CN101428193A - Wet-type desulfuration method for steel scoria with flue gas - Google Patents
Wet-type desulfuration method for steel scoria with flue gas Download PDFInfo
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- CN101428193A CN101428193A CNA2008101533760A CN200810153376A CN101428193A CN 101428193 A CN101428193 A CN 101428193A CN A2008101533760 A CNA2008101533760 A CN A2008101533760A CN 200810153376 A CN200810153376 A CN 200810153376A CN 101428193 A CN101428193 A CN 101428193A
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Abstract
The invention discloses a method for steel slag wet-type desulphurization of flue gas. The method includes the following process: steel slag powder is subjected to hydrolysis and additional dissolution treatment; a steel slag solubilization liquid is obtained, added into a solid-liquid separator and mixed with steel slag absorption pregnant solution; after separation, the supernatant liquid after passing through a steel slag absorption liquid storage tank is pumped to an absorption tower where desulphurization occurs when the supernatant liquid is in contact with flue gas; or the steel slag solubilization liquid is added into the steel slag absorption liquid storage tank and mixed with the supernatant liquid, and then the steel slag solubilization liquid is pumped to the absorption tower where desulphurization occurs when the liquid is in contact with the flue gas; a steel slag absorption pregnant solution produced at the bottom part of the absorption tower is subjected to separation in the solid-liquid separator; precipitum is dehydrated in a hydroextractor, and plaster, a by-product, is obtained; and purified flue gas emitted from the bottom part or the top part of the absorption tower is discharged into the atmosphere. Compared with the traditional lime/limestone-plaster method, the invention has the advantages of ensuring the desulphurization degree of flue gas can be attained, and effectively preventing the absorption tower from scaling. Moreover, the equipment occupies a small area and is operated at a low cost, so that the economic benefits of waste utilization are improved.
Description
Technical field
The present invention relates to a kind of wet-type desulfuration method for steel scoria of flue gas, belong to the desulfur technology that contains sulfur dioxide gas.
Background technology
The flue gas that the flue gas that coal-burning boiler produces and the sintering circuit of steel industry produce all contains SO
2, be to implement desulfurization, the important object of protection environment.
At present, flue gas desulfurization method is control SO
2Pollute effective method, and be most widely used with the limestone/lime-gypsum method in the doctor treatment.But because the sinter fume amount is big, SO
2Concentration is lower, and its flue dust is mainly brown iron oxide, thereby the limestone/lime-gypsum desulfur technology is used for iron and steel enterprise and causes not only that investment is big, operating cost is high; And brown iron oxide makes and the plaster splint redness is unfavorable for the further utilization of gypsum by-product; It is very abundant to add China's gypsum resource, and a large amount of gypsum of by-product find no market, and needs the cost substantial contribution to dispose.
Magnesium method in the tradition sulfur method, ammonia process are owing to the subsequent treatment process complexity, and accessory substance is difficult to realize recycling, thereby has also limited their extensive use.Some new technologies of Chu Xianing thereupon, as sea water desulfuration, the CFB method, the NID method, electronic beam method etc., but these new technologies are because the restriction of various conditions, and application example is also few, can not adapt to the needs of China's total amount of pollutant control policy requirements and enterprise's self-growth.
Based on the desulfur technology difficult point of present existence, need a kind of low cost of exploitation, can resource, operational administrative is simple, the sulfur method of miniaturization and desulfurizer.
Summary of the invention
The object of the present invention is to provide a kind of wet-type desulfuration method for steel scoria of flue gas, the high and low cost of this method efficient.
The present invention is realized by following technical proposals, a kind of wet-type desulfuration method for steel scoria of flue gas, the device that this method adopts comprises: absorption tower, solid-liquid separator, slag absorption liquid storage tank, dewaterer, slag ultrasonic wave solubilising device, pump and slag hydrolysis reactor is characterized in that comprising following process:
With powder particle diameter size order number is that 325 orders-100 purpose slag and water are 1 by mass ratio: the reaction that is hydrolyzed of 2.5-5.0 adding slag hydrolysis reactor, slag-metal reaction liquid adds slag ultrasonic wave solubilising device behind the hydrolysis, and add the wetting agent that comprises detergent alkylate naphthenic acid sodium by slag hydrolysis liquid and wetting agent mass ratio 1: 0.005-0.01 to this slag ultrasonic wave solubilising device, and slag-metal reaction liquid is increased dissolution process 0.2-3 minute with the ultrasonic wave of 0.01～50 watt/square centimeter of power density, handling back slag solubilising liquid adding solid-liquid separator mixes with slag absorption rich solution, in solid-liquid separator through sedimentation separation or centrifugation, the precipitum of solid-liquid separator bottom enters dewaterer and dewaters and obtain the accessory substance gypsum, the supernatant on solid-liquid separator top enters slag absorption liquid storage tank, then the slag absorption liquid is added the top, absorption tower with pump, flue gas feeds absorption tower and the execution of slag absorption liquid and stream or counter current contacting operation by the top or the bottom on absorption tower, has absorbed SO
2Slag absorb rich solution and enter solid-liquid separator by the bottom on absorption tower, through sedimentation separation or centrifugation, the purification flue gas of the desulfurization of being discharged by the bottom or the top on absorption tower enters atmosphere through chimney.
Work as SO in the flue gas in the said process
2Under the lower situation of concentration, adopt the cocurrent cooling operation mode; SO in flue gas
2Under the concentration condition with higher, adopt the operation reflux type.
Two of method is characterized in that comprising following process:
With powder particle diameter size order number is that 325 orders-100 purpose slag and water are 1 by mass ratio: the reaction that is hydrolyzed of 2.5-5.0 adding slag hydrolysis reactor, slag-metal reaction liquid adds slag ultrasonic wave solubilising device behind the hydrolysis, and add the wetting agent that comprises detergent alkylate naphthenic acid sodium by slag hydrolysis liquid and wetting agent mass ratio 1: 0.005-0.01 to this slag ultrasonic wave solubilising device, and slag-metal reaction liquid is increased dissolution process 0.2-3 minute with the ultrasonic wave of 0.01～50 watt/square centimeter of power density, handle back slag solubilising liquid and add slag absorption liquid storage tank as the slag absorption liquid, then the slag absorption liquid is added the top, absorption tower with pump, flue gas feeds absorption tower and the execution of slag absorption liquid and stream or counter current contacting operation by the top or the bottom on absorption tower, has absorbed SO
2Slag absorb rich solution and enter solid-liquid separator by the bottom on absorption tower, through sedimentation separation or centrifugation, the precipitum of solid-liquid separator bottom enters dewaterer and dewaters and obtain the accessory substance gypsum, the supernatant on solid-liquid separator top enters slag absorption liquid storage tank, mix as the slag absorption liquid to recycle with slag solubilising liquid in the slag absorption liquid storage tank, the purification flue gas of the desulfurization of being discharged by the bottom or the top on absorption tower enters atmosphere through chimney.
Work as SO in the flue gas in the said process
2Under the lower situation of concentration, adopt the cocurrent cooling operation mode; SO in flue gas
2Under the concentration condition with higher, adopt the operation reflux type.
Below the present invention is described in detail:
One of key technology of the present invention is the solubilising of slag liquid behind the preliminarily solubilised, and this process is to dissolve more basic anhydride in the following short time of effect rapidly at ultrasonic wave, and the basic component utilization rate that is used for desulfurization in the slag is improved.This process is because action of ultrasonic waves has accelerated to comprise in the slag dissolution velocity and the meltage of CaO, MgO basic anhydride greatly, solved the slow difficult problem of desulfurization alkaline components dissolution velocity in the slag very effectively, not only equipment therefor has the little characteristics of volume, and it is easy to operate, thereby reduce whole process expense and improved the steel slag utilization rate, provide critical technical guarantee for reducing operating cost.
Two of key technology of the present invention is that the liquid after the regeneration carries out process of solid-liquid separation, because the steel slag and desulfurized basic component in regeneration back has MgSO
3And CaSO
3And inert component CaSO
4, insoluble matter silicate etc., and MgSO
3Solubility than CaSO under the same terms
3Solubility big more than 400 times, thereby the composition of the magnesium in the supernatant many than calcium.Along with supernatant as the recycling of absorbent, the magnesium component in the absorption liquid reaches accumulation gradually, calcium salt is then separated with the inertia slag of remnants with the form of precipitation, uses or returns converter and make solvent as cement raw material.Because the Ca in the circulating absorption solution
2+Concentration is very little, thereby the absorption tower also is difficult for stopping up, the situation of fouling.Simultaneously recycling of absorption liquid avoided the generation of a large amount of waste liquids to cause difficult treatment and processing cost to increase, thereby lays a good foundation for the low-cost stable operation of absorption system.
Three of key technology of the present invention is to add wetting agent in the reactant liquor, has improved the compatibility of slag and water, has increased solvability.
The invention has the advantages that, adopt the discarded object slag of steel mill to make desulfurizing agent, coupling by calcium magnesium in the slag is to realize high-efficiency desulfurization, adopt the solubilization of ultrasonic wave simultaneously to slag liquid, not only saved the expense of desulfurizing agent, reach refuse and utilize effectively and reasonably, and the equipment therefor floor space is little, simple to operation, avoided the characteristics of the easy fouling in absorption tower in the gypsum method simultaneously.Compare with traditional lime/lime stone-gypsum method, the present invention has effectively prevented the scale problems on absorption tower when guaranteeing that the sintering flue gas desulfurization rate reaches, reduced the floor space of equipment, reduce operating cost, improved the economic benefit of twice laid greatly.
Description of drawings
Fig. 1: be method one cocurrent cooling operation process flow diagram of the present invention;
Fig. 2: be method one counter-current operation process flow diagram of the present invention;
Fig. 3: be method two cocurrent cooling operation process flow diagram of the present invention;
Among the figure: 1 is flue gas, and 2 is the absorption tower, and 3 is the slag absorption liquid, 4 for purifying flue gas, and 5 is pump, and 6 are slag absorption rich solution, 7 is solid-liquid separator, and 8 is steel-making slag powder, and 9 is water, 10 is hydrolysis reactor, and 11 is ultrasonic wave solubilising device, and 12 is slag solubilising liquid, 13 is supernatant, and 14 is slag absorption liquid storage tank, and 15 is pump, 16 is sediment, and 17 is dewaterer, and 18 is gypsum.
The specific embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments:
Embodiment 1.
As shown in Figure 1, the SO of this technological process import sinter fume
2The way of contact with absorption liquid employing and stream.Sinter fume 1 (the SO of steel plant
2600mg/m3) 2 top enters and contacts with slag absorption liquid 3 and flow downward from the absorption tower, removes SO
2After purification flue gas 4 discharge from the bottom of tower and send into chimney 5 rows to atmosphere.Absorb SO in the flue gas
2After slag absorb rich solution 6 and enter solid-liquid separator 7, with the slag solubilising liquid of sending into from ultrasonic wave solubilising device 11 12 (wherein, iron and oxide thereof, inorganic content beyond the calcium magnesium is bigger, calcium magnesium total content 45%, 200 orders) after the mixing, precipitate and separate obtains supernatant 13 and enters slag absorption liquid storage tank 14, with pump 15 it is sent into the absorption tower as slag absorption liquid 3 afterwards.The sediment 16 that solid-liquid separator 7 produces is sent into dewaterer 17 and is dewatered, and obtains accessory substance gypsum 18 and discharges as cement material utilization.The slag that desulfurization is used obtains steel-making slag powder 8 through after grinding, and is introduced into hydrolysis reactor 10 and carries out preliminarily solubilised with water 9, imports ultrasonic wave solubilising device 11 afterwards.Through 50 watts/square centimeter, the ultrasonic wave effect of 20kHz is sent to solid-liquid separator 7 as slag solubilising liquid 12 after by solubilising.For increasing the dissolubility of slag, in hydrolysis reactor 10, add slag hydrolysis liquid and 1: 0.006 detergent alkylate naphthenic acid sodium (not shown) of wetting agent mass ratio.Wetting agent is not had specific (special) requirements, and the optional nothing corrosion kind of using always with industrial quarters gets final product.
In real process, absorb lean solution and be controlled between the pH6.8-7.2, absorb rich solution and be controlled at pH6.2-6.5.Absorption liquid can make solution, but most applications is the mixed liquor of suspension and emulsion.
Embodiment 2.
Technical process is substantially the same manner as Example 1, and different is that reflux type is adopted on absorption tower 2, as shown in Figure 2.Be flue gas 12 bottom enters from the absorption tower, in uphill process, contact the SO in the absorption flue gas with absorption liquid reverse flow from the top of tower spray
2After purification flue gas 4 discharge from cat head, send into chimney 5 and enter atmosphere.
Embodiment 3.
Present embodiment is the technical process of method two, and is substantially the same manner as Example 1, and different is to absorb rich solution elder generation precipitate and separate, and the supernatant that obtains absorbs rich solution with slag to be mixed, and the technology that recycles, as shown in Figure 3.The slag absorption rich solution 6 that promptly discharge 2 bottom from the absorption tower enters solid-liquid separator 7, and sediment 16 enters dewatering system and handles, and supernatant 13 enters slag absorption liquid storage tank 14, mixes the back with slag solubilising liquid at this and recycles as slag absorption liquid 3.
Claims (4)
1. the wet-type desulfuration method for steel scoria of a flue gas, the device that this method adopts comprises: absorption tower, solid-liquid separator, slag absorption liquid storage tank, dewaterer, slag ultrasonic wave solubilising device, pump and slag hydrolysis reactor is characterized in that comprising following process:
With powder particle diameter size order number is that 325 orders-100 purpose slag and water are 1 by mass ratio: the reaction that is hydrolyzed of 2.5-5.0 adding slag hydrolysis reactor, slag-metal reaction liquid adds slag ultrasonic wave solubilising device behind the hydrolysis, and add the wetting agent that comprises detergent alkylate naphthenic acid sodium by slag hydrolysis liquid and wetting agent mass ratio 1: 0.005-0.01 to this slag ultrasonic wave solubilising device, and slag-metal reaction liquid is increased dissolution process 0.2-3 minute with the ultrasonic wave of 0.01～50 watt/square centimeter of power density, handling back slag solubilising liquid adding solid-liquid separator mixes with slag absorption rich solution, in solid-liquid separator through sedimentation separation or centrifugation, the precipitum of solid-liquid separator bottom enters dewaterer and dewaters and obtain the accessory substance gypsum, the supernatant on solid-liquid separator top enters slag absorption liquid storage tank, then the slag absorption liquid is added the top, absorption tower with pump, flue gas feeds absorption tower and the execution of slag absorption liquid and stream or counter current contacting operation by the top or the bottom on absorption tower, the slag that has absorbed SO2 absorbs rich solution and enters solid-liquid separator by the bottom on absorption tower, through sedimentation separation or centrifugation, the purification flue gas of the desulfurization of being discharged by the bottom on absorption tower or top enters atmosphere through chimney.
2. by the wet-type desulfuration method for steel scoria of the described flue gas of claim 1, it is characterized in that, work as SO in the flue gas in the process
2Under the lower situation of concentration, adopt the cocurrent cooling operation mode; SO in flue gas
2Under the concentration condition with higher, adopt the operation reflux type.
3. the wet-type desulfuration method for steel scoria of a flue gas, the device that this method adopts comprises: absorption tower, solid-liquid separator, slag absorption liquid storage tank, dewaterer, slag ultrasonic wave solubilising device, pump and slag hydrolysis reactor is characterized in that comprising following process:
With powder particle diameter size order number is that 325 orders-100 purpose slag and water are 1 by mass ratio: the reaction that is hydrolyzed of 2.5-5.0 adding slag hydrolysis reactor, slag-metal reaction liquid adds slag ultrasonic wave solubilising device behind the hydrolysis, and add the wetting agent that comprises detergent alkylate naphthenic acid sodium by slag hydrolysis liquid and wetting agent mass ratio 1: 0.005-0.01 to this slag ultrasonic wave solubilising device, and slag-metal reaction liquid is increased dissolution process 0.2-3 minute with the ultrasonic wave of 0.01～50 watt/square centimeter of power density, handle back slag solubilising liquid and add slag absorption liquid storage tank as the slag absorption liquid, then the slag absorption liquid is added the top, absorption tower with pump, flue gas feeds absorption tower and the execution of slag absorption liquid and stream or counter current contacting operation by the top or the bottom on absorption tower, has absorbed SO
2Slag absorb rich solution and enter solid-liquid separator by the bottom on absorption tower, through sedimentation separation or centrifugation, the precipitum of solid-liquid separator bottom enters dewaterer and dewaters and obtain the accessory substance gypsum, the supernatant on solid-liquid separator top enters slag absorption liquid storage tank, mix as the slag absorption liquid to recycle with slag solubilising liquid in the slag absorption liquid storage tank, the purification flue gas of the desulfurization of being discharged by the bottom or the top on absorption tower enters atmosphere through chimney.
4. by the wet-type desulfuration method for steel scoria of the described flue gas of claim 3, it is characterized in that, work as SO in the flue gas in the process
2Under the lower situation of concentration, adopt the cocurrent cooling operation mode; SO in flue gas
2Under the concentration condition with higher, adopt the operation reflux type.
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| CN2008101533760A CN101428193B (en) | 2008-11-26 | 2008-11-26 | Wet-type desulfuration method for steel scoria with flue gas |
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| CN86102862A (en) * | 1986-04-19 | 1987-04-15 | 徐寿浩 | Carry out the external desulfurization of hot metal method with steel-making high-temperature liquid state slag |
| CN101235431A (en) * | 2008-03-05 | 2008-08-06 | 邯郸钢铁股份有限公司 | Convertor tapping washing fining furnace fast desulfurization method |
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| CN102225306A (en) * | 2011-04-20 | 2011-10-26 | 成都信息工程学院 | Slag-sodium alkali dual-alkali wet type flue gas desulfurization process |
| CN105013268A (en) * | 2014-04-30 | 2015-11-04 | 刘炎军 | Process system for improving dust removal, desulfurization and demercuration efficiency of boiler flue gas |
| CN108455678A (en) * | 2018-04-27 | 2018-08-28 | 北京科技大学 | The method that waste material combines the desulfurization of limestone/lime-gypsum method and prepares calcium ferrite |
| CN109092042A (en) * | 2018-08-30 | 2018-12-28 | 华电电力科学研究院有限公司 | It is a kind of that SO in flue gas is removed using steel slag2With SO3System and its working method |
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Effective date of registration: 20201125 Address after: Yang Gangju Dongshe town Tongzhou District 226344 Jiangsu city of Nantong Province Patentee after: Le'er Environmental Technology (Jiangsu) Co., Ltd Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |