CN1073613A - Flue-gas desulfuration method and device thereof - Google Patents
Flue-gas desulfuration method and device thereof Download PDFInfo
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- CN1073613A CN1073613A CN 92111928 CN92111928A CN1073613A CN 1073613 A CN1073613 A CN 1073613A CN 92111928 CN92111928 CN 92111928 CN 92111928 A CN92111928 A CN 92111928A CN 1073613 A CN1073613 A CN 1073613A
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Abstract
The invention belongs to the technical field of prevention and control of air pollution in the environmental protection.
At present general fume desulphurization method, investment is big, and deficiency in economic performance is difficult for promoting.The present invention adopts waste iron filing to add water to absorb SO in the flue gas in the presence of catalyst
2, make it to generate the ferrous sulfate of extensive use.By the desulfurization of multifunctional ceiling receiving apparatus, this device melts the flue gas cooling, absorbs desulfurization, removes water smoke in one with flue gas after the dedusting, and desulfurization degree can reach 72～95%; This device combines cooling, oxygenating, the evaporation and concentration of absorption liquid again, makes things convenient for ferrous sulfate to reclaim, and is good in economic efficiency, suits to promote in the sulphur coal area.
Description
The invention belongs to the technical field of prevention and control of air pollution in the environmental protection.
Because industrial continuous development, many places have produced the harm of acid rain, acid mist, bring disaster to health, the ecosystem and various building, artifact and equipment.Tracing it to its cause, mainly is owing to contain sulphur in the fuel, contains due to a large amount of sulfur dioxide in the flue gas that produces in combustion process.
The method of current flue gas desulfurization is a lot, and various types of process units and flow process have over one hundred kind, about ten kinds of industrial large-scale application, and main have limestone-gypsum method, Arbiso process, ammonium sulfite, an alkaline aluminum sulfate-SO
2Method, alkaline aluminum sulfate-gypsum method, towards grey water law, dry type ash method, activated carbon method, catalytic oxidation etc.But because the investment of these methods is big, consumption is many, the quantity of slag is many, financial burden is heavy and complicated operation, equipment easily stop up; many factories are difficult to bear; thereby fail widespread usage on large numbers of medium and small boilers, cause the harm of acid rain, acid mist serious day by day and (see that national environment protection science and technology calipers draws group: the flue gas desulfurization a collection of selected materials).
It is little that purpose of the present invention just provides a kind of investment, and technology is simple, convenient, flue-gas desulfuration method and the device thereof that can turn waste into wealth and produce ferrous sulfate.
The present invention's multifunctional ceiling receiving apparatus adds water with waste iron filing and absorb sulfur in smoke under the little amount of catalyst effect, makes it to be converted into the ferrous sulfate of extensive use.Investment and floor space is little, easy to operate, can not stop up and certain income arranged economically.To the machine works of the own waste iron filing in sulphur coal area or have medium and small boiler and kiln in other factories in machine repair workshop very suitable.
At work, we find moist flue gas, and are very serious to the corrosion of iron, and installing is eating thrown soon, and residual green crystal ferrous sulfate.This shows having under the situation of moisture content, the sulfur dioxide in iron energy and the flue gas produces following reaction:
Therefore, we think that adding water with waste iron filing can absorb sulfur dioxide in the flue gas.
Obviously, the surface area of the speed of this reaction and iron filings is relevant.Iron filings are Bao Yuxi more the more, its area more then reaction more rapidly, then absorption efficiency is higher, we have carried out following small-scale test in laboratory:
In 500ml Meng Shi wash bottle, add 200ml water, (iron filings are car bits, and average thickness is 0.15mm, and the area of estimating every gram iron filings is 140Cm to add the different iron filings of measuring again
2), be that 7 liters/minute flow velocity feeds the simulated flue gas that the worker prepares then, after stablizing 1 hour, measure the Meng Shi wash bottle simultaneously with iodimetric titration and absorb front and back SO
2Concentration, calculate its absorption efficiency, result such as table one:
Table one varying number iron filings are to SO
2The influence of absorptivity
| Add water number amount (ml) and add iron filings quantity (g) estimation iron filings areas (Cm) | 200 10 1400 | 200 30 4200 | 200 100 14000 | 200 200 28000 |
| SO before absorbing 2Concentration (mg/m 3) absorption back SO 2Concentration (mg/m 3) absorption efficiency (%) | 1430 1015 29.0 | 1951 1077 44.8 | 2206 941 57.3 | 2145 816 61.9 |
| Every gram iron filings are to the influence of absorption efficiency | 2.9 | 1.5 | 0.57 | 0.31 |
This shows, the iron filings of adding the more, the area of iron filings is bigger, absorption efficiency is higher.But too much iron filings influence liquid-solid disturbance, make the raising of absorption efficiency not ideal enough.We tentatively consider in water 200ml to add the 30g iron filings (its area are 0.42m for this reason
2) better.Certainly, this will see that also concrete condition at that time determines.
Consider that from another point of view this reaction is actually a kind of corrosiveness,, a kind ofly make catalyst, make it to form interior electrolysis, must improve the corrosion rate of iron, make SO with iron than the high material in ferroelectric position if add according to the theory of corrosion
2Absorptivity improve.For this reason, we have added the catalyst of variety classes varying number when adding iron filings 30g, and by last method test, the result is as table.
Table two different catalysts exists down SO
2The influence of absorptivity (%)
| Add catalysis kind quantity | 1g | 5g | 15g | 30g |
| Granular active carbon granulated carbon cleaned coal ash tube bits salt | 55.2 54.0 51.0 56.7 55.6 | 68.3 60.3 54.2 62.3 62.5 | 74.5 65.7 55.1 69.1 67.8 | 81.2 70.1 -?- 72.7 69.0 |
This shows, add the salt of higher catalyst of various current potentials and increase electrical conductivity, all can improve SO
2Absorptivity.
But, add salt, salt will be discharged with absorption liquid, increase the ferrous difficulty of reclaim sulfuric acid, increase the pollution of water, should not adopt generally speaking.
Coal ash is that boiler dust remover is collected, and certain catalytic action is also arranged, but dust is too thin, and it is big to account for volume, too dense influences the iron filings disturbance, and effect is bad.
Add other solid catalysts: granular active carbon, granular carbon, copper scale effect are all better.We consider new installed device in practicality, can make catalyst with granular active carbon or carbon, rely on the coal of the next not Ex-all of dedusting to make catalyst later on, can add or not add other catalyst less.
Comprehensive above-mentioned situation has been selected two kinds of representative formulas, carries out desulfurization test with secondary Meng Shi wash bottle series connection, each trial run 72 hours, and sampling analysis in per 8 hours is once calculated its average SO
2Absorptivity, result such as table three:
This shows, carry out secondary by the prescription of sequence number 3 and absorb the desulfurization standard (Chongqing City's regulation desulfurization degree reaches and promptly thinks qualified more than 50%) that can reach regulation.
With what prescription, what adopts absorb as in fact, should be according to local condition, local resources, and the concrete condition that local environment requires determines.
It is thermal response that this chemical reaction is put, so the temperature height to reacting unfavorable, but can improve molecular diffusion speed, also has reacting favourable one side so temperature raises.Therefore, at normal temperatures, temperature is little to the reaction speed influence.More than experiment is had plenty of in about 12 ℃ test in winter; Have plenty of in test in about 30 ℃ of summers, the result all can coincide mutually, but will influence SO according to calculation of thermodynamics more than 80 ℃
2Therefore absorptivity is generally considered still should consider before the desulfurization flue gas is cooled off behind flue gas ash removal, and then with SO
2Absorb.
For implementing the new technology of flue gas desulfurization, designed a kind of multifunctional ceiling receiving apparatus, with cooling, desulfurization absorption, the demist of flue gas, the cooling of absorption liquid, oxygenating, absorption SO
2, evaporation, operation such as concentrate and combine together; To reduce investment outlay, to save floor space, simplify the operation, conveniently to manage.Its structure such as accompanying drawing.
Fig. 1 is the installation drawing of this flue-gas desulfuration method;
Among the figure: 1, air inlet pipe, 2, blower fan, 3, cooling tower, 4, desulfurizing tower, 5, cooling oxygenating tower, 6, demister, 7, escape pipe, 8, circulating pump, 9, the absorption liquid circulating pump, 10, ball-cock assembly, 11, ball-cock assembly, 12, water intaking valve, 13, concentrate liquid pool, 14, absorb liquid pool, 15, the convex duct.
As shown in Figure 1: device of the present invention is that cooling, absorption, oxygenating, evaporation are combined in the structures, concentrated liquid pool 13 and absorption liquid pool 14 that its bottom is and connects, the cooling evaporating column 3 and the desulfurizing tower 4 that on it are and connect, there is convex duct 15 to be connected between two towers, its top is cooling oxygenating tower 5, two circulating pumps 8,9 are arranged with concentrate and absorption liquid circulation, have two ball-cock assemblys 10,11 to control the liquid level of concentrate and absorption liquid automatically.
This device system is arranged on after the flue gas ash removal, current many boilers have all been installed cleaner, flue gas after the dedusting is introduced blower fan 2 by admission line 1, the air quantity of this blower fan should equate with the blower fan of dust pelletizing system, blast should be more than 2000Pa, to overcome the resistance of desulfurizer, the resistance of desulfurizer is looked the shatter value of iron filings and difference is arranged, generally between 1200Pa and 1800Pa.In general, can behind the air-introduced machine of former dedusting, the connect air-introduced machine of a same model specification.If newly-designed dusting and desulfuring system, then the blower fan of two series connection can merge, and dress is that a typhoon amount is identical, the high pressure positive blower that blast is higher.
Flue gas through supercooling enters absorption desulfurizing tower 4 by the bottom.This tower is generally the secondary sieve-plate tower, also can be three grades of sieve-plate towers or one-level packed tower, shatter value and local environmental requirement on iron filings are decided, the void tower wind speed can calculate by 3 meter per seconds, section can be square, the punching rate of sieve plate is 14～15%, adds 10～20 order nylon screens on the every sieve plate and the overflow mouth of pipe, falls to prevent its iron filings and catalyst.Every layer of sieve-plate tower height is more than 1 meter, and its top has nozzle to spray into absorption liquid, flows back to the absorption liquid pool by iron filings, catalyst, foam on the sieve plate by overflow pipe, and the absorption liquid of spray is by every m
31～1.5 liter of meter of flue gas.Peep hole is one in the middle part of every layer of tower, so that regulate the flow velocity of absorption liquid, making foam layer height is 0.6～0.7 meter.
Every layer absorption tower top shower downside is established wicket, the iron filings of can packing into thus, and required iron filings quantity is determined by the iron filings area, absorbs at secondary, requires absorptivity to reach at 72% o'clock, can select absorption coefficient 0.0007KgSO for use
2/ m
2.h, calculate in view of the above to calculate according to the bits average thickness again behind the area and should add iron filings weight.Divide then and be added on the nylon wire of each layer sieve plate.Catalyst is then sneaked in the iron filings by a thirtieth (or suitably increase and decrease according to local environmental requirement) of iron filings.
After demister 6 and pipeline 7 enter chimney, demister can be baffle-type, screen mesh type or Spiralism type to flue gas by the absorption tower desulfurization, and the fog of recovery should flow back in the absorption tower.
The cooling oxygenating tower 5 of absorption liquid, its sizableness in spraying and sprinkling evaporation cooling tower 3 and absorb desulfurizing tower and, for saving floor occupying area, can build by laying bricks or stones at tower 3, above the tower 4, its height should have more than 1 meter, is reverse rare blind window all around, allows the horizontal free flow of air, absorption liquid is sprayed into by the top, and flow design is every m
32～3 liters of flue gases flow back to following absorption liquid pool after the absorption liquid cooling oxygenating automatically.At the bottom of the also available common glass steel cooling tower of cooling oxygenating, effect can be more better, but investment and power consumption increase.
Absorption liquid circulating pump 9 absorbs desulfurizing tower and the cooling oxygenating tower except that supplying with, and also should open some at any time and enter the concentrated liquid pool that absorbs, and feed is gone into the usefulness of flue gas spray cooling, and utilizes the heat of vaporization of flue gas to concentrate absorption liquid, enters and concentrates the every m of absorption liquid pool
3About 0.12 liter of flue gas.The loss of absorption liquid replenishes with running water, controls automatically with ball-cock assembly 10.
During the absorption liquid evaporation and concentration, every m
30.1 liter of the about evaporation water of flue gas.
Circulating pump 8 is except that supplying with the circulation of spray cooling evaporating column, and still needing to pump a part ofly is transported to the ferrous sulfate recycle section by pipeline 12.
Ball-cock assembly 11 is that control concentrates liquid pool liquid level usefulness.
The ferrous sulfate recycle section can be located near the multi-functional flue gas desulfur device, also can be united by several multi-functional flue gas desulfur devices and set up one.
The recovery method of ferrous sulfate is filtration, evaporation, cooling, crystallization, with centrifuge crystallization is leached, the packing warehouse-in.(mother liquor then can return to concentrate with absorbing and further concentrate).Its technology, equipment are identical with usual method, do not give unnecessary details.
Ferrous sulfate is an important chemical material, can be in order to make iron oxide red, iron oxide yellow, Chinese blue, ink, bodied ferric sulfate and other molysite; Can be used as mordant, tanning extracts, water purification agent, timber preservative, disinfectant etc.; Can be used for animal husbandry and make feed addictive, be used for agricultural operation chemical fertilizer, herbicide and agricultural chemicals; Pharmaceutically as local convergence agent and hematinic; Be a kind of best-selling product at present.
The tower body of multi-functional flue gas desulfurization absorption plant, all available blue bricks of pond body (or common brick) are built by laying bricks or stones with acid resisting mortar, but mortar must be full, and front and back are applied the thick acid resisting mortar of 10mm again on the surface.Cover plate reinforcing bar acid-resisting concrete prefabricated board.All the other doors, doorframe, blind window grid can be with plastics or timber.The peep hole heavy sheet glass, epoxy bond, remaining parts is with phenol aldehyde modified expoxy glass or other heat resistant plastices.
Every Km
3Flue gas consumption of power 3～4kwh.
SO per ton
2Consume 700 kilograms of iron filings, theoretical value is 872 kilograms, and actual consumption is on the low side, and this may be because a part of SO
2The H that has become
2SO
4, a part of ferrous sulfate has become the cause of ferric sulphate.
Waste iron filing per ton can make 4.5 tons in ferrous sulfate, and theoretical value is 5.0 tons, and this may be that iron filings are also impure in addition owing to lost when filtering.
Press 200 yuan per ton of waste iron filing, ferrous sulfate 400 elements per ton, economic benefit amount of the present invention is very considerable, for example
One overlaps per hour smoke treatment 30000Nm
3The desulfurizer of/h comprises the device that multifunctional ceiling receiving apparatus and reclaim sulfuric acid are ferrous, need invest 300,000 yuan approximately, handles to contain SO
25000mg/m
3Flue gas, need iron filings 1814Kg every day, can get 8.16 tons in ferrous sulfate, every day revenue and expenditure profit such as following table four:
Calculate thus, go into operation 8 months profitable 300,000 yuan, promptly recoverable fully invested.37.6 ten thousand yuan of annual profits, profit-investment ratio is 125%, the project of high like this profit-investment ratio also is rare.
As for lacking the SO that hands over thus
2Charges for disposing pollutants do not count as yet, and environmental benefit and the social benefit of improving air quality also are beyond measure.
For miniature boiler, kiln, can several Combined Treatment nearby, only need to be connected to the disposal field and get final product with pipeline, economy also is very significant.A spot of ferrous sulfate enters environment, also unlikelyly causes great harm.
By above-mentioned analysis, the characteristics of this law are the treatment of wastes with processes of wastes against one anothers, make a silk purse out of a sow's ear, and turn harm into good, and the coal sulfur content is higher, SO in the flue gas
2Concentration is higher, the iron filings of consumption the more, the ferrous sulfate of gained also the more, economic benefit is also better.
As the present invention is compared with other methods of administering with iron oxide, its superiority is also very remarkable, and is existing by handling SO per ton
2The main material that consumes does one relatively, sees Table five: (continued on next page)
By above analysis as can be known, a new breakthrough of amount fume desulphurization method of the present invention, particularly very suitable to the sulphur coal area, if own waste iron filing is machine works or each class factory that has the machine repair workshop, use this rule benefit more remarkable.
Claims (7)
1, a kind of flue-gas desulfuration method and device thereof is characterized in that: add water with waste iron filing and absorb sulfur in smoke; Can add sorbefacient catalyst in the process that absorbs sulfur dioxide.
2, fume desulphurization method as claimed in claim 1, it is characterized in that: catalyst is selected granular active carbon for use.
3, fume desulphurization method as claimed in claim 1 is characterized in that: catalyst is selected granular carbon for use.
4, fume desulphurization method as claimed in claim 1, it is characterized in that: catalyst is selected copper scale for use.
5, fume desulphurization method as claimed in claim 1, it is characterized in that: catalyst is selected salt for use.
6, fume desulphurization method as claimed in claim 1, it is characterized in that: catalyst is selected coal ash for use.
7, the employed absorption plant of flue-gas desulfuration method as claimed in claim 1, it is characterized in that: with cooling, absorption, oxygenating, evaporate, be combined in the structures, concentrated liquid pool 13 and absorption liquid pool 14 that its bottom is and connects, the cooling tower 3 and the desulfurizing tower 4 that on it are and connect, there is convex duct 15 to be connected between two towers, its top is cooling oxygenating tower 5, there are two pumps 8,9 to make concentrate and absorption liquid circulation, have two ball-cock assemblys 10,11 to control the liquid level of concentrate and absorption liquid automatically.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111928 CN1073613A (en) | 1992-09-30 | 1992-09-30 | Flue-gas desulfuration method and device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111928 CN1073613A (en) | 1992-09-30 | 1992-09-30 | Flue-gas desulfuration method and device thereof |
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| CN1073613A true CN1073613A (en) | 1993-06-30 |
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| CN 92111928 Pending CN1073613A (en) | 1992-09-30 | 1992-09-30 | Flue-gas desulfuration method and device thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101248C (en) * | 2000-03-28 | 2003-02-12 | 林新 | Wet boiler fume desulfurizing and dedusting technology |
| CN1102422C (en) * | 2000-01-18 | 2003-03-05 | 大连理工大学 | Flue gas wet desulfuration and denitration purification process |
| CN100351004C (en) * | 2001-10-17 | 2007-11-28 | 三菱重工业株式会社 | Flue gas desulfurization apparatus, flue gas desulfurization system, and method for operating flue gas desulfurization apparatus |
| CN101306321B (en) * | 2008-07-15 | 2011-02-16 | 李宝林 | Coal smoke desulfurization and dust removal device and its use method |
| CN101474528B (en) * | 2008-12-31 | 2011-05-11 | 宁波金远东工业科技有限公司 | Device for removing sulfuric dioxide in exhaust gas |
| CN107596870A (en) * | 2017-10-30 | 2018-01-19 | 东方电气集团东方锅炉股份有限公司 | A kind of flue gas desulfurization with seawater absorption tower |
| CN107774082A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method and device of flue gas desulfurization |
| CN109276995A (en) * | 2018-11-21 | 2019-01-29 | 安徽工业大学 | A kind of sintering flue gas and kiln gas iron catalytic desulfurization device and method |
-
1992
- 1992-09-30 CN CN 92111928 patent/CN1073613A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102422C (en) * | 2000-01-18 | 2003-03-05 | 大连理工大学 | Flue gas wet desulfuration and denitration purification process |
| CN1101248C (en) * | 2000-03-28 | 2003-02-12 | 林新 | Wet boiler fume desulfurizing and dedusting technology |
| CN100351004C (en) * | 2001-10-17 | 2007-11-28 | 三菱重工业株式会社 | Flue gas desulfurization apparatus, flue gas desulfurization system, and method for operating flue gas desulfurization apparatus |
| CN101306321B (en) * | 2008-07-15 | 2011-02-16 | 李宝林 | Coal smoke desulfurization and dust removal device and its use method |
| CN101474528B (en) * | 2008-12-31 | 2011-05-11 | 宁波金远东工业科技有限公司 | Device for removing sulfuric dioxide in exhaust gas |
| CN107774082A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method and device of flue gas desulfurization |
| CN107596870A (en) * | 2017-10-30 | 2018-01-19 | 东方电气集团东方锅炉股份有限公司 | A kind of flue gas desulfurization with seawater absorption tower |
| CN107596870B (en) * | 2017-10-30 | 2023-07-07 | 东方电气集团东方锅炉股份有限公司 | Seawater flue gas desulfurization absorption tower |
| CN109276995A (en) * | 2018-11-21 | 2019-01-29 | 安徽工业大学 | A kind of sintering flue gas and kiln gas iron catalytic desulfurization device and method |
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