Process technique for discharged doctor solution of HPF desulfurization system of coke-oven plant

A desulfurization system and treatment process technology, applied in chemical instruments and methods, dispersed particle separation, separation methods, etc., can solve the problems of inability to meet the requirements of industrial products, difficult to achieve continuous regeneration, and unsuitable for the treatment of desulfurization liquid. Good economic and social benefits, novel research ideas, and good market prospects

Inactive Publication Date: 2008-07-16
HEBEI IRON AND STEEL
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  • Abstract
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  • Application Information

AI Technical Summary

Problems solved by technology

However, there is a fatal flaw in the HPF desulfurization process: in order to maintain a high desulfurization efficiency, a large amount of desulfurization liquid must be discharged
Although the wet oxidation process can completely solve the problem of desulfurization liquid discharge, the investment is huge and the operating cost is high, which many coking plants cannot afford
[0005] USP5276189 utilizes Ca(OH) 2 Ca(SCN) can be produced by reacting with the desulfurization waste liquid discharged outside 2 , but the production of Ca(SCN) 2 The liquid is dark brown and has a strong odor, which cannot meet the requirements of industrial products
[0006] Patent WO2005 / 100243 proposes adding Fe to sulfur-containing wastewater under acidic conditions 3+ , at Fe 3+ Under the catalytic oxidation of NH 4 SCN to H(SCN) 3 , this complex is easily adsorbed by activated carbon, but this method is only suitable for the treatment of low-concentration thiocyanate waste liquid, and the price of activated carbon is relatively expensive, and continuous regeneration is not easy to achieve in industry, so this method is not suitable Suitable for treating the desulfurization liquid discharged from the HPF desulfurization system
[0007] NH can be directly separated from the desulfurization liquid by direct evaporation using the phase diagram principle of multi-component aqueous solution 4 SCN, due to high operating costs and harsh process conditions, it is difficult to popularize and apply

Method used

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  • Process technique for discharged doctor solution of HPF desulfurization system of coke-oven plant

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] As shown in Figure 1, the complexing agent CuSO 4 . 5H 2 O was added to the complexing kettle, the temperature was adjusted to 20°C, the pH value was adjusted to -1 with sulfuric acid, and the desulfurization liquid was added at a ratio of 1:2.5, and the reaction pressure was set at 1 atm. The reaction that takes place in the complexing kettle is: (NH 4 ) 2 S 2 o 3 and (NH 4 ) 2 SO 3 is oxidized to (NH 4 ) 2 SO 4 , and the complexing agent is reduced at the same time, the complexing agent in the reduced state selects the SCN in the desulfurization solution -1 Ions generate a solid intermediate product—CuSCN. After the reaction is completed, the treated desulfurization liquid and solid intermediate product - CuSCN are separated by filter press. The desulfurization liquid enters the biochemical system for further treatment after ammonia distillation, and the solid intermediate product - CuSCN enters the product generation step.

[0029] The solid intermediate...

Embodiment 2

[0032] As shown in Figure 1, the complexing agent CuSO 4 . 5H 2 O was added to the complexing kettle, the temperature was adjusted to 30°C, the pH value was adjusted to 2 with sulfuric acid, and the desulfurization liquid was added at a ratio of 1:3.5, and the reaction pressure was set at 2atm. The reaction that takes place in the complexing kettle is: (NH 4 ) 2 S 2 o 3 and (NH 4 ) 2 SO 3 is oxidized to (NH 4 ) 2 SO 4 , and the complexing agent is reduced at the same time, the complexing agent in the reduced state selects the SCN in the desulfurization solution -1 Ions generate a solid intermediate product—CuSCN. After the reaction is completed, the treated desulfurization liquid and solid intermediate product - CuSCN are separated by filter press. The desulfurization liquid enters the biochemical system for further treatment after ammonia distillation, and the solid intermediate product - CuSCN enters the product generation step.

[0033] The solid intermediate p...

Embodiment 3

[0036] As shown in Figure 1, the complexing agent CuSO 4 . 5H 2 O was added to the complexing kettle, the temperature was adjusted to 50°C, the pH value was adjusted to 3 with sulfuric acid, and the desulfurization liquid was added in a ratio of 1:4.5, and the reaction pressure was set at 5atm. The reaction that takes place in the complexing kettle is: (NH 4 ) 2 S 2 o 3 and (NH 4 ) 2 SO 3 is oxidized to (NH 4 ) 2 SO 4 , and the complexing agent is reduced at the same time, the complexing agent in the reduced state selects the SCN in the desulfurization solution -1 Ions generate a solid intermediate product—CuSCN. After the reaction is completed, the treated desulfurization liquid and solid intermediate product - CuSCN are separated by filter press. The desulfurization liquid enters the biochemical system for further treatment after being distilled with ammonia, and the solid intermediate product - CuSCN enters the product generation step.

[0037] The solid interm...

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Abstract

The invention relates to a processing technique for discharging desulfurization solution of a coke-oven plant HPF desulfurization system, which pertains to the waste fluid process technical field and is used for solving the problems of reducing COD content in the desulfurization solution and recycling a plurality of thiocyanate products. Particularly, the method comprises the procedures that: A. catalytic oxidation-selection of complexing; B. filter pressing or centrifugal separation; C. product generation; D. regeneration of complexing agents. The method of the invention is characterized in that: 1. using SCN<-> in the desulfurization solution produces chemical products such as NaSCN, KSCN, etc.; 2. the processed COD is reduced from 140000mg/L to 15000mg/L; 3. the invention has relatively small technical investment and simple operation; 4. the complexing agents can be recycled, thus having low operating cost and obvious economic benefits. The invention has novel research thought and reasonable technique, and conforms to a concept of circular economy and has quite good economic and social benefits.

Description

technical field [0001] The invention relates to a processing method for desulfurization liquid discharged from an HPF desulfurization system of a coking plant, and belongs to the technical field of waste liquid treatment. Background technique [0002] Coke oven gas is the most important by-product in the coking process. Coke oven gas contains a large amount of toxic and harmful gases such as hydrogen sulfide and hydrogen cyanide. The desulfurization and decyanation of coke oven gas is very important. Due to the high desulfurization efficiency and low investment, HPF desulfurization process has been widely used. However, there is a fatal flaw in the HPF desulfurization process: in order to maintain a high desulfurization efficiency, a large amount of desulfurization liquid must be discharged. Taking a coking plant with 2 million tons / year as an example, 20-30 tons of desulfurization liquid is discharged every day. Desulfurization waste liquid is a complex mixture containing...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01D53/96B01D53/48
Inventor 张晓力薛德业邵有辉苏海强杨林浩冯天伟刘洪涛刘少阳
Owner HEBEI IRON AND STEEL
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