CN102949924B - Method for applying petrochemical exhausted lye to semidry-method flue gas desulfurization - Google Patents
Method for applying petrochemical exhausted lye to semidry-method flue gas desulfurization Download PDFInfo
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- CN102949924B CN102949924B CN201110255209.9A CN201110255209A CN102949924B CN 102949924 B CN102949924 B CN 102949924B CN 201110255209 A CN201110255209 A CN 201110255209A CN 102949924 B CN102949924 B CN 102949924B
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Abstract
The invention discloses a method for applying petrochemical exhausted lye to semidry-method flue gas desulfurization, belonging to the technical field of environmental protection. The method disclosed by the invention is characterized in that part or all of exhausted lye subjected to pretreatment replaces industrial water and is applied to a semidry-method desulfurization device for boiler flue gas, and injected to a desulfurizing absorption tower according to a required amount, wherein alkaline compounds such as Na2S, NaOH and/or Na2CO3 and the like of the exhausted lye fully react with SO2 in flue gas, then generated sulfur-containing compounds as heavy components are fed into a circulatory ash system and treated along with circulatory ash, and light components are discharged to a desulfurized ash silo of a power plant; and the desulfurization rate of externally-exhausted flue gas is greatly increased and can reach 70-99%, thereby achieving an effect of stable emission on standard. Meanwhile, the application amount of a desulfurizing agent can be saved, the influence of exhausted lye on a sewage treatment system is eliminated, effects of saving energy and reducing consumption are achieved, and the treatment of wastes with processes of wastes against one another is realized, therefore, the method has good economic and social benefits.
Description
Technical field
Petrochemical industry spent lye, for a method for semi-dry process flue gas desulphurization, belongs to environmental technology field, is specifically related to a kind of petrochemical industry spent lye for boiler smoke semi-dry desulphurization method.
Background technology
Produce supporting steam power plant with petrochemical industry and mostly adopt pulverized coal boiler, the flue gas of generation need through desulfurization process up to standard after discharge.Flue gas desulfurization technique is mainly absorbent or the adsorbent that utilizes various alkalescence, the SO in trapping flue gas
2make it to be converted into sulfur-containing compound stable and that easily machinery separates.On the whole, flue gas desulfurization technique can be divided into dry method, semidry method and wet method.Wherein Summary of Semi-dry Flue Gas Desulfurization, is that desulfurization absorption and product are processed and all under dry state, carried out, have flow process short, discharge, purify afterwards flue gas without sewage spent acid and be easy to the advantages such as exhaust diffusion, equipment corrosion be little.The conventional absorbent of flue gas desulfurization has lime stone, ammonia etc.In recent years, some alkaline waste waters are also usually used in flue gas desulfurization.The spent lye producing in petrochemical production process, mainly comprises the alkene spent lye of ethylene cracker generation and the spent lye that TOWER OUTLET IN VINYL CHLORIDE UNIT produces.Alkene spent lye is to adopt alkali wash to remove the CO in cracking gas
2, H
2the sour gas such as S produce.Wherein contain the Na generating in unreacted NaOH, alkaline cleaning procedure
2s, Na
2cO
3etc. component of inorganic salts, contain the organic matter such as part heavy constituent diene hydro carbons, aldehyde material in the cracking gas of alkali liquor absorption simultaneously; CO in the NaOH solution absorption direct chlorination unit of chlor-alkali plant TOWER OUTLET IN VINYL CHLORIDE UNIT employing 20% and the waste gas that oxychlorination unit produces
2with micro-HCl, in supplementing fresh alkali lye, produce a certain amount of VCM spent lye.The Na that contains micro-dichloroethanes and 2-6% in this spent lye
2cO
3, NaHCO
3mixture.
At present, alkene spent lye adopts wet oxidation process to process more, utilizes air, under certain temperature, pressure, the sulfide in spent lye is oxidized to thiosulfate, sulfate, and by other oxidation operation.But it is harsh that wet oxidation requires equipment material, and operation and maintenance cost is higher, and waste liquid after treatment also needs to enter sewage farm, downstream with acid neutralization.A large amount of SO that wet oxidation produces
4 2-with the Ca in the sewage of downstream
2+form CaSO
4hard scale, directly has influence on the operation of sewage disposal system; TOWER OUTLET IN VINYL CHLORIDE UNIT spent lye is because containing the Na of higher concentration
2cO
3, NaHCO
3, with the Ca in the middle and lower reaches sewage of sewage farm
2+form a large amount of CaCO
3dirt, has equally also affected the operation in sewage farm.
Liu Jingjin, Li Liqing, at " alkaline industrial waste water is for the desulfurization and dedusting technology of a coal-burning boiler " literary composition, have introduced a kind of method that adopts waste water of basic printing and dyeing to carry out coal-fired flue gas desulfurization.The method is utilized the wet dedusting system of former boiler, adopts waste water of basic printing and dyeing to remove the SO in coal-fired flue-gas as desulfurizing agent
2, desulfurization degree can reach 75%～95%.The method is wet type desulfurizing, and wet dedusting system takes up an area larger.
Dou Bo, in " application of alkaline industrial waste water in coal burning flue gas desulfurization " literary composition, has introduced a kind of fume wet type desulphurization technology.The outer row's of alumina producing alkaline industrial waste water is applied to the flue gas desulfurization of Industrial Boiler wet type Water Membrane Dedusting System, object is the treatment of wastes with processes of wastes against one another.Alkaline industrial waste water pH value for flue gas desulfurization and dedusting is generally 8.1～11.6, and basicity is (with Na
2o meter) be generally 40～670mg/L, can carry out flue gas desulfurization and dedusting simultaneously, desulfurization degree is generally 70%～80%.The method also exists wet dedusting system to take up an area larger defect.
Wang Yun, in " application of the treatment of wastes with processes of wastes against one another in flue gas desulfurization project " literary composition, has introduced and has utilized the alkaline waste water of printing and dyeing mill's discharge as desulfurizing agent, and the flue gas that boiler combustion is produced carries out desulfurization.That utilizes the introducing of textile and dyeing industry garden contains highly basic sewage as desulfurizing agent, adopts the boiler smoke formation convection current in hollow-spraying-tower mode and tower to realize the desulfurization processing to flue gas.Solid waste after precipitation carries out processed, and solid powder is directly given Building Materials Factory as brick-making raw material, and the waste water separating directly enters the original sewage treatment plant in industry park.This method is wet type desulfurizing, needs larger absorption tower, and the waste water producing also will further be processed.
Patent CN1102072 discloses a kind of industrial smoke sulfur dioxide removal method, comprise: vulcanized sodium absorption liquid is sent in absorption tower from upper end, absorption tower, send into from bottom, absorption tower containing industrial SO 2 fume, control outlet absorption liquid pH value 3.5～7.5, desulfurization degree is 98%.But the party's wet desulphurization owned by France, the handling problems of unresolved waste liquid.Patent CN101444699 discloses a kind of process and equipment that removes sulfur dioxide in flue gas with sodium sulfite, the method comprises the purified treatment, desulfurization, sodium hydrogensulfite thermal decomposition, the separation of sulfate, the electrolysis of sulfate of flue dust, makes desulfurizing agent in the desulfurizing tower that has three absorber portions in upper, middle and lower, carry out three grades of desulfurization with sodium sulfite solution.This invention can be carried out purified treatment to entering desulfurizing tower flue gas before, can absorb preferably the sulfur dioxide in flue gas.But the method technological process complexity, operational management difficulty is larger.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, the method of a kind of petrochemical industry spent lye for boiler smoke semi-dry desulphurization is provided, realize the treatment of wastes with processes of wastes against one another, both can improve smoke desulfurization efficiency, guarantee that (waste gas content of sulfur dioxide can remain on 600mg/Nm to the discharge of discharged gas fume stably reaching standard completely
3below), save partial desulfurization agent, can reduce again the independent disposal cost of spent lye, energy-saving and cost-reducing, also can eliminate spent lye and arrange the impact on sewage farm outward, effectively overcome the shortcomings such as wet desulphurization covers an area of, wastewater treatment cost of investment is large.
The technical solution adopted for the present invention to solve the technical problems is: a kind of petrochemical industry spent lye, for the method for semi-dry process flue gas desulphurization, is characterized in that comprising the following steps:
1, Spent caustic treatment: spent lye comprises the spent lye that alkene spent lye and TOWER OUTLET IN VINYL CHLORIDE UNIT produce, alkene spent lye separates and removes oily substance and suspension through gravitational settling 24～48h, the spent lye that TOWER OUTLET IN VINYL CHLORIDE UNIT produces is removed most of organic matter by rectifying or gas stripping process, and spent lye is dichloroethanes content≤1 μ g/g after pretreatment;
2, semi-dry process flue gas desulphurization: spent lye after pretreatment, in absorption tower, upper part sprays into absorption tower with spray nozzle; First boiler smoke enters dedusting in electrostatic precipitator, then passes into bottom, absorption tower, after accelerating, fully contacts from bottom to top with the spent lye that is spray form, carries out desulphurization reaction;
3, dedusting and Desulphurization Gui Ku: product enters desulfurizing dust-collector with flue gas self-absorption top of tower and carries out gas solid separation, light component in desulfurizing byproduct drains into power plant desulfurization ash storehouse, heavy constituent is back to bottom, absorption tower and repeats desulphurization reaction process, and flue gas enters chimney by air-introduced machine after deduster purifies.
Preferred version is:
Described alkene spent lye, through gravitational settling 30～40h, separates and removes oily substance and suspension.
In described semi-dry process flue gas desulphurization process, spray into spent lye in absorption tower in, spray into desulfurizer powder.
Described desulfurizing agent is calcium oxide or NaOH.
The flow of described boiler smoke is 40～50Nm
3/ h, spent lye straying quatity is 2.0～9.0t/h.
The straying quatity of described desulfurizing agent is 0～1.8t/h.
First spent lye is carried out to pretreatment, prevent spent lye coking and blocking nozzle or cause secondary pollution in boiler flue gas desulfurization process.Alkene spent lye is through gravitational settling 24～48h, and preferably 30～40h, separates and remove oily substance and suspension; The spent lye that TOWER OUTLET IN VINYL CHLORIDE UNIT produces is removed most of organic matter by the method such as rectifying or stripping, makes its concentration lower than 1 μ g/g.
According to semi-dry process flue gas desulphurization flow process, determine that pretreated spent lye adds mode and position.First boiler smoke enters in electrostatic precipitator, removes the most of dust in flue gas.The flue gas of discharging enters absorption tower after the Venturi tube structure of bottom, absorption tower accelerates, and in tower, flows from bottom to top.Pretreated spent lye is squeezed into absorption tower by a certain amount of by noncorrosive pump, from up to down sprays from spray thrower, directly contacts with the flue gas in turbulence state, and fully reaction reaches and removes SO in flue gas
2object.With the difference of spent lye straying quatity, desulfurized effect difference.Ensureing, on flue gas basis up to standard, can suitably to adjust spent lye consumption.
Product enters desulfurizing dust-collector with flue gas self-absorption top of tower and carries out gas solid separation, and desulfurizing byproduct drains into power plant desulfurization ash storehouse, and flue gas enters chimney by air-introduced machine after deduster purifies.
The design of the solution of the present invention based on such: petrochemical industry is containing in alkali waste water (comprising the spent lye that alkene spent lye and TOWER OUTLET IN VINYL CHLORIDE UNIT produce), outside the organic matters such as heavy constituent diene hydro carbons, aldehyde material, dichloroethanes and VCM spent lye, also have a large amount of NaOH, NaHCO
3, the Na that generates in alkaline cleaning procedure
2s, Na
2cO
3etc. component of inorganic salts, the desulfurizing agent that basic component wherein can be used as boiler smoke uses, and this point numerous inventors be verified.On the other hand, the method of common semi-dry process flue gas desulphurization is after desulfurizing agent water spray, to make leather hard, then spray in absorption tower with the state of leather hard powder, participate in the desulphurization reaction of flue gas, this process is to carry out on gas-solid surface, therefore floor space is little, equipment investment is little, and scheme of the present invention is to participate in directly spray into containing alkali waste water in desulphurization reaction in absorption tower, there is alkaline matter containing in alkali waste water on the one hand, can participate in desulphurization reaction, the more important thing is, this desulphurization reaction process is to react on gas-solid and solution-air two interfaces, thereby semi-dry desulphurization method is more outstanding relatively conventionally for desulfuration efficiency, can partly replace the left and right of the desulfurizing agent in common semi-dry desulphurization method even completely, and desulfurized effect is more obvious.This point can fully be proved in follow-up test.
Compared with prior art, the beneficial effect that a kind of petrochemical industry spent lye of the present invention has for the method for semi-dry process flue gas desulphurization is: this boiler fume desulfurizing method floor space is little, equipment investment cost is low, both can improve smoke desulfurization efficiency, guarantee the discharge of discharged gas fume stably reaching standard, by controlling spent lye addition, the SO in flue gas
2can be controlled in≤600mg/Nm of concentration of emission
3, save partial desulfurization agent, can reduce again the independent disposal cost of spent lye, the treatment of wastes with processes of wastes against one another, energy-saving and cost-reducing, also can eliminate spent lye and arrange the impact on sewage farm outward.
Brief description of the drawings
Fig. 1 is process chart of the present invention.
Below in conjunction with accompanying drawing 1, the present invention will be further described:
Detailed description of the invention
Embodiment 1
Alkene spent lye, through gravitational settling 24～48h, separates and removes oily substance and suspension.By spent lye after pretreatment and desulfurizing agent in absorption tower, upper position sprays into absorption tower with spray nozzle, meanwhile, the boiler smoke of removing most of dust in flue gas through electrostatic precipitation is passed into bottom, absorption tower, after the Venturi tube structure of bottom, absorption tower accelerates, enter absorption tower, in tower, flow from bottom to top.In this process, pretreated spent lye is squeezed into absorption tower by noncorrosive pump and spray nozzle, from up to down sprays from spray thrower, directly contacts with the flue gas in turbulence state, and fully reaction reaches and removes SO in flue gas
2object.
In this example, the flow of boiler smoke is 40～50Nm
3/ h, SO
2concentration is 2400～3700mg/Nm
3.When spent lye straying quatity is 2.0t/h, desulfurizing agent is selected calcium oxide, when consumption is 1.8t/h, and the SO in flue gas
2concentration of emission 600～780mg/Nm
3, desulfurization degree is 70%～80%.
Product after the desulphurization reaction of absorption tower enters desulfurizing dust-collector with flue gas self-absorption top of tower and carries out gas solid separation, and the light component in desulfurizing byproduct drains into power plant desulfurization ash storehouse, and Desulphurization color is Dark grey, and main component is Na
2s
2o
35H
2o, Na
2sO
3, Na
2cO
3h
2o, density is 0.6473Kg/dm
3, heavy constituent is back to bottom, absorption tower and repeats desulphurization reaction process, and flue gas enters chimney by air-introduced machine after deduster purifies.
Embodiment 2
Boiler smoke SO in this example
2concentration is 2100～3900mg/Nm
3.When spent lye straying quatity is 4.0t/h, desulfurizing agent is selected NaOH, when consumption is 1.5t/h, and the SO in flue gas
2concentration of emission 500～600mg/Nm
3, desulfurization degree is 75%～85%.Desulphurization color is Dark grey, and main component is Na
2s
2o
35H
2o, Na
2sO
3, Na
2cO
3h
2o, density is 0.7626Kg/dm
3.Other method step is with embodiment 1.
Embodiment 3
In this example, be the spent lye that TOWER OUTLET IN VINYL CHLORIDE UNIT produces containing alkali waste water, remove most of organic matter by rectifying or gas stripping process.After pretreatment, be less than or equal to 1 μ g/g containing the dichloroethanes content of alkali waste water.
Passing into boiler fuel flow to bottom, absorption tower is 40～50Nm
3/ h, SO
2concentration is 2600～4300mg/Nm
3.In by absorption tower, the spent lye straying quatity that sprays into of top is 6.0t/h, when the sodium hydroxide concentration spraying into is 0.8t/h, the SO in flue gas
2concentration of emission 400～500mg/Nm
3, desulfurization degree is 80%～90%.
Desulphurization color is Dark grey, and main component is Na
2s
2o
35H
2o, Na
2sO
3, Na
2cO
3h
2o, density is 0.8434Kg/dm
3.Other method step is with embodiment 1.
Embodiment 4
Alkene spent lye, through gravitational settling 30～40h, separates and removes oily substance and suspension.By spent lye after pretreatment in absorption tower, upper position sprays into absorption tower with spray nozzle.Meanwhile, the boiler smoke of removing most of dust in flue gas through electrostatic precipitation is passed into bottom, absorption tower, after the Venturi tube structure of bottom, absorption tower accelerates, enter absorption tower, in tower, flow from bottom to top.Pretreated spent lye is squeezed into absorption tower by noncorrosive pump, from up to down sprays from spray thrower, directly contacts with the flue gas in turbulence state, and fully reaction reaches and removes SO in flue gas
2object.
In this example, boiler fuel flow is 40～50Nm
3/ h, SO
2concentration is 2500～4100mg/Nm
3.Spent lye straying quatity is 9.0t/h, does not add desulfurizing agent, the SO in flue gas
2concentration of emission 60～200mg/Nm
3, desulfurization degree is 90%～99%.
Product after the desulphurization reaction of absorption tower enters desulfurizing dust-collector with flue gas self-absorption top of tower and carries out gas solid separation, and the light component in desulfurizing byproduct drains into power plant desulfurization ash storehouse, and Desulphurization color is Dark grey, and main component is Na
2s
2o
35H
2o, Na
2sO
3, Na
2cO
3h
2o, density is 0.8779Kg/dm
3, heavy constituent is back to bottom, absorption tower and repeats desulphurization reaction process, and flue gas enters chimney by air-introduced machine after deduster purifies.
The above, be only preferred embodiment of the present invention, is not the restriction of invention being made to other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (1)
1. petrochemical industry spent lye, for a method for semi-dry process flue gas desulphurization, is characterized in that comprising the following steps:
1.1, Spent caustic treatment: spent lye comprises the spent lye that alkene spent lye and TOWER OUTLET IN VINYL CHLORIDE UNIT produce, alkene spent lye separates and removes oily substance and suspension through gravitational settling 30～40h, the spent lye that TOWER OUTLET IN VINYL CHLORIDE UNIT produces is removed most of organic matter by rectifying or gas stripping process, and spent lye is dichloroethanes content≤1 μ g/g after pretreatment;
1.2, semi-dry process flue gas desulphurization: spent lye after pretreatment, in absorption tower, upper part sprays into absorption tower with spray nozzle; First boiler smoke enters dedusting in electrostatic precipitator, then passes into bottom, absorption tower, after accelerating, fully contacts from bottom to top with the spent lye that is spray form, carries out desulphurization reaction;
1.3, dedusting and Desulphurization Gui Ku: product enters desulfurizing dust-collector with flue gas self-absorption top of tower and carries out gas solid separation, light component in desulfurizing byproduct drains into power plant desulfurization ash storehouse, heavy constituent is back to bottom, absorption tower and repeats desulphurization reaction process, and flue gas enters chimney by air-introduced machine after deduster purifies;
In semi-dry process flue gas desulphurization process described in step 1.2, spray into spent lye in absorption tower in, spray into desulfurizer powder;
Described desulfurizing agent is calcium oxide or NaOH;
The flow of described boiler smoke is 40～50Nm
3/ h, spent lye straying quatity is 2.0～9.0t/h;
The straying quatity of described desulfurizing agent is 0～1.8t/h.
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Cited By (2)
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| CN108097008A (en) * | 2018-01-26 | 2018-06-01 | 黄石新泰碱业有限公司 | A kind of method and device that flue gas desulfurization is carried out using vulcanized sodium production solid waste |
| CN108178471A (en) * | 2018-01-26 | 2018-06-19 | 黄石新泰碱业有限公司 | A kind of method and device of vulcanized sodium production solid waste comprehensive utilization |
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| CN103239985B (en) * | 2013-05-14 | 2016-04-20 | 中国环境科学研究院 | Efficient fuel coal flue gas desulfurizing and hydrargyrum-removing method and device thereof |
| CN104353351B (en) * | 2014-12-02 | 2016-08-17 | 成都华西堂投资有限公司 | A kind of by converting waste caustic soda for the industrialized process for preparing of sodium bicarbonate in gas cleaning |
| CN109824285B (en) * | 2017-11-23 | 2020-08-04 | 湖南昌迪环境科技有限公司 | Cement flue gas desulfurizer and application thereof |
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