CN1265934A - Flue gas wet desulfuration and denitration purification process - Google Patents
Flue gas wet desulfuration and denitration purification process Download PDFInfo
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- CN1265934A CN1265934A CN00101556A CN00101556A CN1265934A CN 1265934 A CN1265934 A CN 1265934A CN 00101556 A CN00101556 A CN 00101556A CN 00101556 A CN00101556 A CN 00101556A CN 1265934 A CN1265934 A CN 1265934A
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Abstract
The present invention utilizes the industrial residue of iron chipings and aluminium chipings as desulfurizer to imptement the technological process of removing sulfur dioxide and nitrogen oxide from flue gas and making reaction to produce water treatment chemicals. Said technological process only needs supplementing water and desulfurizer, and does not produce any three-wastes. Said invention can use conventional boiler, boiler of steam-power plant and metal-smelting tail gas to implement desulfurization and denitration.
Description
The invention belongs to the pollution control and the resource recycling technology thereof that contain sulfur dioxide, nitrogen oxide containing gas.
China is maximum in the world coal production state and country of consumption, also is that a few is one of country of main energy sources with the coal in the world.Therefore China's atmosphere pollution is based on coal smoke type, and major pollutants are sulfur dioxide, nitrogen oxide and flue dust.The present atmospheric environment situation of China still allows of no optimist, and along with rapid development of economy in recent years, atmospheric environment is also in continuous deterioration.Urban atmosphere SO
2Very serious etc. pollution level.Announce that according to 1997 " China Environmental State Bulletin " the sulfur dioxide (SO2) emissions total amount is 2,346 ten thousand tons, wherein, the discharge capacity of industrial source is 1,852 ten thousand tons, accounts for 78.9%.The total amount Zhong Xian of industrial discharge and be 1,363 ten thousand tons more than the county accounts for 73.6%.The acid rain of China pollutes also on the rise.On the south the Changjiang river, to the east of the Qinghai-Tibet Platean and the Sichuan Basin, acid rain center P H value is minimum 4.0, acid rain frequency 80%.National precipitation pH value average out to 3.74-7.79 in 1997 is lower than 44 in 5.6 city, accounts for 47.8% of statistics city.
In order to prevent and treat sulfur dioxide pollution and acid rain problem, the domestic and international method of taking is a lot of at present, as flue gas desulfurization technique, clean coal technology, power-saving technology etc.Because the sulphur in the flue gas is with SO
2Form exists, remove easier, so flue gas desulfurization is comparatively practical at present approach, countries in the world research also more.Fume desulphurization method roughly is divided into two classes, dry method and wet method.Dry desulfurization efficient is low, and equipment is huge, and operating technology requires high, develops slower.Wet desulphurization equipment is little, processing ease, and desulfuration efficiency height.Therefore, pay attention to the research of wet desulphurization abroad, especially get at most with Japan, the U.S., German Research.Whether flue gas desulfurization also can useful according to product, is divided into the method for abandoning and absorption method.Absorption method is because of its economic factor people's attention extremely.People such as army Jing Xiong had proposed to absorb sulfur in smoke with basic aluminium sulphate in 1987, adopted steam heating to reclaim the method for sulfur dioxide then; The virtuous porous adsorbing material that has proposed to utilize raw materials such as industrial residue, cigarette mud, active carbon, grain flour to make of Wu Ju adsorbed sulfur in smoke in 1986, thereby reclaimed the technology of sulfur dioxide; People such as Sun Peishi have studied the ferrum-based catalyst absorption liquid and have purified sulfur in smoke technology; European Atomic Energy Community had applied for once that (application number: 87103118), proposed with disodium salt iron was that absorbent absorbs the nitrogen oxide in the flue gas to Chinese patent, adopts electrolytic regeneration then; People such as Yang Dejun have invented (number of patent application: 92111928) utilize waste iron filing to add water and absorb the new technology that sulfur dioxide generates ferrous sulfate under the catalyst condition; Beans dam power plant has also tested and adopted iron particulate material and the sulfur in smoke reaction of selecting from lime-ash, generates the ferrous sulfate accessory substance.The two kinds of technology in back are identical with starting point of the present invention, but technical process is different with product, and effect also differs widely.
Simultaneously, water treatment agent is that the important chemical, the particularly application of inorganic coagulant class of feedwater and sewage disposal is more extensive, and what receive much attention in recent years is inorganic polymer coagulant such as bodied ferric sulfate and polyaluminium sulfate etc.Raw materials such as ferrous sulfate, aluminium oxide are used in the production of such high-molecular coagulant adopting at present more, in the presence of catalyst and sulfuric acid, be polymerized through air oxidation or oxidant oxidation, raw materials for production particularly catalyst cost height cause product price to be much higher than conventional inorganic coagulant, and its application is restricted.Utilizing flue gas desulfurization course directly to reclaim the polyaluminum sulfate salt still is not reported.
The purpose of this invention is to provide a kind of no waste water, waste sludge discharge, sulfur dioxide clearance height, the smoke-gas wet desulfurization denitrating technique technology of the recyclable utilization of resource, the byproduct polymerised sulphur hydrochlorate that makes simultaneously can be used as the medicament of water treatment.
The present invention is achieved like this:
The principle of smoke-gas wet desulfurization denitration is to be desulfurizing agent and absorb the acid reaction that is generated after the sulfur in smoke with shower water with waste iron filing or aluminium scrap bits, generate ferrous sulfate or aluminum sulfate, with they process air oxidations, the mixture that just can make bodied ferric sulfate (aluminium) and ferric sulfate (aluminium) is as efficient water treatment agent again.And the basic process of denitrating flue gas reaction is that nitrogen oxide and acid reaction become nitrous acid, is desulfurized agent then and is reduced into the innoxious discharging of nitrogen, and removal efficiency reaches more than 90%.
Accompanying drawing is seen in the technological process of flue gas desulfurization and denitrification, the body of reaction tower (1) among the figure, air inlet (2), filler gripper shoe (3), filler (4), last water distributing plate (5), shower nozzle (6), exhaust outlet (7), absorption liquid feed pipe (8), absorption liquid flowmeter (9), absorption liquid storage tank (10), absorption liquid reflux pump (11), absorption liquid return pipe (12), liquid level gauge (13), filler add inlet (14).Reaction tower is commonly used cylindrical, also can adopt squarely, and its material can adopt stainless steel (small-sized: below 10 cubic metres), plastic-steel (medium-sized: below 100 cubic metres), or preservative treatment (large-scale: more than 100 cubic metres) in the armored concrete.
The filler of reaction tower (4) divides two kinds: a kind of is inert filler, it only provides phase contact area as Gas-Liquid Absorption, itself does not react, solid desulfurating agent (iron filings) joins and absorbs in the liquid bath (circulating slot), reclaiming chemical reaction carries out in the absorption liquid storage tank, such filler comprises corrosion resistance goods such as ceramic, plastic products, stainless steel products, and its diameter is between the 50-100 millimeter.Another kind is a reactive filler, and directly as filler, recovery is reflected at packed tower directly to be carried out with solid desulfurating agent, and such filler comprises such as metal or its oxides such as iron filings, aluminium bits.
The basic technology condition of flue gas desulfurization and denitrification comprises following parameters: gas residence time is 0.1-1.0 minute, the time of staying short (0.1-0.2 minute) when low-concentration sulfur dioxide removes, the high concentration time of staying long (every grade 0.8-1.0 minute).It is 0.01--0.04 that liquid circulation amount keeps gas liquid ratio.The intermediate product crystalline sulfuric acid that reclaims is ferrous to be oxidized to ferric sulfate and to aggregate into poly-iron in the fluidised bed dehydration oxidizing tower, reaction temperature is 250-300 ℃, and reaction pressure is a normal pressure, residence time of material 2-4 hour.
The consumption of desulfurizing agent and the output of coagulant are as follows: the norm quota of consumption that in the desulfurization amount is benchmark is: 0.9 kilogram of desulfurizing agent (with iron, down together)/per kilogram SO2; If it is 1000 milligrams/standard cubic meter that flue gas contains amount of sulfur dioxide, then be equivalent to the contained amount of sulfur dioxide of 1000 standard cubic meter flue gases.The water treatment agent productive rate that the reaction back is generated is: 4 kilograms/per kilogram SO2 also can be converted into 4.4 kilograms of water treatment agents/per kilogram desulfurizing agent.
Reaction tower in this technology and other annex all adopt anti-corrosion material or do preservative treatment, and the absorption liquid system also adopts anticorrosion equipment and pipeline.
In this technology when adopting iron filings as desulfurizing agent, technological process can be adopted preposition or rearmounted (high concentration sulfur dioxide) ferrous sulfate oxidizing tower, the excellent polyaluminum sulfate salt coagulant of available energy increases substantially economic benefit, and has fully utilized flue gas waste heat and surplus oxygen.
The present invention according to flue gas source with contain sulfur dioxide, nitrous oxides concentration is different, can adopt two kinds of different process programs:
For the high concentration sulfur dioxide that discharges in the metal smelt process (usually at 1%--10%), adopt the above course of reaction of two-stage, to reach the maximum rate of recovery and removal efficiency.Its technological process is: enter into successively in the first order, the second level, the third level reaction absorption tower by flowmeter through the flue gas after the dedusting, all there is spray absorption system at the corresponding levels on each grade absorption tower, this system comprises that circulating absorption solution groove, water circulating pump, water-locator, spray are first-class, add the desulfurizing agent iron filings in the circulating water chennel, when absorption reaction makes sulphate of iron when saturated, absorption liquid reclaims the byproduct bodied ferric sulfate with hot-air (flue gas) oxidation.
Low-concentration sulfur dioxide tail gas for conventional coal-burning boiler or the discharging of other combustion process, contain the sulfur dioxide concentration scope in 200 milligrams/standard cubic meter to 2000 milligram/standard cubic meter according to different its tail gas of the coal sulfur content of being burnt, can adopt one-level or two-stage reaction tower to come desulfurization, the following flue gas of 1000 milligrams/standard cubic meter adopts one-level, 1000 milligrams/can adopt two-stage more than the standard cubic meter.Its technical process is: the flue gas through dedusting at first enters preposition oxidizing tower by flowmeter, and the circulation fluid that the back is absorbed the sulfur dioxide generation carries out air oxidation, generates the final products bodied ferric sulfate; This moment, sulfur in smoke can partly be absorbed, and had oxidation and desulfurization double effects; Flue gas enters the first order, second level absorption reaction tower then, filling iron filings desulfurizing agent in the tower, every grade all is provided with the absorption liquid circulatory system simultaneously, the flue gas qualified discharge after absorbing through two-stage, and absorption liquid is delivered to preposition oxidizing tower ferrous sulfate is oxidized to the recycling of polymerization iron.
The effect that the present invention can reach is:
1. applied widely, this technology and equipment can be used for removing all kinds of contain sulfur dioxide and (or) tail gas and the flue gas of nitrogen oxide, comprise boiler for domestic, heating boiler, Industrial Boiler, power plant large-sized boiler, metal smelt tail gas etc.
2. concentration range that be suitable for to handle sulfur dioxide is wide, and for high concentration (sulfur dioxide concentration reaches more than 1%), this technology of low concentration (sulfur dioxide concentration 2000 milligrams/below the standard cubic meter) all can effectively be handled.Its treatment effeciency all remains on more than 99.9%, be at present other sulfur method can not compare.
3. the recyclable utilization of resource and do not have the sharpest edges that the three wastes are these technology, in this process treatment process, with sulfur dioxide, nitrogen oxide and reactive desulfurizing agent, 100% generation water treatment agent does not have any waste water and dregs discharging.Reaction raw materials is solid desulfurating agent and water, and product is a solid water treating agent, and the Recycling Mother Solution of water treatment agent is applied mechanically, and is typical process for cleanly preparing.
4. another advantage that to have tangible economic benefit be this technology, the present technique desulfurizer therefor is industrial processes waste material (iron filings, aluminium bits etc.), the about 100-300 of cost of material unit/ton, desulfurizing agent per ton is produced 4.4 tons of water treatment agents, the water treatment agent price is still pressed 300 yuan of/ton calculating of lowest price, 1020 yuan of ton desulfurizing agent gross profits, the deduction operating cost whenever removes 1 ton of sulfur dioxide and has 453 yuan (500 milligrams/standard cubic meter sulfur dioxide), 730 yuan (1500 milligrams/standard cubic meter sulfur dioxide) and 900 yuan (4% sulfur dioxide concentration).
Embodiment 1: it is as follows that resource recovery FGD process denitration technology is applied to the embodiment of boiler:
With 4 tons of boilers, 10000 mark rice/hour be example
It is 1500ppm (3300mg/ cubic meter) that flue gas contains content of sulfur dioxide
Unit interval removal sulfur dioxide amount: 33 kilograms/hour; 792 kilograms/day; 285.2 ton/year;
Water treatment agent output: 132 kilograms/hour
The gas reaction time of staying is: 0.1 minute
The reaction tower volume is: 17 cubic metres/10000 cubic metres flue gases/hour
Power consumption is: the 0.0015KW/ cubic meter; Total energy consumption 15KW.
2.3 meters of reaction tower body diameters; High 4 meters; Filler is iron filings
Its technical process is: the flue gas through dedusting at first enters preposition oxidizing tower by flowmeter, and the ferrous sulfate that the back is absorbed the sulfur dioxide generation carries out air oxidation, generates the final products bodied ferric sulfate; This moment, sulfur in smoke can partly be absorbed, and had oxidation and desulfurization double effects; Flue gas enters into the first order, second level absorption reaction tower more then, filling iron filings desulfurizing agent in the tower, every grade all is provided with the absorption liquid circulatory system simultaneously, and through the flue gas qualified discharge behind the two-stage absorption reaction, absorption liquid is delivered to preposition oxidizing tower ferrous sulfate is oxidized to the recycling of polymerization iron.
Embodiment 2: it is as follows that resource recovery FGD process denitration technology is applied to the embodiment of copper smelting exhaust:
With certain copper smelting plant is example, 40000 mark rice/hour calculating
It is 4% that flue gas contains content of sulfur dioxide
Unit interval removal sulfur dioxide amount: 1600 kilograms/hour; 38 ton per days; 1.38 ten thousand tons/year:
Water treatment agent output: 6400 kilograms/hour
The gas reaction time of staying is: 1.0 minutes
The reaction tower volume is: 667 cubic metres/40000 cubic metres flue gases/hour
Power consumption is: the 0.0015KW/ cubic meter; Total energy consumption 60KW.
8.0 meters of reaction tower body diameters; High 6 meters; Two; Filler is iron filings
Its technical process is as follows: enter into successively in the first order, the second level, the third level reaction absorption tower by flowmeter through the flue gas after the dedusting, all there is spray absorption system at the corresponding levels on each grade absorption tower, this system comprises that circulating absorption solution groove, water circulating pump, water-locator, spray are first-class, add the desulfurizing agent iron filings in the circulating water chennel, when absorption reaction makes ferrous sulfate when saturated, the byproduct bodied ferric sulfate is reclaimed in absorption liquid reusable heat air (flue gas) oxidation.
Claims (4)
1. the desulphurization denitration technology of a hydrometallurgic recovery sulfur dioxide in flue gas, it is characterized in that this desulfurizing and denitrifying process technology is at 1-3 order reaction packed tower or absorbs in the liquid bath, metal processing waste iron filings or aluminium bits are housed as desulfurizing agent, utilize aqueous medium to absorb acid and reactive desulfurizing agent that sulfur in smoke produces, generate ferrous sulfate or aluminum sulfate, in oxidizing tower, make water treatment agent bodied ferric sulfate or polyaluminium sulfate then through air oxidation; Nitrogen oxide in the flue gas and acid reaction generate nitrous acid, are desulfurized agent and are reduced into nitrogen discharge; The time of staying of flue gas in reaction tower is 0.1-1.0 minute, and liquid circulation amount is gas-water ratio 0.01-0.04; The air oxidation reaction temperature is 250--300 ℃, and reaction pressure is a normal pressure, and residence time of material is 2-4 hour.
2. according to the described desulfurizing and denitrifying process of claim 1, it is characterized in that this technology is applicable to the recovery of the 1%--10% high concentration sulfur dioxide that discharges in the metal smelt process, its technological process is: flue gas → flowmeter → first order reaction tower → second level reaction tower → third level reaction tower → exhaust; Also be applicable to the processing of sulfur dioxide concentration scope in the conventional fire coal boiler fume in 200 milligrams/standard cubic meter to 2000 milligram/standard cubic meter, can adopt one-level or two-stage reaction tower to come desulfurization this moment, and technical process is: flue gas → flowmeter → first order reaction tower → (second level reaction tower) → exhaust.
3. according to the described desulfurizing and denitrifying process of claim 1, it is characterized in that when iron filings or aluminium bits desulfurizing agent during desulfurization is reclaimed and is reflected at packed tower and directly carries out as the reaction tower filler; When adopting void tower or pottery, plastics, stainless steel inert filler, desulfurizing agent is added in the circulating water chennel, and desulfurization is reclaimed to be reflected to absorb in the liquid bath and carried out.
4. according to the described desulfurizing and denitrifying process of claim 1, it is characterized in that when adopting iron filings or aluminium bits as desulfurizing agent, its air oxidation device can adopt postposition (high concentration) or preposition oxidizing tower, obtains performance excellent more bodied ferric sulfate (aluminium) coagulant and remarkable economic efficiency.
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| CN00101556A CN1102422C (en) | 2000-01-18 | 2000-01-18 | Flue gas wet desulfuration and denitration purification process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348301C (en) * | 2005-11-21 | 2007-11-14 | 孙克勤 | Suspension type smoke denitration reactor |
| CN101785965A (en) * | 2010-03-02 | 2010-07-28 | 浙江菲达环保科技股份有限公司 | Complex absorption cycle semi-dry desulfurization and denitrification integral process and device |
| CN102989301A (en) * | 2012-09-12 | 2013-03-27 | 河南绿典环保节能科技有限公司 | Flue gas wet reduction integrated desulfurization, denitrification, harmless treatment and resource utilization method |
| CN101637688B (en) * | 2009-08-14 | 2013-06-12 | 暨南大学 | Treatment method and device for waste gas containing nitrogen oxides |
| CN106268263A (en) * | 2016-10-17 | 2017-01-04 | 浙江大学 | A kind of preposition oxidation spray multiple pollutant cooperative control system and method |
| CN109603429A (en) * | 2018-11-14 | 2019-04-12 | 惠州宇新化工有限责任公司 | A kind of raw air preprocess method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344552C (en) * | 2005-06-24 | 2007-10-24 | 大连理工大学 | Method and apparatus for treating urban sewage by means of flue gas desulfurization of power plant and fly ash |
| US7993616B2 (en) * | 2007-09-19 | 2011-08-09 | C-Quest Technologies LLC | Methods and devices for reducing hazardous air pollutants |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4497902A (en) * | 1979-04-11 | 1985-02-05 | Standard Oil Company (Indiana) | Composition for removing sulfur oxides from a gas |
| LU86407A1 (en) * | 1986-04-24 | 1986-09-02 | Euratom | METHOD AND DEVICE FOR NICKNING SMOKE GASES |
| CN1073613A (en) * | 1992-09-30 | 1993-06-30 | 杨德俊 | Flue-gas desulfuration method and device thereof |
| DE4338332A1 (en) * | 1993-11-10 | 1995-05-11 | Bischoff Gasreinigung | Wash tower for a flue gas desulfurization plant |
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2000
- 2000-01-18 CN CN00101556A patent/CN1102422C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348301C (en) * | 2005-11-21 | 2007-11-14 | 孙克勤 | Suspension type smoke denitration reactor |
| CN101637688B (en) * | 2009-08-14 | 2013-06-12 | 暨南大学 | Treatment method and device for waste gas containing nitrogen oxides |
| CN101785965A (en) * | 2010-03-02 | 2010-07-28 | 浙江菲达环保科技股份有限公司 | Complex absorption cycle semi-dry desulfurization and denitrification integral process and device |
| CN101785965B (en) * | 2010-03-02 | 2013-06-12 | 浙江菲达环保科技股份有限公司 | Complex absorption cycle semi-dry desulfurization and denitrification integral process and device |
| CN102989301A (en) * | 2012-09-12 | 2013-03-27 | 河南绿典环保节能科技有限公司 | Flue gas wet reduction integrated desulfurization, denitrification, harmless treatment and resource utilization method |
| CN102989301B (en) * | 2012-09-12 | 2014-05-28 | 河南绿典环保节能科技有限公司 | Flue gas wet reduction integrated desulfurization, denitrification, harmless treatment and resource utilization method |
| CN106268263A (en) * | 2016-10-17 | 2017-01-04 | 浙江大学 | A kind of preposition oxidation spray multiple pollutant cooperative control system and method |
| CN109603429A (en) * | 2018-11-14 | 2019-04-12 | 惠州宇新化工有限责任公司 | A kind of raw air preprocess method |
| CN109603429B (en) * | 2018-11-14 | 2021-03-05 | 惠州宇新新材料有限公司 | Raw material air pretreatment method |
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| CN1102422C (en) | 2003-03-05 |
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