CN101992017A - Device and method for treating sodium salt-containing desulfurization waste liquid in coking industry - Google Patents
Device and method for treating sodium salt-containing desulfurization waste liquid in coking industry Download PDFInfo
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- CN101992017A CN101992017A CN 201010285187 CN201010285187A CN101992017A CN 101992017 A CN101992017 A CN 101992017A CN 201010285187 CN201010285187 CN 201010285187 CN 201010285187 A CN201010285187 A CN 201010285187A CN 101992017 A CN101992017 A CN 101992017A
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- desulfurization
- gas desulfurization
- waste liquid
- power plant
- flue gas
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Abstract
The invention relates to the field of waste liquid treatment, in particular to a device and a method for treating sodium salt-containing desulfurization waste liquid in coking industry. The invention solves the problems of environmental pollution, influence on coke quality and high power plant flue gas desulfurization cost of the desulfurization waste liquid in the existing coking plant in a discharging mode. The device comprises a coke oven gas desulfurization device comprising a gas desulfurization tower, a circulating slot and the like, and a power plant flue gas desulfurization device comprising a flue gas desulfurization tower and the like. A shunting branch is connected with a pipe between the gas desulfurization tower and a regeneration tower. The other end of the shunting branch is communicated with a raw stock tank. The coke oven gas desulfurization waste liquid enters into the power plant flue gas desulfurization device through the shunting branch. The mixing ratio of the coke oven gas desulfurization waste liquid to the power plant desulfurization waste liquid is 1:15-20. The device can supply alkali source for the power plant; and secondary salt in the coking plant desulfurization liquid and SO2 undergo reaction, thereby improving the desulfurization efficiency of the original power plant, treating the waste liquid with the other waste in an innocent mode, solving the problem of environmental pollution due to the discharge of the desulfurization waste liquid, saving resources and reasonably using resources.
Description
Summary of the invention
The present invention relates to the liquid waste processing field, be specially treating apparatus and method that a kind of coking industry contains the sodium salt desulfurization waste liquor.
Background technology
At present, during the coke oven gas desulfurization of the big-and-middle-sized coking industry of China, great majority adopt wet oxidation method sulfur removal technologies, the composite catalyst of tannin extract+vanadium wherein, and soda ash provides alkali source, and air oxidation regeneration is a kind of of wet oxidation method sulfur removal technology.Follow some side reactions to take place in sweetening process, produce a certain amount of secondary salt, main component is Na
2S
2O
3And NaCNS, and after these secondary salts reach finite concentration, can worsen the coal gas desulfurization process, and reduce desulfuration efficiency, cause H in the coal gas
2S exceeds standard.Domestic most of coke-oven plant is not because the cost problem is established desulfurization waste liquor and carried the salt device, and many employings efflux a part of doctor solution and go coal yard to be sprayed onto in the coking coal, and the way of replenishing the new liquid of part configuration again solves the problem of secondary salt excessive concentration.But the waste liquid that effluxes can cause environmental pollution on the one hand, corrosion coal blending equipment, and sodium ion can cause coke quality and silica brick performance to reduce in the desulfurization waste liquor on the other hand, in addition, free sulphur in the doctor solution is finally got back to system again, and the load of coal gas desulfurization is strengthened, and has increased operating cost.
And that existing most of means of flue gas desulfurization of power plant employings is sodalime double alkali method (Na
2CO
3-Ca (OH)
2), adopt soda ash startup, soda to absorb SO
2, the method for acetylene sludge as recycling needs constantly to replenish alkali source in the process of desulfurization, and production cost is higher.
Summary of the invention
The present invention contains the sodium salt desulfurization waste liquor and adopts the mode of effluxing to have contaminated environment, etching apparatus and influence coke quality in order to solve existing coking industry, the high problem of while means of flue gas desulfurization of power plant operating cost, the treating apparatus and the method that provide a kind of coking industry to contain the sodium salt desulfurization waste liquor.
The present invention adopts following technical scheme to realize: coking industry contains the treating apparatus of sodium salt desulfurization waste liquor, comprise by coal gas desulfurization tower, circulating slot, regenerator and connecting successively with pipeline and the coke oven gas desulfurization device that constitutes, also comprise by fume desulfurizing tower, sedimentation basin, former stock tank and former stock pump and connect successively with pipeline and the means of flue gas desulfurization of power plant device that constitutes, innovative point of the present invention is to be connected with shunt pipe on the pipeline between waste liquid import of coal gas desulfurization tower and the regenerator waste liquid outlet, and the shunt pipe other end is communicated with the former stock tank of means of flue gas desulfurization of power plant device.
Measuring pump and control valve are housed on the described shunt pipe, are convenient to control the flow that desulphurization waste liquid of coke oven gas enters the means of flue gas desulfurization of power plant waste liquid.
Utilize said apparatus to finish the processing method that coking industry contains the sodium salt desulfurization waste liquor, the desulfurization waste liquor that is flowed out by the coke oven gas desulfurization device is in shunt pipe flows into the former stock tank of means of flue gas desulfurization of power plant device, and coke-oven plant's desulfurization waste liquor is 1: 15～20 with the mixed proportion that adds the power plant desulfurization waste liquid in the former stock tank.In this proportion, all can satisfy the requirement of means of flue gas desulfurization of power plant, this ratio is the applicant through repeatedly laboratory test and industrial test and summary of experience and obtains.
The present invention is different according to the composition of coke-stove gas and power-plant flue gas, and different in kind takes off H
2S and take off SO
2The technology difference, various technological parameter differences, the composition difference of doctor solution, but have a common ground in doctor solution, all to add some Na exactly
2CO
3, according to this principle, coke oven gas desulfurization liquid is mixed with power plant desulfurization liquid by a certain percentage, come along and take off SO
2, scheme of the present invention is the applicant through repeatedly laboratory test and industrial test and summary of experience and obtains, all obtained good effect from the laboratory lab scale to industrial test.
The present invention incorporates coke-oven plant's desulfurization waste liquor into power plant desulfurization liquid and carries out flue gas desulfurization, and because of its mixed liquor complicated component, reaction mechanism is also very complicated, does following analysis with regard to its main reaction mechanism:
(1) carbide slag reaction mechanism: key reaction is the SO in the flue gas
2Be dissolved in absorption liquid (Ca (OH) earlier
2Solution) in, be dissociated into H then
+And HSO
3 -:
The solubility of carbide slag is very low, and its solubilizing reaction formula is:
CaO+H
2O＝Ca(OH)
2
Ca(OH)
2(s)＝Ca
2++2OH
-
(2) in former stock tank, add coke-oven plant's desulfurization waste liquor in proportion, following reaction mainly take place:
Na
2CO
3+Ca(OH)
2＝CaCO
3↓+2NaOH
NaHCO
3+Ca(OH)
2＝CaCO
3↓+NaOH+H
2O
(3) in fume desulfurizing tower, because the generation of NaOH, to SO
2Affinity strong, reaction speed is fast, has increased reactive activity, has improved desulfuration efficiency.Because CO in the flue gas
2Concentration is SO up to more than 13%
2The 50-100 of concentration times, so PH 〉=9 at first are and CO
2Reaction, when PH＜9 just and SO
2Reaction, desulphurization reaction is as follows:
PH is main 8～12:
Ca(OH)
2+CO
2＝CaCO
3+H
2O
Na
2CO
3+CO
2+H
2O→2NaHCO
3
2NaOH+CO
2←→Na
2CO
3+H
2O
CaCO
3+SO
2＝＝＝CaSO
3+CO
2
Ca(OH)
2+SO
2＝CaSO
3+H
2O
When PH is low 5～8:
Na
2CO
3+H
2SO
3→Na
2SO
3+H
2O+CO
2
NaHCO
3+H
2SO
3→Na
2SO
3+H
2O+CO
2
CaCO
3+2SO
2+H
2O→Ca(HSO
3)
2+CO
2
CaSO
3+SO
2+H
2O＝Ca(HSO
3)
2
Na
2SO
3+SO
2+H
2O←→2NaHSO
3
(4) regenerative response: the suspension of calcium sulfite and sodium sulfite is mainly used in this method desulfurization, desulfurization generates very big calcium bisulfite and the sodium hydrogensulfite of solubility in tower, react with calcium hydroxide and calcium bisulfite, sodium hydrogensulfite at former stock tank again, the calcium sulfite of regenerating, sodium sulfite circulation desulfurization:
2NaHSO
3+Ca(OH)
2←→Na
2SO
3+CaSO
3↓+2H
2O
Na
2SO
3+Ca(OH)
2←→2NaOH+CaSO
3↓
Ca(OH)
2+Ca(HSO
3)
2＝2CaSO
3+2H
2O
(5) side reaction
Na
2SO
3+1/2O
2←→Na
2SO
4
CaSO
3+1/2O
2＝CaSO
4↓
2NaVO
3+Ca(OH)
2＝Ca(VO
3)
2↓+2NaOH
Ca(VO
3)
2+H
2SO
3＝CaSO
3↓+2HVO
3
According to above analysis, can draw: the component part of coke-oven plant's sodium method desulfurization waste liquor and the Ca (OH) of power plant desulfurization liquid to draw a conclusion
2Some chemical reactions take place, product all with SO
2Reaction, NaCO
3, NaHCO
3, NaOH is the activating agent of desulfurization, can provide the desulfurization alkali source for power plant desulfurization, and secondary salt NaCNS, the Na at coke-oven plant's sodium method desulfurization waste liquor end
2S
2O
3Hardly with Ca (OH)
2Reaction does not influence Ca (OH)
2Concentration.NaCNS, Na
2S
2O
3Can with HSO
3 -Reaction has improved the desulfuration efficiency of former power plant greatly.Realize the treatment of wastes with processes of wastes against one another and accomplish the harmless treatment of waste liquid, can kill two birds with one stone, both solved the problem of desulfurization waste liquor discharging environmental pollution, provide alkali source to power plant again, reduced the use of power plant's soda ash, economize on resources, turn waste into wealth, reached the reasonable resources utilization.Coking industry desulfurization waste liquor (sodium salt waste liquid) is incorporated the technical research of means of flue gas desulfurization of power plant system into, be domestic initiation, favorable economic benefit and economic benefit have been obtained, can solve the coking industry desulfurization waste liquor handles, not only reduced investment but also free from environmental pollution, have good economic benefit and social benefit, the industrial applications effect is remarkable, wide popularization and application in the worth same industry at home.
Description of drawings
Fig. 1 is the structural representation of device of the present invention;
Among the figure: 1-coal gas desulfurization tower; The 2-circulating slot; 3-coal gas regenerator; The 4-fume desulfurizing tower; The 5-sedimentation basin; The former stock tank of 6-; The former stock pump of 7-; The 8-pipeline; The 9-shunt pipe; The 10-measuring pump; The 11-control valve.
The specific embodiment
Coking industry contains the treating apparatus of sodium salt desulfurization waste liquor, as shown in Figure 1, comprise by coal gas desulfurization tower 1, circulating slot 2, regenerator 3 and connecting successively with pipeline and the coke oven gas desulfurization device that constitutes, also comprise by fume desulfurizing tower 4, sedimentation basin 5, former stock tank 6 and former stock pump 7 and connect successively with pipeline and the means of flue gas desulfurization of power plant device that constitutes, be connected with shunt pipe 9 on the pipeline 8 between 1 waste liquid import of coal gas desulfurization tower and regenerator 3 waste liquid outlets, shunt pipe 9 other ends are communicated with the former stock tank 7 of means of flue gas desulfurization of power plant device.Measuring pump 10 and control valve 11 are housed on the shunt pipe 9.
Utilizing said apparatus to finish the processing method that coking industry contains the sodium salt desulfurization waste liquor is to be flowed in the former stock tank of means of flue gas desulfurization of power plant devices through shunt pipe 9 by the desulfurization waste liquor that the coke oven gas desulfurization device flows out, and coke-oven plant's desulfurization waste liquor is 1: 15～20 with the mixed proportion that adds the power plant desulfurization waste liquid in the former stock tank 7.
In order further to prove effect of the present invention, the spy enumerates following industrial example:
There are three cover systems in former power plant desulfurization system, is generally two and opens one and be equipped with, and average every cover system adds 2 bags of soda ash every day, adds 4 bags of soda ash normal average every day.Every bag of 40kg adds alkali 160kg every day, could satisfy the technological requirement of the two alkaline process of calcium sodium.Composition Na according to coke-oven plant's doctor solution
2CO
3Content is at 4g/L, NaHCO
3More than 14g/L, other soda does not consider that doctor solution per ton contains more than the alkali 18kg, if every day 10 tons of sodium alkali desulfurization liquid are squeezed into the power plant desulfurization system, contains alkali 180kg approximately, can substitute the amount of 4 bags of alkali.In order to confirm this point, in the process of industrial test, power plant stops to add alkali, through two step-by-step tests, confirm power plant or else to add soda ash fully, so just can save the alkali source of power plant if 10 tons of coke-oven plant's desulfurization waste liquor average every days be sent to power plant continuously.If alkali is per ton by 2300 yuan, alkali expense: 0.16 * 365 * 2300=13.4 ten thousand yuan/year every year on average economizes in raw materials.
If coke-oven plant's desulfurization waste liquor has been sprayed onto coal yard, suspension sulphur and sodium salt have finally been got back to the coal-blending coking system again in the waste liquid, NaCNS in the waste liquid, Na2S2O3, suspension sulphur average content is respectively 150g/L, 250g/L, 0.7g/L, NaCNS wherein, Na2S2O3 content S is 40%, conversion S amount is 160g/L, by entering 10 tons every day, the sulfur content that enters is 160*10=1600Kg/d, by the amount 40% that changes sulphur in the coal gas over to, enter sulfur content 1600*40%=640Kg/d in the coal gas every day,, produce sulphur cream if sulphur in these coal gas is all reclaimed, need increase expense 1730*0.64=1107 unit/d, annual increase expense is ten thousand yuan of 1107*365=40.4.Create for two and make 53.8 ten thousand yuan of economic benefits.
If all incorporate the desulfurization waste liquor of 750,000 tons of/year coke-oven plants into the power plant desulfurization system, carry out flue gas desulfurization, every year can be less to more than 3650 ton of coal yard removal waste fluid, save certain energy consumption, and can alleviate the sodium salt high temperature pyrolysis time to charcoal reactivity, coke mechanical strength and coke structure injurious effects and blast furnace operating.Simultaneously, incorporate power plant desulfurization liquid into and carry out desulfurization, can improve SO in the flue gas
2Removal efficiency reduces the pollution sources that pollute urban atmosphere, for city " clear water blue sky " engineering is contributed.
Claims (3)
1. a coking industry contains the treating apparatus of sodium salt desulfurization waste liquor, comprise by coal gas desulfurization tower (1), circulating slot (2), regenerator (3) connects successively with pipeline and the coke oven gas desulfurization device that constitutes, also comprise by fume desulfurizing tower (4), sedimentation basin (5), former stock tank (6) and former stock pump (7) connect successively with pipeline and the means of flue gas desulfurization of power plant device that constitutes, it is characterized in that being connected with shunt pipe (9) on the pipeline (8) between coal gas desulfurization tower (1) waste liquid import and regenerator (3) waste liquid outlet, shunt pipe (9) other end is communicated with the former stock tank (7) of means of flue gas desulfurization of power plant device.
2. a kind of coking industry according to claim 1 contains the treating apparatus of sodium salt desulfurization waste liquor, it is characterized in that being equipped with on the shunt pipe (9) measuring pump (10) and control valve (11).
3. utilize as claimed in claim 1 or 2 device to finish the processing method that coking industry contains the sodium salt desulfurization waste liquor, the desulfurization waste liquor that it is characterized in that being flowed out by the coke oven gas desulfurization device is in shunt pipe (9) flows into the former stock tank (7) of means of flue gas desulfurization of power plant device, and coke-oven plant's desulfurization waste liquor is 1: 15～20 with the mixed proportion that adds the power plant desulfurization waste liquid in the former stock tank.
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|---|---|---|---|
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|---|---|---|---|
| CN 201010285187 CN101992017A (en) | 2010-09-13 | 2010-09-13 | Device and method for treating sodium salt-containing desulfurization waste liquid in coking industry |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105441686A (en) * | 2016-01-06 | 2016-03-30 | 湘潭大学 | Reducing method for lead dioxide in waste lead plaster |
| CN112537784A (en) * | 2020-12-16 | 2021-03-23 | 攀钢集团攀枝花钢钒有限公司 | System and method for extracting sodium thiocyanate from coal gas desulfurization solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402884A (en) * | 2008-11-16 | 2009-04-08 | 李大路 | Process and apparatus for removing and recovering sulphur in coke oven gas |
| CN101502754A (en) * | 2009-02-09 | 2009-08-12 | 河南省泰隆科技开发应用有限公司 | Dual alkali desulphurization energy-saving technique |
| CN201807283U (en) * | 2010-09-13 | 2011-04-27 | 太原煤气化股份有限公司焦化厂 | Treatment device for sodium salt-containing desulfuration waste liquid in coking industry |
-
2010
- 2010-09-13 CN CN 201010285187 patent/CN101992017A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402884A (en) * | 2008-11-16 | 2009-04-08 | 李大路 | Process and apparatus for removing and recovering sulphur in coke oven gas |
| CN101502754A (en) * | 2009-02-09 | 2009-08-12 | 河南省泰隆科技开发应用有限公司 | Dual alkali desulphurization energy-saving technique |
| CN201807283U (en) * | 2010-09-13 | 2011-04-27 | 太原煤气化股份有限公司焦化厂 | Treatment device for sodium salt-containing desulfuration waste liquid in coking industry |
Non-Patent Citations (1)
| Title |
|---|
| 《煤化工》 20091031 王平山，李久明，杨任全 以焦化氨为碱源用于锅炉烟道气脱硫的探讨 38-40 1-3 , 第5期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105441686A (en) * | 2016-01-06 | 2016-03-30 | 湘潭大学 | Reducing method for lead dioxide in waste lead plaster |
| CN112537784A (en) * | 2020-12-16 | 2021-03-23 | 攀钢集团攀枝花钢钒有限公司 | System and method for extracting sodium thiocyanate from coal gas desulfurization solution |
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Application publication date: 20110330 |