CN101143293A - Deodorant waste lye absorbing treating smoke method - Google Patents

Deodorant waste lye absorbing treating smoke method Download PDF

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Publication number
CN101143293A
CN101143293A CNA2006100477938A CN200610047793A CN101143293A CN 101143293 A CN101143293 A CN 101143293A CN A2006100477938 A CNA2006100477938 A CN A2006100477938A CN 200610047793 A CN200610047793 A CN 200610047793A CN 101143293 A CN101143293 A CN 101143293A
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China
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absorption
gas
flue gas
waste lye
accordance
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CNA2006100477938A
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CN101143293B (en
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韩建华
朱峰
赵景霞
回军
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention relates to a method of absorbing and treating gases by using deodorization waste lye. The invention uses deodorization waste lye processed wet air oxidation treatment to absorb sulfur dioxide, dust and nitrogen oxides in the gas. The invention uses two-stage absorption mode, and the forepart uses the absorption liquid discharged in posterior part to contact directly with the gas to reduce gas temperature, and at the same time to remove part of the pollutants in the gas. The posterior part uses deodorization waste lye as absorption liquid to contact with the cooled gas in the forepart, and the absorption pollutants in this stage contains sulfoxides or nitrogen oxides, and the purified gas can be released. The removal efficiency of sulfur dioxide and dust processed treatment by the invention can be achieved above 90 percent, and the removal efficiency of nitrogen oxides can be achieved above 40 percent. The method not only can effectively purify the gas, but also can effectively utilize waste lye. The invention has the advantages of that the method is extremely stable, is not easy to scale, has low investment, simple operation, low operation cost and so on.

Description

The method of deodorant waste lye absorbing treating smoke
Technical field
The present invention relates to a kind of method of utilizing deodorant waste lye (as liquid hydrocarbon alkali refining deodorant waste lye, gasoline alkali refining deodorant waste lye, ethene alkali refining deodorant waste lye) absorbing treating smoke.Relate in particular to the deodorant waste lye of a kind of utilization after wet oxidation is handled) absorb the method for sulfur dioxide in flue gas, flue dust, nitrogen oxide.
Background technology
The employed fuel of coal-burning boiler and oil burning boiler can produce pollutants such as sulfur dioxide, flue dust, nitrogen oxide in combustion process, if do not handled, these pollutants in atmosphere, will produce serious pollution with fume emission to atmosphere.Some other industrial plants as fluidized catalytic cracker, catalyst regeneration device, sulfuric acid production plant etc., all can be discharged the waste gas that contains pollutants such as sulfur dioxide, and these waste gas are identical with boiler smoke, all are serious atmosphere pollutions.
The present common processing sulfur method of this part flue gas is had dry method, wet method, semidry method, and wherein wet desulphurization technology is the most ripe, and flue gas desulfurization technique is also many based on lime stone-gypsum method both at home and abroad.Its principle mainly is that flue gas is drawn from boiler, lowers the temperature through entering heat exchanger after the deduster dedusting, and the cooling back enters absorber by the air blast supercharging.As absorbent, generate two water calcium sulfites with the sulfur in smoke reaction with lime stone slurry in absorber, and go into force air oxidation generation calcium sulphate dihydrate at slurries pond pucking, technical process such as process concentrates, dehydration obtain by-produced gypsum.This processing method, the first, because the solubility of calcium salt in water is less, the easy fouling of equipment is stopped up; The second, the processing of desulfurization product is cumbersome, makes whole technology more complicated, and pulping equipment is huge, the operating cost height, and floor space and investment are bigger; The 3rd, lime stone-gypsum method is release of carbon dioxide (greenhouse gases) in absorbing treating smoke; The 4th, lower the temperature owing to before flue gas enters absorber, will be introduced into heat exchanger, and exhaust gas volumn is bigger usually, the heat exchanger overall heat-transfer coefficient is lower again, makes the needed heat exchange area of heat exchanger bigger, and therefore big operating cost of investment is higher.
The spent lye that contains inorganic sulphide, organic sulfur compound is discharged in oil product alkali refining unit in petroleum refining and petrochemical production process.This part spent lye is after wet oxidation is handled, and the content of sulfide can be reduced to less than 5mg/L from 5000~150000mg/L.But deodorant waste lye need add acid usually and carry out just sending sewage treatment plant further to handle after the acidifying neutralization because pH value is higher.
CNl393281A will contain organic hydrochlorate or organic acid industrial wastewater, waste residue adds in lime (stone) the wet flue gas desulfurization system, to improve lime (stone) utilization rate, and utilize refuse, but still based on lime (stone) wet flue gas desulfurization, its intrinsic deficiency fails to solve.
Summary of the invention
At the deficiencies in the prior art, the invention provides the method that a kind of smoke absorption is handled, utilize deodorant waste lye absorbing treating smoke, can absorb simultaneously sulfur in smoke, flue dust, nitrogen oxide, and not produce carbon dioxide (greenhouse gases).This method efficient stable, less scaling, small investment, easy and simple to handle and operating cost is low, handle the back flue gas and reach discharge standard.Simultaneously deodorant waste lye is carried out effective utilization, saved the acid that is used for acidifying and deodorant waste lye on the one hand, saved the alkali that is used for the smoke absorption processing on the other hand.And when efficiently solving the flue gas heat exchange cooling, heat transfer efficiency is low, the problem that equipment cost is high.
Deodorant waste lye absorbing treating smoke method of the present invention specifically comprises following process:
(1) will carry out the wet oxidation deodorization from the spent lye that industries such as petroleum refining, petrochemical industry produce and handle, be sulphite and/or sulfate with wherein sulfide oxidation;
(2) deodorant waste lye that obtains adopts two sections absorption patterns to carry out gas cleaning and handles as the gas cleaning absorbent.
Two sections absorption patterns described in the step (2) are first section: the absorption liquid of second section discharging directly contacts with flue gas, to reduce flue-gas temperature, removes wherein part pollutant simultaneously; Second section: the deodorant waste lye that step (1) obtains with contact through the flue gas after first section cooling, absorb the pollutant comprise oxysulfide or nitrogen oxide, the flue gas after being purified discharging.
In petroleum refining and the petrochemical industry industry, generation for pollutants such as sulfur dioxide in the quality that guarantees product and the use of control product, carry out alkali refining for the sulfur content high product, as liquid hydrocarbon alkali refining deodorant waste lye, gasoline alkali refining deodorant waste lye, ethene alkali refining deodorant waste lye etc. one or more.Inorganic sulphide and organic sulfur compound content are higher in the spent lye of discharging in this process.The spent lye deodour method adopts the wet oxidation method, and after oxidation deodorizing was handled, the content of sulfide can be reduced to less than 5mg/L from 5000~150000mg/L, but the deodorant waste lye pH value is higher, and basicity (NaOH mass fraction) is generally 2%~5%.The wet oxidation of spent lye is the knowledge of this area, as wet oxidation method that CN98121081.3 introduced etc.
Flue gas from boiler produces wherein contains sulfur dioxide 100~20000mg/m 3, flue dust 100~2000mg/m 3, flue gas 100~3000 mg/m of nitrogen oxide 3Flue gas adopts two sections absorption techniques of the present invention after dedusting and supercharging, two sections absorptions can be adopted various conventional absorber forms, as plate column, and packed tower, spray column, bubble tower etc.Can adopt vertical absorber form, also can adopt horizontal absorber form.When adopting vertical absorber, flue gas and absorption liquid can adopt counter current contacting mode (flue gas flows from bottom to up, and absorption liquid flows from top to bottom); When adopting horizontal absorber, flue gas and absorption liquid can adopt the cross-flow way of contact (flue gas flows from a side direction opposite side, and absorption liquid flows from the top down).First section absorption liquid that adopts second section (back segment) to discharge for (leading portion) is absorption liquid, directly contact with flue gas, mainly act as the master with the cooling dedusting, the absorption liquid that utilizes second section discharge is to the flue gas dedusting of lowering the temperature, and sulfur in smoke and nitrogen dioxide are carried out preliminary absorption.First section is provided with the absorption liquid closed circuit, and cooling systems such as heat exchanger are set on closed circuit.The absorption liquid of first section discharge enters the sewage-farm or aftertreatment device is further handled.Second section is absorption liquid with the deodorant waste lye, with the cooling after flue gas directly contact, based on absorption, utilize deodorant waste lye that pollutants such as sulfur in smoke and nitrogen dioxide are absorbed.Second section also can be provided with the circulating absorption solution closed circuit, to adjust liquid-gas ratio, improves the purification assimilation effect.
First section in two sections absorption patterns can be 1 absorption reaction district, also can be the absorption reaction district of 2~5 parallel connections.Second section in two sections absorption patterns can be 1 absorption reaction district, also can be 2~6 series connection and/or absorption reaction district in parallel.Absorption reaction district in parallel refers to that flue gas enters different absorption reaction districts side by side, and the absorption reaction district of series connection refers to that flue gas enters different absorption reaction districts successively.When in each section a plurality of absorption reactions district being set, the structure in each absorption reaction district and operating condition can be identical, also can be different.The concrete quantity in absorption reaction district can be determined according to the flow of flue gas and the factors such as manufacturing processing of equipment.
The operating condition in each absorption reaction district in two sections absorption processes, those skilled in the art can require to determine according to character, the gas cleaning of flue gas.In general, the condition in each absorption reaction district is: in first section absorption process, the control exit gas temperature is 60~120 ℃, and the flue gas air speed is 300~3000h -1, liquid-gas ratio is 0.01~0.1L/m 3, the relief liquor pH value is 3~10, is preferably 4~8; In second section absorption process, the flue gas air speed is 200~2500h -1, liquid-gas ratio is 1~10L/m 3, the exhanst gas outlet temperature is 20~80 ℃, preferred 40~70 ℃.The removal efficiency of handling back sulfur dioxide in flue gas and flue dust can reach more than 90%, and removal efficiency of nitrogen oxides can reach more than 30%.Flue gas after the processing can be directly by smoke stack emission after heating up.
The inventive method is utilized deodorant waste lye absorbing treating smoke, can absorb simultaneously sulfur in smoke, flue dust, nitrogen oxide, and do not produce carbon dioxide (greenhouse gases), this method efficient stable, less scaling, small investment, easy and simple to handle and operating cost is low, handle the back flue gas and reach discharge standard.Simultaneously deodorant waste lye is carried out effective utilization, saved the acid that is used for acidifying and deodorant waste lye on the one hand, saved the alkali that is used for the smoke absorption processing on the other hand.The inventive method adopts the liquid phase heat exchanger can realize the cooling problem of flue gas easily, with flue gas cool-down with remove sulfur dioxide, flue dust, nitrogen oxide and carry out simultaneously in absorber.Increased the heat transfer coefficient of heat exchanger, the cost of investment and smoke treatment is reduced.
Description of drawings
Fig. 1 is the horizontal process flow diagram of the inventive method.
Fig. 2 is the vertical process flow diagram of the inventive method.
The specific embodiment
Further specify technical scheme of the present invention below in conjunction with accompanying drawing.
The flue gas that boiler is discharged enters the air blast supercharging after the deduster dedusting, flue gas 4 and deodorant waste lye 3 enter respectively to absorb in the absorber 1 and react after the supercharging.React with sulfur dioxide and nitrogen dioxide in NaOH in the deodorization alkali lye 3 and the flue gas 4, making Sulphur Dioxide wherein is sodium sulfite and/or sodium hydrogensulfite and/or sodium sulphate, make nitrogen dioxide be converted into sodium nitrate, flue dust is left in the absorption liquid.The removal efficiency of handling back sulfur dioxide and flue dust can reach more than 90%, and removal efficiency of nitrogen oxides can reach more than 30%.Flue gas after the processing is discharged from absorber 1 outlet, can be directly by smoke stack emission after the intensification.
The inlet amount of deodorant waste lye 3 is decided by the concentration and the removal efficiency index of pollutant in the flue gas 4.The absorption liquid temperature can be controlled by control absorber leading portion absorption liquid internal circulating load in the absorber 1.The absorption liquid pH value can be controlled by the control inlet amount in the absorber 1.The removal efficiency of sulfur dioxide in flue gas and nitrogen dioxide can be controlled by control absorber 1 back segment absorption liquid internal circulating load.Reacted absorption liquid leading portion from absorber 1 is drawn, and cools off through cooler 2, and a cooling back absorption liquid part reenters absorber 1 leading portion, and another part enters sewage-farm or aftertreatment device.
Further specify technical scheme of the present invention by the following examples, every section is adopted an absorption reaction district.In conjunction with this area general knowledge, adopt in every section the mode of operation in a plurality of absorption reactions district can be easy to implement.Embodiment adopts the technological process of Fig. 1.
Embodiment 1
190 ℃ of flue gases that oil burning boiler produces are through after the dedusting, and wherein containing sulfur dioxide is 3250mg/m 3Flue dust is 305mg/m 3Nitrogen oxide is 610mg/m 3Ethene alkali refining deodorization alkali lye in the petrochemical production process, 25 ℃ of temperature, wherein COD is 4000mg/L; Sulfide is 5mg/L; Basicity (NaOH mass fraction) is 3%.Under following treatment conditions, through PROCESS FOR TREATMENT of the present invention.
In first section (leading portion) absorption process, controlling first section exit gas temperature is 60 ℃, and the flue gas air speed in first section absorption is 1500 H-1, liquid-gas ratio is 0.05, the relief liquor pH value is 5.5.Flue gas air speed during second section (back segment) absorbs is 1000h -1, liquid-gas ratio is 4, and the exhanst gas outlet temperature is 50 ℃, and the pH value of circulating absorption solution is 6 in second section.
Containing sulfur dioxide in the flue gas after handling is 300mg/m 3, flue dust is 30mg/m 3, nitrogen oxide is 360mg/m 3, after the intensification by smoke stack emission.The absorption liquid of discharging is sent into sewage treatment plant and is further handled.
Embodiment 2~5
Adopt different technology conditions, handle the flue gas of variable concentrations, its condition and result see Table 1.As can be seen from Table 1, the inventive method can be utilized the deodorant waste lye after wet oxidation is handled, and " treatment of wastes with processes of wastes against one another " handles the various flue gases that contain pollutants such as sulfur dioxide, flue dust, nitrogen oxide.The entire process perfect technology is handled the back flue gas and can be reached discharge standard.
Table 1 embodiment 2~5 treatment conditions and result
Example 2 Example 3 Example 4 Example 5
The content of pollutant in the flue gas Sulfur dioxide mg/m 3 3750 2520 4970 12850
Flue dust mg/m 3 410 260 450 620
Nitrogen oxide mg/m 3 530 480 640 690
Deodorant waste lye is formed Basicity % 3.0 4.2 3.8 3.5
First section absorbs processing Exhanst gas outlet temperature ℃ 60 80 50 100
The flue gas air speed, h -1 1500 1200 1350 2800
Liquid-gas ratio, L/m 3 0.05 0.08 0.03 0.09
The relief liquor pH value 5 4 6 5
Second section absorbs processing The flue gas air speed, h -1 1200 1000 1150 1400
Liquid-gas ratio, L/m 3 4 8 6 10
The pH value of circulating absorption solution 6 5 7 6
Flue-gas temperature ℃ 50 50 35 65
Handle the content of pollutant in the flue gas of back Sulfur dioxide mg/m 3 360 230 420 480
Flue dust mg/m 3 37 24 40 53
Nitrogen oxide mg/m 3 302 276 376 398

Claims (12)

1. the method for a deodorant waste lye absorbing treating smoke comprises following process:
(1) spent lye being carried out the wet oxidation deodorization and handle, is sulphite and/or sulfate with wherein sulfide oxidation;
(2) deodorant waste lye that obtains adopts two sections absorption patterns to carry out gas cleaning and handles as the gas cleaning absorbent;
Two sections absorption patterns described in the step (2) are first section: the absorption liquid of second section discharging directly contacts with flue gas, to reduce flue-gas temperature, removes wherein part pollutant simultaneously; Second section: the deodorant waste lye that step (1) obtains with contact through the flue gas after first section cooling, absorb the pollutant comprise oxysulfide or nitrogen oxide, the flue gas after being purified discharging.
2. in accordance with the method for claim 1, it is characterized in that described spent lye comes from petroleum refining and the petrochemical industry industry.
3. according to claim 1 or 2 described methods, it is characterized in that described spent lye source comprises liquid hydrocarbon alkali refining deodorant waste lye, gasoline alkali refining deodorant waste lye or ethene alkali refining deodorant waste lye.
4. in accordance with the method for claim 1, it is characterized in that it is plate column that the absorber form is adopted in described two sections absorptions, packed tower, spray column, or bubble tower.
5. according to claim 1 or 4 described methods, it is characterized in that described two sections absorption absorbers adopt vertical absorber form, or adopt horizontal absorber form.
6. in accordance with the method for claim 5, when it is characterized in that the vertical absorber of described employing, flue gas and absorption liquid adopt the counter current contacting mode; When adopting horizontal absorber, flue gas and absorption liquid adopt the cross-flow way of contact.
7. in accordance with the method for claim 1, it is characterized in that described first section is provided with the absorption liquid closed circuit, and heat exchanger is set on closed circuit.
8. in accordance with the method for claim 1, it is characterized in that described second section is provided with the circulating absorption solution closed circuit,, improve the purification assimilation effect to adjust liquid-gas ratio.
9. in accordance with the method for claim 1, it is characterized in that in described first section absorption process that the control exit gas temperature is 60~120 ℃, the flue gas air speed in first section absorption reaction district is 300~3000h -1, liquid-gas ratio is 0.01~0.1L/m 3, the relief liquor pH value is 3~10.
10. in accordance with the method for claim 1, the flue gas air speed that it is characterized in that described second section absorption reaction district is 200~2500h -1, liquid-gas ratio is 1~10L/m 3, the exhanst gas outlet temperature is 20~80 ℃.
11. in accordance with the method for claim 1, it is characterized in that first section in described two sections absorption patterns is 1 absorption reaction district, perhaps is the absorption absorption reaction district of 2~5 parallel connections.
12. in accordance with the method for claim 1, it is characterized in that second section in described two sections absorption patterns is 1 absorption reaction district, perhaps is 2~6 series connection and/or absorption reaction district in parallel.
CN2006100477938A 2006-09-15 2006-09-15 Method for deodorant waste lye for absorbing treating smoke Active CN101143293B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102949924A (en) * 2011-08-31 2013-03-06 中国石油化工股份有限公司 Method for applying petrochemical exhausted lye to semidry-method flue gas desulfurization
CN103865581A (en) * 2012-12-11 2014-06-18 中国石油化工集团公司 Scale inhibitor for inhibiting scale formation on flue gas turbine blade
CN107008106A (en) * 2016-01-27 2017-08-04 Aws有限公司 Apparatus and method for making gas and liquid formation contact
CN108892279A (en) * 2018-08-06 2018-11-27 陈式好 A kind of liquid waste treating apparatus

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1117664B (en) * 1977-01-14 1986-02-17 Italsider Spa METHOD FOR THE ABATEMENT OF SULFUR DIOXIDE
DE3818255C1 (en) * 1988-05-28 1989-10-19 Saacke Gmbh & Co Kg, 2800 Bremen, De Process for the desulphurisation of flue gas and reactor usable for this
CN2635194Y (en) * 2003-08-26 2004-08-25 天津市东方暖通设备股份合作公司 Spent alkaline liquid desulfur reaction tower
CN1272088C (en) * 2004-08-24 2006-08-30 北京中科通用能源环保有限责任公司 Method of proceeding desulfurzation of smoke using waste alkali slag

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102949924A (en) * 2011-08-31 2013-03-06 中国石油化工股份有限公司 Method for applying petrochemical exhausted lye to semidry-method flue gas desulfurization
CN102949924B (en) * 2011-08-31 2014-11-26 中国石油化工股份有限公司 Method for applying petrochemical exhausted lye to semidry-method flue gas desulfurization
CN103865581A (en) * 2012-12-11 2014-06-18 中国石油化工集团公司 Scale inhibitor for inhibiting scale formation on flue gas turbine blade
CN103865581B (en) * 2012-12-11 2016-01-13 中国石油化工集团公司 A kind of antisludging agent suppressing turbine blade fouling
CN107008106A (en) * 2016-01-27 2017-08-04 Aws有限公司 Apparatus and method for making gas and liquid formation contact
CN107008106B (en) * 2016-01-27 2021-10-15 洛拉技术股份公司 Apparatus and method for bringing a gas and a liquid into contact
CN108892279A (en) * 2018-08-06 2018-11-27 陈式好 A kind of liquid waste treating apparatus

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