CN102949924A - 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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- CN102949924A CN102949924A CN2011102552099A CN201110255209A CN102949924A CN 102949924 A CN102949924 A CN 102949924A CN 2011102552099 A CN2011102552099 A CN 2011102552099A CN 201110255209 A CN201110255209 A CN 201110255209A CN 102949924 A CN102949924 A CN 102949924A
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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
A kind of petrochemical industry spent lye is used for the method for semi-dry process flue gas desulphurization, belongs to environmental technology field, is specifically related to a kind of petrochemical industry spent lye and is used 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 needs discharging after the desulfurization processing is up to standard.Flue gas desulfurization technique mainly is absorbent or the adsorbent that utilizes various alkalescence, captures the SO in the flue gas
2Make it to be converted into the sulfur-containing compound that stable and easy machinery separates.On the whole, flue gas desulfurization technique can be divided into dry method, semidry method and wet method.Summary of Semi-dry Flue Gas Desulfurization wherein is that desulfurization absorption and product are processed all and carried out under the state of doing, have flow process short, discharge, purify rear flue gas without the sewage spent acid and be easy to the advantages such as exhaust diffusion, equipment corrosion be little.Flue gas desulfurization absorbent commonly used has lime stone, ammonia etc.In recent years, some alkaline waste waters also are usually used in flue gas desulfurization.The spent lye that produces in the 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.The alkene spent lye is that the employing alkali wash removes the CO in the cracking gas
2, H
2The sour gas such as S produce.Wherein contain the Na that generates in unreacted NaOH, the alkaline cleaning procedure
2S, Na
2CO
3Etc. component of inorganic salts, contain simultaneously the organic matters such as a part restructuring minute diene hydro carbons, aldehyde material in the cracking gas of alkali liquor absorption; CO in the waste gas that the NaOH solution absorption direct chlorination unit of chlor-alkali plant TOWER OUTLET IN VINYL CHLORIDE UNIT employing 20% and oxychlorination unit produce
2With micro-HCl, when replenishing 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, the alkene spent lye adopts wet oxidation process to process more, namely utilizes air, under certain temperature, pressure, the sulfide in the spent lye is oxidized to thiosulfate, sulfate, and with other oxidation operation.But it is harsh that wet oxidation requires equipment material, and operation and maintenance cost is higher, and the waste liquid after processing also needs to enter the sewage-farm, downstream with the 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; The 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 have introduced a kind of method that adopts waste water of basic printing and dyeing to carry out coal-fired flue gas desulfurization at " alkaline industrial waste water is used for the desulfurization and dedusting technology of a coal-burning boiler " literary composition.The method is utilized the wet dedusting system of former boiler, adopts waste water of basic printing and dyeing to remove SO in the 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 has introduced a kind of fume wet type desulphurization technology in " application of alkaline industrial waste water in coal burning flue gas desulfurization " literary composition.The alkaline industrial waste water that alumina producing is effluxed is applied to the flue gas desulfurization of Industrial Boiler wet type Water Membrane Dedusting System, and purpose is the treatment of wastes with processes of wastes against one another.The alkaline industrial waste water pH value that is used for flue gas desulfurization and dedusting is generally 8.1～11.6, and basicity is (with Na
2The O meter) be generally 40～670mg/L, can carry out simultaneously flue gas desulfurization and dedusting, desulfurization degree is generally 70%～80%.The method also exists wet dedusting system to take up an area larger defective.
Wang Yun in " application of the treatment of wastes with processes of wastes against one another on the flue gas desulfurization project " literary composition, introduced utilize printing and dyeing mill discharging alkaline waste water as desulfurizing agent, 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 in hollow-spraying-tower mode and the tower to form the convection current realization to the desulfurization processing of flue gas.Solid waste after the precipitation carries out processed, and solid powder is directly given Building Materials Factory as brick-making raw material, and the waste water that separates directly enters the original sewage treatment plant in industry park.This method is wet type desulfurizing, needs larger absorption tower, and the waste water that produces also will further be processed.
Patent CN1102072 discloses a kind of industrial smoke sulfur dioxide removal method, comprise: the vulcanized sodium absorption liquid is sent in the absorption tower from the upper end, absorption tower, contain industrial SO 2 fume and send into from the bottom, absorption tower, control outlet absorption liquid pH value is 3.5～7.5, and 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 with sodium sulfite solution and carry out three grades of desulfurization in the desulfurizing tower that three absorber portions in upper, middle and lower are arranged.This invention can be carried out purified treatment to entering desulfurizing tower flue gas before, can absorb preferably the sulfur dioxide in the flue gas.But the method technological process is complicated, and the 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, provide a kind of petrochemical industry spent lye to be used for the method for boiler smoke semi-dry desulphurization, realize the treatment of wastes with processes of wastes against one another, both can improve smoke desulfurization efficiency, guarantee that (the waste gas content of sulfur dioxide can remain on 600mg/Nm to the discharging of discharged gas fume stably reaching standard fully
3Below), save the partial desulfurization agent, can reduce again the independent disposal cost of spent lye, energy-saving and cost-reducing, also can eliminate spent lye and efflux impact on the sewage-farm, effectively overcome the shortcomings such as wet desulphurization covers an area of, the 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 is used for the method for semi-dry process flue gas desulphurization, it is characterized in that may further comprise the steps:
1, Spent caustic treatment: spent lye comprises the spent lye that alkene spent lye and TOWER OUTLET IN VINYL CHLORIDE UNIT produce, the alkene spent lye separates through gravitational settling 24～48h removes oily substance and suspension, 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 the absorption tower, the upper part sprays into the absorption tower with spray nozzle; Boiler smoke at first enters dedusting in the electrostatic precipitator, then passes into the bottom, absorption tower, after accelerating, fully contacts with the spent lye that is spray form from bottom to top, 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 the desulfurizing byproduct drains into power plant desulfurization ash storehouse, recombinating to divide is back to bottom, absorption tower repetition desulphurization reaction process, and flue gas enters chimney by air-introduced machine after deduster purifies.
Preferred version is:
Described alkene spent lye separates and removes oily substance and suspension through gravitational settling 30～40h.
In the described semi-dry process flue gas desulphurization process, when in the absorption tower, spraying into spent lye, 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 are 2.0～9.0t/h.
The straying quatity of described desulfurizing agent is 0～1.8t/h.
At first spent lye is carried out preliminary treatment, prevent spent lye coking and blocking nozzle or cause secondary pollution in the boiler flue gas desulfurization process.The alkene spent lye is through gravitational settling 24～48h, and preferred 30～40h separates and removes oily substance and suspension; The spent lye that TOWER OUTLET IN VINYL CHLORIDE UNIT produces is removed most of organic matter by methods such as rectifying or strippings, makes its concentration be lower than 1 μ g/g.
According to the semi-dry process flue gas desulphurization flow process, determine that pretreated spent lye adds mode and position.Boiler smoke at first enters in the electrostatic precipitator, removes the most of dust in the flue gas.The flue gas of discharging enters the absorption tower after the Venturi tube structure of bottom, absorption tower accelerates, flow from bottom to top in tower.Pretreated spent lye is squeezed into the absorption tower by a certain amount of by noncorrosive pump, from up to down sprays from spray thrower, directly contacts with flue gas in being in the turbulence state, and fully reaction reaches and removes SO in the flue gas
2Purpose.With the difference of spent lye straying quatity, desulfurized effect is different.Guaranteeing suitably to adjust the spent lye consumption on the flue gas basis up to standard.
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 solution of the present invention is based on such design: petrochemical industry contains in the alkali waste water (comprising the spent lye that alkene spent lye and TOWER OUTLET IN VINYL CHLORIDE UNIT produce), outside recombinate organic matters such as dividing a diene hydro carbons, aldehyde material, dichloroethanes and VCM spent lye, also have a large amount of NaOH, NaHCO
3, the Na that generates in the 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 to make leather hard behind the desulfurizing agent water spray, then the state with the leather hard powder sprays in the absorption tower, participate in the desulphurization reaction of flue gas, this process is to carry out on gas-solid surface, so floor space is little, equipment investment is little, and scheme of the present invention is directly to spray into and participate in desulphurization reaction in the absorption tower containing alkali waste water, contain on the one hand alkaline matter is arranged in the alkali waste water, can participate in desulphurization reaction, the more important thing is that this desulphurization reaction process is to react at gas-solid and solution-air two interfaces, thereby the semi-dry desulphurization method is more outstanding relatively usually for desulfuration efficiency, can part in addition replace fully desulfurizing agent in the common semi-dry desulphurization method about, and desulfurized effect is more obvious.This point can access sufficient proof in follow-up test.
Compared with prior art, a kind of petrochemical industry spent lye of the present invention is used for the beneficial effect that the method for semi-dry process flue gas desulphurization has: this boiler fume desulfurizing method floor space is little, equipment investment cost is low, both can improve smoke desulfurization efficiency, guarantee the discharging of discharged gas fume stably reaching standard, by control spent lye addition, the SO in the flue gas
2Concentration of emission can be controlled in≤600mg/Nm
3, save the 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 efflux impact on the sewage-farm.
Description of drawings
Fig. 1 is process chart of the present invention.
The present invention will be further described below in conjunction with accompanying drawing 1:
The specific embodiment
Embodiment 1
The alkene spent lye separates and removes oily substance and suspension through gravitational settling 24～48h.With spent lye after pretreatment and desulfurizing agent in the absorption tower, upper position sprays into the absorption tower with spray nozzle, meanwhile, to pass into the bottom, absorption tower through the boiler smoke of most of dust in the electrostatic precipitation removal flue gas, after the Venturi tube structure of bottom, absorption tower accelerates, enter the absorption tower, in tower, flow from bottom to top.In this process, pretreated spent lye is squeezed into the absorption tower by noncorrosive pump and spray nozzle, from up to down sprays from spray thrower, directly contacts with flue gas in being in the turbulence state, and fully reaction reaches and removes SO in the flue gas
2Purpose.
The flow of boiler smoke is 40～50Nm in this example
3/ h, SO
2Concentration is 2400～3700mg/Nm
3When the spent lye straying quatity is 2.0t/h, desulfurizing agent is selected calcium oxide, when consumption is 1.8t/h, and the SO in the flue gas
2Concentration of emission 600～780mg/Nm
3, desulfurization degree is 70%～80%.
Enter desulfurizing dust-collector through the product behind the desulphurization reaction of absorption tower with flue gas self-absorption top of tower and carry out gas solid separation, the light component in the desulfurizing byproduct drains into power plant desulfurization ash storehouse, and the 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, recombinating to divide is back to bottom, absorption tower repetition 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
3When the spent lye straying quatity is 4.0t/h, desulfurizing agent is selected NaOH, when consumption is 1.5t/h, and the SO in the flue gas
2Concentration of emission 500～600mg/Nm
3, desulfurization degree is 75%～85%.The 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
3Other method step is with embodiment 1.
Embodiment 3
Containing alkali waste water in this example is the spent lye that TOWER OUTLET IN VINYL CHLORIDE UNIT produces, and removes most of organic matter by rectifying or gas stripping process.After pretreatment, contain the dichloroethanes content of alkali waste water less than or equal to 1 μ g/g.
Passing into boiler fuel flow to the bottom, absorption tower is 40～50Nm
3/ h, SO
2Concentration is 2600～4300mg/Nm
3In by the absorption tower, the spent lye straying quatity that sprays into of top is 6.0t/h, when the sodium hydroxide concentration that sprays into is 0.8t/h, the SO in the flue gas
2Concentration of emission 400～500mg/Nm
3, desulfurization degree is 80%～90%.
The 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
3Other method step is with embodiment 1.
Embodiment 4
The alkene spent lye separates and removes oily substance and suspension through gravitational settling 30～40h.With spent lye after pretreatment in the absorption tower, upper position sprays into the absorption tower with spray nozzle.Meanwhile, will pass into the bottom, absorption tower through the boiler smoke of most of dust in the electrostatic precipitation removal flue gas, after the Venturi tube structure of bottom, absorption tower accelerates, enter the absorption tower, in tower, flow from bottom to top.Pretreated spent lye is squeezed into the absorption tower by noncorrosive pump, from up to down sprays from spray thrower, directly contacts with flue gas in being in the turbulence state, and fully reaction reaches and removes SO in the flue gas
2Purpose.
Boiler fuel flow is 40～50Nm in this example
3/ h, SO
2Concentration is 2500～4100mg/Nm
3The spent lye straying quatity is 9.0t/h, does not add desulfurizing agent, the SO in the flue gas
2Concentration of emission 60～200mg/Nm
3, desulfurization degree is 90%～99%.
Enter desulfurizing dust-collector through the product behind the desulphurization reaction of absorption tower with flue gas self-absorption top of tower and carry out gas solid separation, the light component in the desulfurizing byproduct drains into power plant desulfurization ash storehouse, and the 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, recombinating to divide is back to bottom, absorption tower repetition desulphurization reaction process, and flue gas enters chimney by air-introduced machine after deduster purifies.
The above only is preferred embodiment of the present invention, is not to be the restriction of invention being made 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 break away to any simple modification, equivalent variations and remodeling that above embodiment does, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (6)
1. a petrochemical industry spent lye is used for the method for semi-dry process flue gas desulphurization, it is characterized in that may further comprise the steps:
1.1, Spent caustic treatment: spent lye comprises the spent lye that alkene spent lye and TOWER OUTLET IN VINYL CHLORIDE UNIT produce, the alkene spent lye separates through gravitational settling 24～48h removes oily substance and suspension, 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 the absorption tower, the upper part sprays into the absorption tower with spray nozzle; Boiler smoke at first enters dedusting in the electrostatic precipitator, then passes into the bottom, absorption tower, after accelerating, fully contacts with the spent lye that is spray form from bottom to top, 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 the desulfurizing byproduct drains into power plant desulfurization ash storehouse, recombinating to divide is back to bottom, absorption tower repetition desulphurization reaction process, and flue gas enters chimney by air-introduced machine after deduster purifies.
2. a kind of petrochemical industry spent lye according to claim 1 is used for the method for semi-dry process flue gas desulphurization, it is characterized in that: the described alkene spent lye of step 1.1 separates and removes oily substance and suspension through gravitational settling 30～40h.
3. a kind of petrochemical industry spent lye according to claim 1 is used for the method for semi-dry process flue gas desulphurization, it is characterized in that: in the semi-dry process flue gas desulphurization process described in the step 1.2, spray into desulfurizer powder spraying into spent lye in the absorption tower when.
4. a kind of petrochemical industry spent lye according to claim 4 is used for the method for semi-dry process flue gas desulphurization, and it is characterized in that: described desulfurizing agent is calcium oxide or NaOH.
5. a kind of petrochemical industry spent lye according to claim 1 is used for the method for semi-dry process flue gas desulphurization, and it is characterized in that: the flow of described boiler smoke is 40～50Nm
3/ h, spent lye straying quatity are 2.0～9.0t/h.
According to claim 4 or 5 described a kind of petrochemical industry spent lyes be used for the method for semi-dry process flue gas desulphurization, it is characterized in that: the straying quatity of described desulfurizing agent is 0～1.8t/h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014183364A1 (en) * | 2013-05-14 | 2014-11-20 | 中国环境科学研究院 | High-efficiency method for removing sulfur and mercury of coal-fired flue gas, and apparatus thereof |
| CN104353351A (en) * | 2014-12-02 | 2015-02-18 | 成都华西堂投资有限公司 | Industrial preparation method for preparing sodium hydrogen carbonate for smoke purification from waste alkali |
| CN109647167A (en) * | 2019-01-25 | 2019-04-19 | 内蒙古乌海化工有限公司 | A kind of comprehensive recycling system and method for PVC salkali waste and gas burning kiln exhaust gas |
| CN109824285A (en) * | 2017-11-23 | 2019-05-31 | 湖南昌迪环境科技有限公司 | Cement fume desulfurizing agent and its application |
| CN113813772A (en) * | 2021-09-27 | 2021-12-21 | 上海麦雀斯环境工程技术有限公司 | Synergistic semi-dry desulfurization process and system of landfill leachate concentrate and lime slurry |
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| CN108178471B (en) * | 2018-01-26 | 2021-06-22 | 湖北振华化学股份有限公司 | Method and device for comprehensively utilizing solid waste in sodium sulfide production |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014183364A1 (en) * | 2013-05-14 | 2014-11-20 | 中国环境科学研究院 | High-efficiency method for removing sulfur and mercury of coal-fired flue gas, and apparatus thereof |
| CN104353351A (en) * | 2014-12-02 | 2015-02-18 | 成都华西堂投资有限公司 | Industrial preparation method for preparing sodium hydrogen carbonate for smoke purification from waste alkali |
| CN109824285A (en) * | 2017-11-23 | 2019-05-31 | 湖南昌迪环境科技有限公司 | Cement fume desulfurizing agent and its application |
| 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 |
| CN109647167A (en) * | 2019-01-25 | 2019-04-19 | 内蒙古乌海化工有限公司 | A kind of comprehensive recycling system and method for PVC salkali waste and gas burning kiln exhaust gas |
| CN113813772A (en) * | 2021-09-27 | 2021-12-21 | 上海麦雀斯环境工程技术有限公司 | Synergistic semi-dry desulfurization process and system of landfill leachate concentrate and lime slurry |
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