CN102688683B - Method and device for performing oxidization desulfurization with carbide slag as desulfurizer outside tower - Google Patents
Method and device for performing oxidization desulfurization with carbide slag as desulfurizer outside tower Download PDFInfo
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- CN102688683B CN102688683B CN201210166916.5A CN201210166916A CN102688683B CN 102688683 B CN102688683 B CN 102688683B CN 201210166916 A CN201210166916 A CN 201210166916A CN 102688683 B CN102688683 B CN 102688683B
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 105
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 61
- 239000002893 slag Substances 0.000 title claims abstract description 52
- 230000023556 desulfurization Effects 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 171
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000003546 flue gas Substances 0.000 claims abstract description 101
- 230000003647 oxidation Effects 0.000 claims abstract description 94
- 238000010521 absorption reaction Methods 0.000 claims abstract description 90
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 22
- 239000010440 gypsum Substances 0.000 claims abstract description 22
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- 239000007787 solid Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
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- 238000000926 separation method Methods 0.000 claims description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 36
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 27
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 abstract description 23
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- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
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Abstract
The invention discloses a method and a device for performing oxidization desulfurization with carbide slag as desulfurizer outside a tower. The device comprises an absorption tower, an oxidation pond and pulping pond, a stirrer and an oxidation air pipe are disposed on the oxidation pond, a vertical flue communicated with the oxidation pond is disposed on the upper side of the oxidation pond, a flue gas inlet is arranged on the inner lower portion of the vertical flue, a washing spraying layer is arranged on the inner upper portion of the vertical flue and communicated with the pulping pond by a pipeline with a pump, an oblique flue is arranged in the middle of the vertical flue and communicated with the absorption tower, and a kettle of the absorption tower is communicated with the pulping pond by a pipeline with a pump. Flue gas in the vertical flue reversely contacts with carbide slag and calcium sulfite slurry, sulfur dioxide and heat in the flue gas are absorbed, so that the pH (potential of hydrogen) value of the slurry is reduced, the temperature of the slurry is increased, sulfide in the slurry volatilizes into the flue gas in the form of H2S and flows to the absorption tower along with the flue gas, a part of the H2S in the absorption tower is absorbed by carbide slag slurry in the absorption tower, and a part of the H2S is exhausted along with the flue gas. By the aid of the method and the device, oxidization rate of calcium sulfite is guaranteed, and the quality of gypsum is improved.
Description
Technical field
The present invention relates to flue gas desulfurization field, be specifically related to a kind of tower external oxidation sulfur method and device that carbide slag is desulfurizing agent of take.
Background technology
Carbide slag is the discarded object after industry acetylene processed, and main component is Ca (OH)
2, also containing plurality of impurities simultaneously, main manifestations is a small amount of sulfide, cyanide, the oxides of iron magnesium-aluminum-calcium etc., because of Ca in carbide slag (OH)
2dissolution rate is compared with CaCO
3greatly, and content is generally in 65 ~ 85% left and right, can be used for desulfurization, and desulfuration efficiency generally can reach 95 ~ 98%.
For example, notification number is that the Chinese invention patent of CN 101642674 B discloses the pretreated wet fuel gas desulfurizing technology of a kind of carbide slag, the carbide slag slurry of usining carries out wet desulphurization processing as desulfurizing agent to flue gas, in carbide slag slurry, add catalyst, and blast air and carry out oxidation reaction, the carbide slag slurry after oxidation reaction is re-used as desulfurizing agent and carries out smoke-gas wet desulfurization processing.Application publication number is that the Chinese invention patent document of CV101816891 A discloses the pretreated ozonation and wet-method flue gas desulphurization process of a kind of carbide slag, the carbide slag of usining carries out wet desulphurization as desulfurizing agent to flue gas, in calcium carbide scorification slag process, pass into the gaseous mixture of ozone and oxygen, carry out oxidation reaction, the carbide slag slurry after oxidation carries out flue gas desulfurization as desulfurizing agent.Above technique all be take carbide slag as desulfurizing agent, and its desulfuration efficiency all reaches more than 95%.
But, because contain plurality of impurities, great many of experiments work and engineering practice have proved carbide slag medium sulphide content in carbide slag, do not affect carbide slag slurry and absorb SO in flue gas
2, but inferior sulfate radical oxidizing process is had to material impact, sulfide a small amount of in carbide slag-gypsum slurries can reduce the average oxidation rate of calcium sulfite, when sulfide content surpasses 10mmol/L, blasts inferior sulfate radical in air 5h oxidation reaction occurs hardly.
When carbide slag-gypsum slurries pH value is lower, the sulfide in carbide slag-gypsum slurries can be with H
2the form of S escapes out, thereby can effectively avoid the enrichment in slurries of carbide slag medium sulphide content to impact calcium sulfite oxidation process, but in general carbide slag sulfur removal technology, lower slurry pH value will be unfavorable for SO in flue gas
2absorption.
Publication number is that the Chinese invention patent document of CN101229473A discloses a kind of tower external oxidation lime/acetylene sludge-gypsum process desulphurization technology and device, its technique comprises that initial flue gas is passed into desulfurizing tower to react with lime/carbide slag slurry, after sulfur dioxide in flue gas is absorbed by lime/carbide slag slurry, gas cleaning is discharged, lime/carbide slag slurry becomes desulfurization slurry in desulfurizing tower after sulfur dioxide absorption, desulfurization slurry is discharged desulfurizing tower and is passed into oxidation tank, a described initial flue gas part passes in desulfurizing tower reacts with lime/carbide slag slurry, another part passes into oxidation tank and adjusts slurry pH value to 3.0 ~ 5.5, to passing into oxygen and desulfurization slurry in oxidation tank, carry out oxidation reaction and generate desulfurated plaster and reclaim again.In this tower external oxidation technique, flue gas adopts the form of bubbling, blasts in oxidation pond, reduces slurry pH value, and because slurries do not disperse, and temperature is lower, the H of generation
2s is difficult to volatilization, can not effectively reduce the content of slurries medium sulphide content, and in the higher carbide slag-gypsum slurries of sulfide enrichment, oxidation rate still can be suppressed, and affects gypsum qualitt.
Summary of the invention
The invention provides a kind of sulfur method and device that carbide slag is desulfurizing agent of take, overcome the inhibitory action of carbide slag medium sulphide content to calcium sulfite oxidation, desulfuration efficiency that can stable electrical rock ballast, can guarantee again calcium sulfite slurries oxidation rate, improves gypsum qualitt.
The tower external oxidation sulfur method that the carbide slag of take is desulfurizing agent, take carbide slag as desulfurizing agent carries out wet desulphurization to flue gas, comprising:
(1) described flue gas and carbide slag-calcium sulfite slurries haptoreaction obtain desulfurization slurry A, the pH value of described desulfurization slurry A is 3 ~ 5, after oxidation gypsum slurries, described gypsum slurries must push up stream slurries and underflow slurries after cyclonic separation, the described underflow slurries gypsum that dewaters to obtain;
(2) flue gas described in and after carbide slag-calcium sulfite slurries haptoreaction enters in absorption tower and obtains purifying smoke and desulfurization slurry B with carbide slag slurry haptoreaction, and described desulfurization slurry B makes described carbide slag-calcium sulfite slurries after changing slurry.
Carbide slag carries out flue gas desulfurization as desulfurizing agent, and its desulfuration efficiency is higher, but the reducing substances containing in carbide slag (being mainly sulfide) can produce inhibitory action to the oxidation of calcium sulfite, is unfavorable for the recovery of desulfurated plaster and utilization.When slurry pH value is lower, the sulfide in slurries can be with H
2the form of S escapes out, but too low pH value is unfavorable for the absorption of sulfur dioxide, so the present invention adopts tower external oxidation method, under high pH value condition, and SO in slurries absorption flue gas
2, under low ph condition, calcium sulfite slurries generation oxidation reaction, can guarantee desulfuration efficiency, also can avoid slurries medium sulphide content to suppress calcium sulfite oxidation, improves oxidation efficiency and gypsum qualitt.Described flue gas is before entering absorption tower, carry out pre-wash with carbide slag-calcium sulfite slurries in advance, these carbide slag-calcium sulfite slurries are that the desulfurization slurry B in origin self-absorption tower is formulated, carbide slag-calcium sulfite slurries absorb a part of sulfur dioxide and obtain desulfurization slurry A, the pH value of desulfurization slurry A will be low to moderate 3 ~ 5, be beneficial to the oxidation of calcium sulfite and the S in slurries
2-with H
+react and generate H
2s, meanwhile, the heat that carbide slag-calcium sulfite slurries absorb in flue gas raises the temperature of desulfurization slurry A, is beneficial to H
2the volatilization of S.
In flue gas desulfurization course, with how many meetings of solid concentration in the catalytic slurries of flue gas, the absorption of sulfur dioxide in flue gas is affected, when solid concentration is lower in slurries in general situation, be conducive to the absorption of sulfur dioxide, but too low solid content can affect desulfuration efficiency, therefore, a kind of preferred technical scheme in the present invention, the solid concentration in described carbide slag-calcium sulfite slurries is less than 7%.
More preferably, described solid concentration is less than carbide slag-calcium sulfite slurries of 7% and take volume ratio as 7 ~ 10 by described desulfurization slurry B and described top stream slurries: 1 ratio is mixed.
In described carbide slag-calcium sulfite slurries, contain mainly with S
2-the sulfide that form exists, this S
2-pH value be 3 ~ 5 o'clock with slurries in H
+reaction generates H
2s, this H
2s enters in flue gas after volatilizing with gas form, has so just reduced the content of desulfurization slurry A medium sulphide content, is conducive to the oxidation of calcium sulfite in desulfurization slurry A, improves the purity of desulfurated plaster and the moisture content of reduction desulfurated plaster, H
2the volatilization of S needs slurries to rise to certain temperature, therefore, a kind of preferred technical scheme, the temperature of described desulfurization slurry A is 50 ~ 75 ℃, this temperature reaches by the heat absorbing in flue gas.
Due to flue gas before entering absorption tower with carbide slag-calcium sulfite slurries haptoreaction, the heat that carbide slag-calcium sulfite slurries sponge in flue gas reduces the temperature of flue gas, therefore, flue gas did not need the processing of lowering the temperature before entering absorption tower, save cooling treatment facility, saved production cost.
In flue gas desulfurization course, according to the content of sulfur dioxide in flue gas, regulate desulfurizer slurry pH value, when general sulfur dioxide in flue gas content is higher, require the pH value of desulfurizer slurry higher, preferably, the pH value of described carbide slag slurry is 5 ~ 8.Within the scope of this pH value, can guarantee the high-efficiency desulfurization efficiency of flue gas.
Described flue gas and the catalytic liquid-gas ratio of carbide slag-calcium sulfite slurries are 0.5 ~ 1L/m
3, according to pH in absorption tower and slurries treating capacity, regulate liquid-gas ratio; Flue gas after described and carbide slag-calcium sulfite slurries haptoreaction enters on the absorption tower in and the catalytic liquid-gas ratio of carbide slag slurry is 3 ~ 5L/m
3.The control of liquid-gas ratio is according to the content adjustment of sulfur dioxide to be absorbed in flue gas, the haptoreaction main purpose of flue gas and carbide slag-calcium sulfite slurries is the pH values that reduce in slurries, remove the sulfide in slurries, only absorb the small part sulfur dioxide in flue gas, and with the catalytic main purpose of carbide slag slurry be the sulfur dioxide absorbing in flue gas, so its liquid-gas ratio will exceed flue gas and the catalytic liquid-gas ratio of carbide slag-calcium sulfite slurries.
The present invention also provides a kind of tower external oxidation desulfurizer that carbide slag is desulfurizing agent of take, and comprises absorption tower, oxidation pond and change stock tank, is provided with agitator and oxidation airduct in described oxidation pond; Described oxidation pond top is provided with the vertical flue being communicated with it; In described vertical flue, bottom is provided with smoke inlet, and top is provided with wash spray layer, and described wash spray layer is communicated with describedization stock tank by the pipeline with pump; Described vertical flue middle part is provided with inclination flue and is communicated with described absorption tower, and one end that described inclination flue is communicated with described absorption tower is lower than the one end being communicated with described vertical flue; The tower reactor on described absorption tower is communicated with describedization stock tank by the pipeline with pump.
Described flue gas is entered in vertical flue by smoke inlet, and motion from bottom to top, with reverse contact of carbide slag-calcium sulfite slurries of wash spray layer atomization, the SO of described carbide slag-calcium sulfite slurries absorption portion
2rear formation desulfurization slurry A, desulfurization slurry A falls in oxidation pond, in oxidation pond, blasts oxidation air, is oxidized to gypsum slurries.
Owing to having absorbed the SO in flue gas
2, the pH value of desulfurization slurry A is down to 3 ~ 5, and simultaneously because flow of flue gas is very fast, flue-gas temperature is higher, and carbide slag-calcium sulfite slurries have absorbed the heat in flue gas makes the temperature of desulfurization slurry A rise to 50 ~ 75 ℃, the S under lower pH value in slurries drop
2-with H
+react and generate H
2s, at the lower H of higher temperature (50 ~ 75 ℃)
2s is easier to volatilize in flue gas with the form of gas, by flue gas, is taken away, and reduces the sulfide content in slurries, is conducive to the oxidation of calcium sulfite, is conducive to the oxidation of calcium sulfite under simultaneously lower pH value.
There is vaporization and with flow of flue gas in the liquid of part, the segment distance that declines after the upper end face buffering of vertical flue enters absorption tower through inclination flue, flue gas is in decline process, the liquid condensation again that part is vaporized, by inclination flue, fallen after rise to the tower reactor of absorption tower, the liquid that remainder is vaporized continues in absorption tower with flue gas to move upward.
Enter the flue gas on absorption tower, contact and mass-and heat-transfer reaction, most SO in flue gas occur with the carbide slag slurry of atomization is reverse
2by slurries, absorbed, and generate calcium sulfite, because of H
2s is water-soluble far below SO
2, part H in flue gas
2s is again absorbed by slurries in absorption tower, and part will be discharged with purifying smoke, H in purifying smoke
2s content seldom, can't impact environment, meets discharging standards.The pH value of carbide slag slurry is controlled at 5 ~ 8, and higher pH value is conducive to SO in flue gas
2absorption, improve desulfuration efficiency.
In absorption tower, carbide slag slurry absorbs the SO in flue gas
2after fall in the tower reactor on absorption tower, in the tower reactor on absorption tower, be mixed to get desulfurization slurry B with fresh carbide slag slurry, a mixed desulfurization slurry B part continues circulated sprinkling, a part of in delivering to of the pipeline stock tank with pump, after changing slurry, obtain described carbide slag-calcium sulfite slurries, for the flue gas spray washing in vertical flue, the flue gas after purifying in absorption tower is discharged by the exhanst gas outlet at top, absorption tower.
In flue gas desulfurization course, according to the content of sulfur dioxide in flue gas, need in the time of staying in vertical flue, control flue gas, therefore, a kind of preferred technical scheme, described vertical flue cross section is rectangle, and the width on top is greater than bottom, and its change width place is communicated with described inclination flue, in described vertical flue, be provided with along vertical dividing plate with inclination flue connectivity part, on described dividing plate, edge is higher than described wash spray layer.The time of staying of flue gas in vertical flue controlled by adjusting the height of dividing plate.
More preferably, described vertical flue top is arc, is set to ellipse or semicircle.After the slurries haptoreaction that described flue gas moves upward with downward spray in vertical flue, slurries fall to oxidation pond, and flue gas is carried part steam secretly and continued to fall after the arc dome buffering by top upwards after the distance of 3 ~ 5m and enter absorption tower by inclination flue.
Owing to being entrained with part steam in the flue gas that enters absorption tower by vertical flue, therefore, described vertical flue is set to skewed with the flue that is communicated with between absorption tower, entrance on absorption tower is downward-sloping, like this, flue gas when entering absorption tower, after the part steam condensation of carrying secretly in flue gas by the landing of inclination flue to the tower reactor on absorption tower, a preferred technical scheme, the center line of described inclination flue becomes 15 ~ 75 ° of angles with the center line on described absorption tower.
In oxidation pond, pass into oxidation air, agitator stirs slurries, and slurries are fully mixed with oxidation air, for oxidation air can be contacted to greatest extent with slurries, a preferred technical scheme, the shaft of described agitator is horizontal by 15 ~ 45 ° of angles, and blade is downward; Described oxidation airduct air outlet is positioned at described blade the place ahead 45 ~ 50cm, 20 ~ 25cm region, side.The bubbling mouth of oxidation airduct is that air outlet is arranged on before stirrer paddle, and bubble out just can disperse under the effect of stirrer paddle, guarantees that gas-liquid better contacts, and contact area is large as far as possible.
In this region, pass into oxidation air, oxidation air can reach to greatest extent and contact with slurries, and the calcium sulfite in slurries can be fully oxidized.
Described oxidation airduct can level insert, and also can vertically insert, as long as the air outlet of oxidation airduct is in above-mentioned zone.
The number of plies of described wash spray layer is 3 layers, the some nozzles on pipeline and pipeline, consists of.
Described absorption tower is optional from spray column, eddy flow tower, sieve-plate tower etc., preferably, select spray column, in tower, be from top to bottom demister, atomizing spray pipe, smoke absorption district and tower reactor, at top, absorption tower, exhanst gas outlet is set, between tower reactor and spraying layer, by circulating pump, be communicated with, the tower reactor on absorption tower by the pipeline with pump with change stock tank and be communicated with.
Beneficial effect of the present invention:
(1) before absorption tower, set up the vertical flue of spray, can effectively reduce carbide slag-calcium sulfite slurry pH value, reduce the content of slurries medium sulphide content, improve calcium sulfite oxidation speed and gypsum qualitt.
(2) vertically the interior sprayed slurry of flue can play the effect that reduces flue-gas temperature simultaneously, in not using the desulphurization system of flue gas heat-exchange unit (GGH), can save sulfur removal technology Central Plains smoke temperature reducer; Oxidation pond is communicated with vertical flue, can save flue gas air mixing device.
(3) flue gas is through twice spray-absorption, and desulfuration efficiency is higher.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
In figure, Reference numeral is as follows:
1-demister, 2-atomizing spray pipe, 3-absorption tower
4-circulating pump 1-oxidation airduct, 6-agitator
7-oxidation pond 8-change stock tank, 9-smoke inlet
10-vertical flue 11-dividing plate 12-wash spray layer
13-dome, 14-inclination flue, 15-exhanst gas outlet
16-smoke absorption district, 17-tower reactor, 18-circulating pump two
19-circulating pump, three C-raw flue gas D-gypsum slurries
Flue gas G after the F-purification of E-carbide slag slurry-cyclone top stream slurries.
The specific embodiment
As shown in Figure 1, a kind of tower external oxidation desulfurizer, comprises absorption tower 3, oxidation pond 7, vertical flue 10, inclination flue 14 and changes stock tank 8.
Spray column is selected on absorption tower 3,3 inside, absorption tower are followed successively by demister 1, atomizing spray pipe 2, smoke absorption district 16 and tower reactor 17 from top to bottom, on absorption tower, 3 tops arrange exhanst gas outlet 15, atomizing spray pipe 2 arranges three layers, every one deck is all communicated with tower reactor 17 by circulating pump 1, circulating pump 1 is set to three, corresponding three layers of atomizing spray pipe 2, and absorption tower 3 is communicated with desulfurizing agent adding set (not shown).
Vertically the top of flue 10 is set to oval-shaped dome 13, vertically in flue 10, arranging along vertically to the dividing plate 11 paralleling with vertical flue 10 sidewalls with inclination flue 14 connectivity parts, a side that is vertically positioned at dividing plate 11 in flue 10 is communicated with inclination flue 14, opposite side top arranges wash spray layer 12, bottom arranges smoke inlet 9, the upper edge of dividing plate 11 is higher than wash spray layer 12, and the height of dividing plate 11 is adjustable, but along remaining, exceed wash spray layer 12 on it.
At near setting stock tank 8 oxidation pond 7, change between stock tank 8 and wash spray layer 12 and passing through the pipeline connection with circulating pump 2 18, with the pipeline of circulating pump 2 18, be set to three, corresponding with the number of plies of wash spray layer 12.
Between change stock tank 8 and tower reactor 17, by the pipeline connection with circulating pump 3 19, change the interior top agitator that arranges of stock tank 8.
Technological process of the present invention is as follows:
Raw flue gas C is entered in vertical flue 10 by smoke inlet 9, and motion from bottom to top, with reverse contact of carbide slag-calcium sulfite slurries being sprayed by wash spray layer 12, the SO of carbide slag-calcium sulfite slurries absorption portion
2rear formation desulfurization slurry A, desulfurization slurry A falls in oxidation pond 7, by oxidation airduct 5, in oxidation pond 7, blasts oxidation air, is oxidized to gypsum slurries D.
Gypsum slurries D sends to hydrocyclone, after cyclonic separation, underflow slurries are sent to gypsum dehydration equipment, in cyclone top sending to of stream slurries G stock tank 8, mix and make carbide slag-calcium sulfite slurries that solid concentration is less than 7% with desulfurization slurry B from tower reactor 17, for the flue gas washing spray in vertical flue 10.
Owing to having absorbed the SO in flue gas
2, the pH value of desulfurization slurry A is down to 2 ~ 5, and simultaneously owing to having absorbed the heat in flue gas, the temperature of desulfurization slurry A rises to 50 ~ 75 ℃, due to H
2the water-soluble pH value with slurries of S changes greatly, the S under lower pH value in slurries
2-with H
+react and generate H
2s, H at 50 ~ 75 ℃ of higher temperature
2s volatilizees in flue gas with the form of gas, by flue gas, is taken away, and reduces the sulfide content in desulfurization slurry A, is conducive to the oxidation of calcium sulfite, is conducive to the oxidation of calcium sulfite under simultaneously lower pH value.
In the interior flue gas continuation rising after spray washing of vertical flue 10, carrying some steam decline 4 ~ 5m after the dome face buffering of vertical flue 10 secretly is entered in absorption tower 3 by the flue 14 that tilts, steam in flue gas through 14 landings of inclination flue to tower reactor 17, on absorption tower, 3 interior continuation move upward flue gas, the reverse contact of carbide slag slurry with downward spray, carry out mass transfer and the reaction of conducting heat, most SO in flue gas
2by slurries, absorbed, and generate calcium sulfite, H in flue gas
2s concentration is very low, not higher than 10mg/Nm
3, but small part H
2s contacts with slurries and still has the possibility again being absorbed by slurries, and major part is discharged by exhanst gas outlet 15 after demister 1 demist with flue gas, because discharging H in flue gas
2s content seldom, can not impact environment, meets discharging standards.In absorption tower 3, the pH value of carbide slag slurry is controlled at 5 ~ 8, and higher pH value is conducive to the absorption of sulfur dioxide in flue gas, improves desulfuration efficiency.
In absorption tower 3, carbide slag slurry absorbs the SO in flue gas
2after fall in tower reactor 17, in tower reactor 17, be mixed to get desulfurization slurry B with fresh carbide slag slurry, a mixed desulfurization slurry B part continues circulated sprinkling, a part of in delivering to of the pipeline stock tank 8 with circulating pump 1, stream slurries G is hybridly prepared into carbide slag-calcium sulfite slurries that solid concentration is less than 7% with cyclone top, for the flue gas spray washing in vertical flue 10, cyclone top stream slurries G is 7 ~ 10: 1 with the mixed volume ratio of desulfurization slurry B from tower reactor.
Carbide slag slurry E adds equipment by desulfurizing agent and inputs in absorption tower 3.
In flue gas desulfurization course, according to SO in flue gas
2content need in the time of staying in vertical flue 10, control flue gas, this time of staying is controlled by adjusting the height of dividing plate 11.
Following examples all adopt said apparatus and technique to complete.
Embodiment 1
From the raw flue gas of boiler, exhaust gas volumn 150000m
3/ h, gas approach sulfur dioxide concentration 2000mg/Nm
3, design liquid-gas ratio 0.5L/m in vertical pipeline
3, design liquid-gas ratio 3L/m in absorption tower
3, pH value 6.5 in absorption tower, temperature 50 C, changes the interior slurries medium sulphide content content of stock tank (with S
2-meter) 200mg/L, pH value 3.0 in oxidation pond, 65 ℃ of temperature, sulfide content is (with S
2-meter) 35mg/L, changing stock tank inward eddy device top stream slurries and absorption tower prime cement liquid mixed proportion is 9: 1, solid content is 4%, desulfuration efficiency 95%, desulfurated plaster moisture content is less than 10%, purity 91%, particle diameter 60 ~ 100 μ m, remaining calcium sulfite amount 0.002%.
From the raw flue gas of boiler, exhaust gas volumn 200000m
3/ h, gas approach sulfur dioxide concentration 2500mg/Nm
3, design liquid-gas ratio 0.6L/m in vertical pipeline
3, design liquid-gas ratio 3L/m in absorption tower
3, pH value 7.0 in absorption tower, 55 ℃ of temperature, change the interior slurries medium sulphide content content of stock tank (with S
2-meter) 150mg/L, pH value 3.2 in oxidation pond, 68 ℃ of temperature, sulfide content is (with S
2-meter) 30mg/Lization stock tank inward eddy device top stream slurries and absorption tower prime cement liquid mixed proportion are 9: 1, and solid content is 5%, desulfuration efficiency 96%, and desulfurated plaster moisture content is less than 10%, purity 90%, particle diameter 54 ~ 95 μ m, remaining calcium sulfite amount 0.001%.
From the raw flue gas of boiler, exhaust gas volumn 250000m
3/ h, gas approach sulfur dioxide concentration 5000mg/Nm
3, design liquid-gas ratio 0.8L/m in vertical pipeline
3, design liquid-gas ratio 5L/m in absorption tower
3, pH value 7.2 in absorption tower, 55 ℃ of temperature, change the interior slurries medium sulphide content content of stock tank (with S
2-meter) 186mg/L, pH value 4.1 in oxidation pond, 68 ℃ of temperature, sulfide content 35mg/L, changing stock tank inward eddy device top stream slurries and absorption tower prime cement liquid mixed proportion is 8: 1, solid content is 7%, desulfuration efficiency 94.1%, desulfurated plaster moisture content is less than 9%, purity 91%, particle diameter 50 ~ 100 μ m, remaining calcium sulfite amount 0.004%.
Embodiment 4
From the raw flue gas of boiler, exhaust gas volumn 190000m
3/ h, gas approach sulfur dioxide concentration 3400mg/Nm
3, design liquid-gas ratio 0.5L/m in vertical pipeline
3, design liquid-gas ratio 4L/m in absorption tower
3, pH value 7.0 in absorption tower, 52 ℃ of temperature, change the interior slurries medium sulphide content content of stock tank (with S
2-meter) pH value 3.6 in 200mg/L oxidation pond, 65 ℃ of temperature, sulfide content is (with S
2-meter) 28mg/L, changing stock tank inward eddy device top stream slurries and absorption tower prime cement liquid mixed proportion is 9: 1, solid content is 4.6%, desulfuration efficiency 96.5%, desulfurated plaster moisture content 10%, purity 91%, particle diameter 43 ~ 90 μ m, remaining calcium sulfite amount 0.015%.
The foregoing is only better implementation example of the present invention, be not limited to the present invention, all within the present invention spirit and principle, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the tower external oxidation sulfur method that the carbide slag of take is desulfurizing agent, take carbide slag as desulfurizing agent carries out wet desulphurization to flue gas, it is characterized in that, comprising:
(1) described flue gas and carbide slag-calcium sulfite slurries haptoreaction obtain desulfurization slurry A, the pH value of described desulfurization slurry A is 3～5, after oxidation gypsum slurries, described gypsum slurries must push up stream slurries and underflow slurries after cyclonic separation, the described underflow slurries gypsum that dewaters to obtain;
(2) flue gas described in and after carbide slag-calcium sulfite slurries haptoreaction enters in absorption tower and obtains purifying smoke and desulfurization slurry B with carbide slag slurry haptoreaction, and described desulfurization slurry B makes described carbide slag-calcium sulfite slurries after changing slurry;
The tower external oxidation desulfurizer of realizing described tower external oxidation sulfur method comprises: absorption tower (3), oxidation pond (7) and change stock tank (8), be provided with agitator (6) and oxidation airduct (5) in described oxidation pond (7); Described oxidation pond (7) top is provided with the vertical flue (10) being communicated with it; The interior bottom of described vertical flue (10) is provided with smoke inlet (9), and top is provided with wash spray layer (12), and described wash spray layer (12) is communicated with describedization stock tank (8) by the pipeline with pump; Described vertical flue (10) middle part is provided with inclination flue (14) and is communicated with described absorption tower (3), and one end that described inclination flue (14) is communicated with described absorption tower (3) is lower than the one end being communicated with described vertical flue (10); The tower reactor on described absorption tower (3) is communicated with describedization stock tank (8) by the pipeline with pump.
2. tower external oxidation sulfur method according to claim 1, is characterized in that, the solid concentration in described carbide slag-calcium sulfite slurries is less than 7%.
3. tower external oxidation sulfur method according to claim 2, is characterized in that, described carbide slag-calcium sulfite slurries be take by described desulfurization slurry B and described top stream slurries the ratio that volume ratio is 7～10:1 and are mixed.
4. tower external oxidation sulfur method according to claim 1, is characterized in that, the temperature of described desulfurization slurry A is 50～75 ℃.
5. tower external oxidation sulfur method according to claim 1, is characterized in that, the pH value of described carbide slag slurry is 5～8.
6. the tower external oxidation desulfurizer that the carbide slag of take is desulfurizing agent, comprises absorption tower (3), oxidation pond (7) and changes stock tank (8), it is characterized in that, is provided with agitator (6) and oxidation airduct (5) in described oxidation pond (7); Described oxidation pond (7) top is provided with the vertical flue (10) being communicated with it; The interior bottom of described vertical flue (10) is provided with smoke inlet (9), and top is provided with wash spray layer (12), and described wash spray layer (12) is communicated with describedization stock tank (8) by the pipeline with pump; Described vertical flue (10) middle part is provided with inclination flue (14) and is communicated with described absorption tower (3), and one end that described inclination flue (14) is communicated with described absorption tower (3) is lower than the one end being communicated with described vertical flue (10); The tower reactor on described absorption tower (3) is communicated with describedization stock tank (8) by the pipeline with pump.
7. tower external oxidation desulfurizer according to claim 6, it is characterized in that, described vertical flue (10) cross section is rectangle, and the width on top is greater than bottom, its change width place is communicated with described inclination flue (14), in described vertical flue (10), be provided with along vertical dividing plate (11) with inclination flue (14) connectivity part, the upper edge of described dividing plate (11) is higher than described wash spray layer (12).
8. tower external oxidation desulfurizer according to claim 7, is characterized in that, described vertical flue (10) top is arc.
9. tower external oxidation desulfurizer according to claim 8, is characterized in that, the center line of described inclination flue (14) becomes 15～75 ° of angles with the center line of described absorption tower (3).
10. tower external oxidation desulfurizer according to claim 6, is characterized in that, the shaft of described agitator (6) is horizontal by 15～45 ° of angles, and blade is downward; Described oxidation airduct (5) air outlet is positioned at described blade the place ahead 45～50cm, 20～25cm region, side.
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| CN104959018A (en) * | 2015-06-25 | 2015-10-07 | 浙江天蓝环保技术股份有限公司 | Device and method for redesulfuration with desulfurization ash |
| CN111847495B (en) * | 2020-08-21 | 2024-09-06 | 华润电力登封有限公司 | Process and device for producing carbide slag desulfurized gypsum |
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| CN100546698C (en) * | 2007-10-31 | 2009-10-07 | 浙江天蓝脱硫除尘有限公司 | An Oxidized Lime/Carbide Slag-Gypsum Desulfurization Process and Device Outside the Tower |
| CN102284239B (en) * | 2011-06-16 | 2012-07-18 | 煤炭工业济南设计研究院有限公司 | Desulfurization process and device based on out-of-tower circulation and independent oxidization dual-alkali methods |
| CN202590613U (en) * | 2012-05-23 | 2012-12-12 | 杭州天蓝环保设备有限公司 | Tower outside desulfurization device utilizing carbide slag as desulfurization agents |
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