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Method for processing sulfur paste as coke oven gas desulfuration by-product

A technology of coke oven gas and by-products, which is applied in chemical instruments and methods, thiosulfate/dithionite/polythionate, thiocyanate, etc., and can solve the problem of heavy pollution in the purification process, poor economic benefits, Low extraction rate and other issues to achieve the effect of avoiding further pollution, ensuring clean production, and high recycling rate

Active Publication Date: 2013-08-28
张建利
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

At present, the purification of sulfur can be roughly divided into two categories: (1) the purification method of molten sulfur (CN200910153102.6, CN200910150565.7, CN200410020529.6, CN00256049.6); (2) the organic solvent purification method (CN200310114627.1, CN200810229462.5), although the above patents all claim that high-purity sulfur can be obtained, comprehensive analysis from the perspectives of environmental protection, energy and economy, the above-mentioned processes all have high energy consumption, large pollution in the purification process and low extraction rate, especially sulfur paste Harmful substances (mainly ammonium thiocyanate, ammonium thiosulfate) and other impurities contained in the purified waste liquid cannot be harmlessly treated, so the waste liquid after sulfur paste purification still causes environmental pollution and other disadvantages
[0005] There are currently three main treatment methods for the waste liquid after desulfurization by-product sulfur paste purification and HPF desulfurization waste liquid: the first is to use the principle of co-saturated multi-component system phase diagram to concentrate multiple times and crystallize the thiocyanate in a step-by-step manner Separation and purification of ammonium and ammonium thiosulfate (CN201110180361.5, CN200810128357.2). Since the solubility difference between ammonium thiocyanate and ammonium thiosulfate is not large, the process is cumbersome and requires high crystallization concentration and temperature control. The salt purity is low, the economic benefits are poor, and it is not suitable for wastewater solutions with high ammonium sulfate content; the second is to oxidize the ammonium thiosulfate in the desulfurization liquid to ammonium sulfate through a catalyst, and then fractionally crystallize and purify ammonium thiocyanate and sulfuric acid Ammonium (CN201210147582.7, CN2007101395747, Japanese Patent Publication No. 55-126531), the disadvantage of this method is that copper salt needs to be regenerated at high temperature when using copper salt to purify ammonium thiocyanate, and ammonium thiosulfate with high economic value cannot be purified. The benefit is poor, the copper salt lost in the purification process becomes a new source of pollution, and more industrial wastewater is discharged; the third is to convert all the ammonium salt in the wastewater into ammonium sulfate under high temperature and pressure and under the action of a catalyst for recovery ( Japanese Patent Publication No. 57-7852), this method requires high equipment conditions, high operating costs, and the economic value of ammonium sulfate obtained by oxidation is low, and general enterprises cannot use this method

Method used

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  • Method for processing sulfur paste as coke oven gas desulfuration by-product
  • Method for processing sulfur paste as coke oven gas desulfuration by-product

Examples

Experimental program
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Effect test

Embodiment 1

[0034] refer to figure 1 , coke oven gas desulfurization and decyanation by-product sulfur paste 1000kg (the composition content is about 42% of sulfur, 13% of sulfur salt (ammonium thiosulfate, ammonium thiocyanate, ammonium sulfate), 3% of solid impurities such as coal ash , moisture 40%, desulfurization catalyst 0.02%, a small amount of coal tar components such as naphthalene 300ppm, NH 3 1.2%)

[0035] Sulfur paste processing steps:

[0036] Step 1: Dissolving sulfur and removing impurities: 1000kg of desulfurization paste and 8000kg of tetrachlorethylene are stirred and mixed in the dissolution tank at a weight ratio of 1:8, and the temperature is raised to 110°C. After maintaining this temperature for 1 hour, the tetrachlorethylene The upper brine-containing phase is separated and introduced into the desulfurization waste liquid salt extraction process, and the remaining organic phase is subjected to heat preservation and thermal filtration to obtain sulfur-containing ...

Embodiment 2

[0041] refer to figure 1 , Coke oven gas desulfurization and decyanation by-product sulfur paste 1000kg (sulfur 39%, sulfur salt (ammonium thiosulfate, ammonium thiocyanate, ammonium sulfate) 14%, coal ash and other solid impurities 2%, moisture 43%, desulfurization catalyst 0.03%, a small amount of coal tar components such as naphthalene 400ppm, NH 3 1.5%)

[0042] Sulfur paste processing steps:

[0043] Step 1: Dissolving sulfur and removing impurities: 1000kg of desulfurization paste and 8000kg of tetrachlorethylene are stirred and mixed in the dissolution tank at a weight ratio of 1:8, and the temperature is raised to 100°C. After maintaining this temperature for 1 hour, the tetrachlorethylene The upper brine-containing phase is separated and introduced into the desulfurization waste liquid salt extraction process, and the remaining organic phase is subjected to heat preservation and thermal filtration to obtain sulfur-containing perchlorethylene filtrate and a small amo...

Embodiment 3

[0047] Embodiment 3: refer to figure 2

[0048] Waste liquid treatment:

[0049] 1000kg of waste liquid from coke oven gas desulfurization and decyanation paste (ammonium thiocyanate content 13%, ammonium thiosulfate content 9%, ammonium sulfate content 8%)

[0050] Step 1: Decolorization and impurity removal: add 1kg of 0.1% (w / w) activated carbon to the desulfurization waste liquid, keep it warm at 100°C for 30 minutes, and then filter to obtain the decolorized filtrate and activated carbon filter cake (the activated carbon filter cake will be sent to a professional recycling enterprise for regeneration treatment ).

[0051] Step 2: Concentrate the decolorized solution under reduced pressure: Concentrate the filtrate of step 1 under reduced pressure at 70°C (vacuum degree 70mmHg) until the specific gravity of the system is 1.24 (g / ml) and stop concentrating (water content is 18% (w / w) ), transfer the concentrated system to the crystallizer with heat preservation, distill...

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Abstract

The invention relates to a method for processing sulfur paste as a coke oven gas desulfuration by-product. The method is characterized in that a sulfur paste processing procedure comprises the steps of dissolving sulfur and removing impurities, decoloring and removing impurities, lowering temperature and crystallizing, drying the product and the like; and a waste liquid treatment procedure comprises the steps of decoloring and removing impurities, carrying out vacuum concentration on filtrate containing salt, separating ammonium thiocyanate, concentrating the ammonium thiocyanate ethyl alcohol filtrate for crystallization, drying an ammonium thiocyanate product, separating ammonium sulfate, concentrating the ammonium thiosulfate filtrate for crystallization, drying the ammonium thiosulfate product, and the like. The method can be used for thoroughly processing the sulfur paste and the waste liquid containing sulfur, the recycling rate of the product is high, no mixed salt and waste water are discharged without cause secondary pollution, so that the method is clean and environment-friendly. The method also has the outstanding characteristics of strong adaptive capacity, large production elasticity, high resource utilization ratio and the like.

Description

technical field [0001] The invention belongs to the technical field of coking industry waste treatment. It specifically relates to a treatment method for coke oven gas desulfurization by-product sulfur paste, that is, a process for further purifying sulfur paste produced in the HPF or PDS desulfurization production process of a coking plant and performing harmless treatment of the purified sulfur-containing waste liquid . Background technique [0002] The coke oven gas produced during the coal coking process contains 5-8g / m 3 of hydrogen sulfide (H 2 S) and 1~1.5g / m 3 Hydrogen cyanide (HCN), the sulfur oxides and nitrogen oxides generated after its combustion seriously pollute the environment, and the above two gases are toxic substances. Therefore, at present, domestic coking enterprises are equipped with coke oven gas desulfurization and decyanation equipment, and the desulfurization and decyanation processes used by the equipment can be divided into two categories: ox...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B17/027C01B17/64C01C3/20C01F11/46
CPCC01B17/64C01B17/0216C01B17/0232C01C3/20C01F11/46C01P2006/80
Inventor 陈宏闫鹏籍文武
Owner 张建利
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