with the input terminus of lean solution groove, on described lean solution groove, have sylvite and supplement mouth, the output terminal of described lean solution groove is communicated with the lean solution entrance at thionizer hypomere top.
Further, the output terminal of described rich solution groove is communicated with by the thermal medium pipeline of interchanger and the rich solution entrance at regenerator column top; The lean solution outlet of described regenerator column bottom is connected with the input terminus of lean solution groove by the cold medium pipeline of interchanger.
Compared with prior art, tool of the present invention has the following advantages:
One, the present invention changes the auxiliary point of KOH in the salt of wormwood lean solution replenishing after regeneration into by replenishing in sulfur removing pregnant solution, salt of wormwood lean solution is owing to causing adding of KOH its pH value to raise, pH value after this rising is conducive to the absorption of thionizer inner acidic gas, thereby improve desulfuration efficiency, further reduced H in coal gas
2the concentration of S, has stablized the coal gas index of dispatching from the factory, and coal gas qualified rate is raise.
Its two, because of the arbitrary way of no longer taking KOH is mixed with rich solution, make rich solution pH value constant, avoided adding of KOH to cause the rising of rich solution pH value, thereby optimized the processing condition that in regenerator column, acid gas is resolved, reduced H in the salt of wormwood lean solution after regeneration
2the concentration of S, has stablized the quality of salt of wormwood lean solution, and then has improved its follow-up desulfuration efficiency in thionizer, and make regenerator column resolve the acid gas composition obtaining to tend towards stability, and has improved the yield of sulphur in subsequent handling or sulfuric acid product.
Its three, the change of KOH auxiliary point does not affect the supplementary result of system sylvite.
Brief description of the drawings
Fig. 1 is a kind of structural representation of the equipment that improves vacuum potassium carbonate method coke oven gas desulfurization efficiency.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated, but the present invention is not limited to following embodiment.
The equipment of the raising vacuum potassium carbonate method coke oven gas desulfurization efficiency shown in Fig. 1, comprise the thionizer 1 for absorbing coke-oven gas sour gas and the regenerator column 2 for sulfur removing pregnant solution is regenerated, the washings entrance 3 at described thionizer 1 epimere top is connected with the output terminal of alkali groove 4, the sulfur removing pregnant solution outlet 5 of described thionizer 1 hypomere bottom is connected with the input terminus of rich solution groove 6, the output terminal of described rich solution groove 6 is communicated with the rich solution entrance 7 at regenerator column 2 tops by the thermal medium pipeline of interchanger 12, the lean solution outlet 8 of described regenerator column 2 bottoms is connected with the input terminus of lean solution groove 9 by the cold medium pipeline of interchanger 12, on described lean solution groove 9, have sylvite and supplement mouth 10, the output terminal of described lean solution groove 9 is communicated with the lean solution entrance 11 at thionizer 1 hypomere top.
The technical process of aforesaid device is as follows: import H
2s concentration is 5 ~ 7g/m
3coke-oven gas first flow through from bottom to top thionizer 1 hypomere and salt of wormwood lean solution counter current contact, more than 90% H in coke-oven gas
2s, HCN, CO
2be absorbed Deng sour gas, salt of wormwood lean solution changes into and has absorbed a large amount of H
2the salt of wormwood rich solution of S; Salt of wormwood rich solution flows out and pumps in rich solution groove 6 through the rich solution outlet 5 of thionizer 1 hypomere bottom, rich solution groove 6 is for cushioning rich solution flow, then salt of wormwood rich solution pumps in regenerator column 2 and carries out desorb through the rich solution entrance 7 at regenerator column 2 tops again after by interchanger 12 heat exchange, obtains the salt of wormwood lean solution after regeneration; Salt of wormwood lean solution after regeneration pumps in lean solution groove 9 from the lean solution outlet 8 of regenerator column 2 bottoms is flowed out, on described lean solution groove 9, have sylvite and supplement mouth 10, the KOH solution that is 50% by mass percent concentration supplements mouth 10 with constant flow rate from sylvite by volume pump and squeezes into lean solution groove 9, after it is fully mixed with the salt of wormwood lean solution in lean solution groove 9, again this mixed solution being delivered to thionizer 1 hypomere through the lean solution entrance 11 at thionizer 1 hypomere top sprays, contact with coke-oven gas air-flow is reverse, cyclically utilizing, to sponge the most of sour gas in coke-oven gas; Then, the NaOH solution that the mass percent concentration that employing was diluted is 5% is stored in alkali groove 4 as washing composition, washing composition is pumped into thionizer 1 epimere from alkali groove 4 through the washings entrance 3 at thionizer 1 epimere top, coke-oven gas is carried out to secondary washing, to absorb remaining small portion H in coke-oven gas
2the sour gas such as S, make H in coal gas after treatment
2s concentration is reduced to 150 ~ 200mg/m
3, the waste lye producing is sent to follow-up biochemical water treatment operation.In addition, also can from lean solution groove 9, distribute a part of mixed solution being mixed by salt of wormwood lean solution and KOH solution and at thionizer 1 epimere, coke-oven gas be carried out to secondary washing as washing composition, now, the sweetening agent of thionizer 1 epimere and thionizer 1 hypomere is all sylvite, scrub raffinate after secondary washing can be returned desulfurization-reprocessing cycle systemic circulation and be used, the scrub raffinate amount that thionizer 1 epimere is produced is reduced to zero, and therefore total generation of desulfurization waste liquor also significantly reduces.For ensureing gas washing effect, before entering lean solution groove 9, outward arrange mouthful 13 regular discharge unit lean solutions by lean solution by regenerator column 2 bottoms salt of wormwood lean solution out, with lean solution quality after ensureing repeatedly to regenerate.The acid gas of discharging from regenerator column 2 top acid gas relief outlets 14 enters claus oven and produces sulphur or sulfuric acid.
The present invention changes the auxiliary point of KOH in the salt of wormwood lean solution replenishing after regeneration into by replenishing in sulfur removing pregnant solution, salt of wormwood lean solution is because its pH value that adds of KOH can be increased to 11 ~ 12 by original 10 ~ 11, be conducive to the absorption of thionizer 1 inner acidic gas, improved the desulfuration efficiency of thionizer 1; KOH no longer replenishes in rich solution groove 6, make sulfur removing pregnant solution pH value constant between 9 ~ 10, avoid adding of KOH to cause the rising of rich solution pH value, thereby the processing condition of the interior acid gas desorb of regenerator column 2 are optimized, stablize salt of wormwood lean solution quality, further improved desulfuration efficiency, the coal gas treatment capacity of system of the present invention can reach 1.5 × 10
5m
3/ h.
Claims (2)
1. a method that improves vacuum potassium carbonate method coke oven gas desulfurization efficiency, is characterized in that: it comprises the steps:
1) adopt salt of wormwood lean solution to contact with coke-oven gas air-flow is reverse at thionizer hypomere as sweetening agent, salt of wormwood lean solution generates sulfur removing pregnant solution after absorbing the sour gas in coke-oven gas;
2) by step 1) in the sulfur removing pregnant solution that produces send into regenerator column regeneration, sour gas is desorbed from rich solution, obtain the salt of wormwood lean solution of regeneration;
3) KOH solution is added by step 2) fully mix in the salt of wormwood lean solution that obtains, then this mixed solution is delivered to thionizer hypomere, contact cyclically utilizing with coke-oven gas air-flow is reverse;
4) from step 3) distribute a part of mixed solution as washing composition the mixed solution that obtains, at thionizer epimere, coke-oven gas is carried out to secondary washing with this washing composition, the scrub raffinate after secondary washing is returned desulfurization-reprocessing cycle systemic circulation and is used.
2. the method for raising vacuum potassium carbonate method coke oven gas desulfurization efficiency according to claim 1, is characterized in that: the mass percent concentration scope of described KOH solution is 10～50%.
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Families Citing this family (8)
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| CN103849437B (en) * | 2014-03-21 | 2016-09-21 | 武汉钢铁(集团)公司 | A kind of vacuum potassium carbonate desulfurization technique method and apparatus |
| CN104946315A (en) * | 2014-03-31 | 2015-09-30 | 江苏联峰能源装备有限公司 | Method for purifying coke oven gas and recycling desulfurated liquid waste by virtue of vacuum potassium carbonate method |
| CN104560224B (en) * | 2015-01-14 | 2017-02-22 | 宁波科新化工工程技术有限公司 | Vacuum carbonate multistage-circulation step-by-step desulfurization process and device thereof |
| CN105112110B (en) * | 2015-08-19 | 2019-03-22 | 攀钢集团西昌钢钒有限公司 | Coal gas vacuum potassium carbonate desulfurization alkaline cleaner and method |
| CN108202055B (en) * | 2018-02-13 | 2021-08-20 | 鞍钢股份有限公司 | Cleaning method for upper section of desulfurizing tower and acid-making tail gas alkaline washing tower |
| CN109012110B (en) * | 2018-06-28 | 2021-04-16 | 北京科技大学 | Method for capturing carbon dioxide by using sodium hydroxide and sodium carbonate |
| CN109012089B (en) * | 2018-06-28 | 2021-04-16 | 北京科技大学 | Method for capturing carbon dioxide by using potassium hydroxide and potassium carbonate |
| CN113526471A (en) * | 2021-05-17 | 2021-10-22 | 杨想全 | Process for purifying acid gas and recovering sulfur from steel blast furnace gas and coking raw gas |
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Effective date of registration: 20170714 Address after: 430083, Hubei Wuhan Qingshan District Factory No. 2 Gate joint stock company organs Patentee after: Wuhan iron and Steel Company Limited Address before: 15 Wuchang, Wuhan Friendship Avenue, No. 999, block A, layer (Wuhan Iron and steel science and technology innovation department), No. 430080, Patentee before: Wuhan Iron & Steel (Group) Corp. |
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