CN102228777A - Double-oxidation ammonia desulfurization process and device - Google Patents
Double-oxidation ammonia desulfurization process and device Download PDFInfo
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- CN102228777A CN102228777A CN2011101328541A CN201110132854A CN102228777A CN 102228777 A CN102228777 A CN 102228777A CN 2011101328541 A CN2011101328541 A CN 2011101328541A CN 201110132854 A CN201110132854 A CN 201110132854A CN 102228777 A CN102228777 A CN 102228777A
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Abstract
The invention discloses a double-oxidation ammonia desulfurization process and a double-oxidation ammonia desulfurization device. The device comprises an ammonia water preparation device, an absorption tower, a pre-scrubber, a buffer oxidation tank, a cyclone, a centrifugal machine, a drying bed, a tail gas scrubber, a packaging machine and an ammonia water storage tank. Sulfur dioxide is removed from flue gas by liquid ammonia, and ammonium sulfate crystals with the purity of over 99 percent are obtained; and the invention has the advantages that: the cost of the conventional ammonia desulfurization is reduced, the absorption efficiency is improved, the desulfurization efficiency is over 95 percent, the yield is improved, the ammonium sulfate crystals with the purity of over 99 percent are obtained, the waste is changed into treasure, economic benefit is increased, the ammonium sulfate yield is over 96 percent, and the ammonia escape volume is reduced and is less than 8mg/m<3>.
Description
Technical field
The present invention relates to a kind of flue gas desulfurization technique, specifically a kind of dioxygen ammonia desulfurizing process and device adopt liquefied ammonia to remove sulfur in smoke, belong to chemical field.
Background technology
Along with expanding economy, the progress of society and the enhancing of people's environmental consciousness, industrial smoke removes SO2, comes into one's own day by day.
Ammonia desulfurizing process is according to ammonia and SO
2, water reaction generates that the basic mechanism of desulfurization product carries out, and mainly contains wet-type ammonia, electron beam ammonia process, impulse electric corona ammonia process, simple and easy ammonia process etc.
The wet ammonia process desulfurizing technology system is mainly by desulfurization washing system, flue gas system, ammonia storage system, ammonium sulfate production system compositions such as (if not ammonia-ammonium sulfate method, then being and the corresponding accessory substance manufacturing system of its technology).Nucleus equipment is a desulfurization washing tower.Usually adopt ammoniacal liquor as desulfurizing agent, absorption liquid adopt usually the mode of spray enter in the absorption tower with flue gas in the SO2 reaction, generate accessory substance ammonium sulfate and ammonium bisulfite, utilize the method for air aeration that ammonium bisulfite is oxidized to ammonium sulfate in desulfurizing tower bottom, after ammonium sulfate is discharged through producing sulfuric acid money crystal after filtration, dehydration, evaporation, the drying.
At present, desulfurizing tower mainly adopts the mode that absorption liquid spray absorbs in most of ammonia desulfurizing process, and the mode that this spray absorbs mainly can cause in the outlet flue gas ammonia-spillage amount big, and surrounding environment is caused secondary pollution.Also have and adopt column plate to absorb the form of sulfide in some desulfurizing towers, but because flue-gas temperature is by column plate the time, be difficult to drop to 60 ℃ of the optimum temperatures of desulfurization, after the column plate absorption liquid has absorbed the sulfide in the flue gas, under high-temperature condition, can decompose out very soon again, have only by adding excess ammonia and absorb sulfide in the flue gas, so just cause the absorbent consumption big, uneconomical, the outlet ammonia-spillage amount is also big, and sulfide and ease ammonia that outlet decomposes out also can continue reaction, accessory substance can be attached on the exhaust pass, and the amount of by-products that can collect is few, and exhaust pass easily stops up.The form that adds spray below the desulfurizing tower column plate is also arranged, but this absorption pattern, basically mainly rely on column plate to absorb, in order to guarantee desulfurization degree, must guarantee the reaction time of flue gas, so the pitch-row of tray designs is little by absorption liquid on column plate and the column plate, resistance is big, when energy consumption height, flue gas passed from the column plate liquid film, drop was carried secretly more serious.
Yet pass through to absorb oxidation in the Tata, be difficult to guarantee that the ammonium sulfate oxidization time was 5.5 greater than 2 hours with optimal pH, thereby be difficult to output ammonium sulfate; Another kind is the enriching section oxidation, yet because sulfurous acid ammonia instability, temperature just begins to decompose more than 60 ℃, if the enriching section oxidation, the high-temperature flue gas more than 130 ℃ will make a large amount of sulfurous acid ammonia decompose, and cause the absorption efficiency reduction equally, be difficult to output ammonium sulfate.
A kind of integrated desulfurization gas wash tower of ammonia process is provided in the Chinese patent 200310115523.2, this desulfurization and dedusting tower from bottom to top is provided with one-level spray section, column plate layer and demister, the deficiency of this device is to be not suitable for handling big exhaust gas volumn, and the solution on the column plate is difficult to evenly distribute when the tower diameter of desulfurizing tower is big.
Void tower type ammonia desulfurizing process and device are provided in the Chinese patent application 200510040800.7, have used this technology and device to carry out desulfurization and can when guaranteeing desulfuration efficiency, can reduce investment outlay.But this technology and device can influence the desulfurization degree of whole desulphurization system like this owing to adopted oxidation processes in the tower, if in order to guarantee desulfurization degree, add excess of ammonia gas and absorb, and the ease ammonia in the outlet flue gas is exceeded standard.
Summary of the invention
In order to address the above problem, the present invention has designed a kind of dioxygen ammonia desulfurizing process and device, comprises ammoniacal liquor preparation facilities, absorption tower, prewashing tower, buffer oxide case, cyclone, centrifuge, drying bed, exhaust scrubber, packing machine, oxidation fan, circulating pump; By carry out dioxygenization, reach effective reduction amount of ammonia slip, reduce the purpose that ammonium sulfate loses on absorption tower and buffering oxidation case.
Technical scheme of the present invention is:
The dioxygen ammonia desulfurizing process may further comprise the steps:
(1) preparation desulfurizing agent ammoniacal liquor, ammoniacal liquor is prepared by liquefied ammonia by the ammoniacal liquor preparation facilities, and the ammoniacal liquor mass fraction for preparing is 20%, is stored in the ammoniacal liquor storage tank, squeezes into absorption tower bottom circulating line by circulating pump during use;
Described ammoniacal liquor preparation process is: liquefied ammonia enters two liquefied ammonia gasification heat-exchanger rigs respectively, the ammoniacal liquor gasification is the endothermic reaction, can be with the circulating water cooling that feeds, the ammoniacal liquor cooling that will discharge simultaneously, ammoniacal liquor gas mixture after the gasification enters spraying ammoniacal liquor absorption plant, the recirculated water that feeds is mixed with preparation water, preparation quality concentration 20% ammoniacal liquor, ammoniacal liquor is tentatively lowered the temperature by ammoniacal liquor cooling device and the recirculated water that cooled off from liquefied ammonia gasification heat-exchanger rig, temperature is reduced to below 50 ℃, again by another liquefied ammonia gasification heat-exchanger rig by with the heat exchange of liquefied ammonia gasification, obtain temperature less than 25 ℃ ammoniacal liquor.The ammoniacal liquor preparation process is utilized the liquefied ammonia vaporization endothermic reaction, cooling circulating water, and the ammoniacal liquor of cooling preparation reduces cooling water amount then, reduces operating cost, removes recirculated water, equipment support that whole process is unpowered;
(2) after flue gas enters from the top of prewashing tower, cool to 60 ℃ in the prewashing tower, and spray desulfurization, spray liquid is the mixed liquor of ammoniacal liquor, ammonium sulfate and sulfurous acid ammonia, and flue gas enters the absorption tower through the bottom from the prewashing tower after the elementary desulfurization;
(3) flue gas that enters the absorption tower at first passes through porous plate, flow velocity by porous plate is 6-10m/s, flue gas evenly distributes, and form strong convection with the spray liquid of spraying layer, the liquid gas volume ratio of flue gas and spray liquid is controlled at 3～5 ﹕ 1, thereby increased the contact area of flue gas and spray liquid, further carried out desulfurization, SO in the flue gas
2With the spray liquid reaction that contains ammonium sulfate, sulfurous acid ammonia and ammonium bisulfite that discharge on the absorption tower, finish removing of sulfur dioxide, absorbed SO in the flue gas
2Spray liquid fall into the slurries pond of absorption tower bottom;
The prewashing tower is used for to flue gas cool-down, simultaneously by the SO in the flue gas
2Come the concentrated vitriol ammonium salt solution, the prewashing tower is provided with one deck spray, supplies with spray liquid by circulating pump, and the absorption tower is provided with three layers of spray, respectively corresponding three circulating pumps;
Flue gas is 3～5m/s by the flow velocity behind the porous plate in the absorption tower, does not increase the tower height on absorption tower when increasing absorption efficiency.
(4) flue gas after the desulfurization contains small amount of ammonia gas colloidal sol, removes most of ammonia of escaping by rotating plate convection current ammonia absorption plant, and then by demister dehydration, demist, removes the water smoke in the flue gas, the flue gas that is purified;
(5) be mainly saturated ammonium sulfate solution in the slurries pond, also contain sulfurous acid ammonia and ammonium bisulfite, the slurries pond is according to the height of prewashing tower liquid level, by circulating pump the ammonium sulfate in the slurries pond is drained into the prewashing tower, in the prewashing tower, ammonium sulfate is concentrated, when the mixed solution in the prewashing tower reaches weight fraction 10% through being concentrated into solid content, enter the buffer oxide case by circulating pump;
(6) oxidation sulfurous acid ammonia and ammonium bisulfite in the buffer oxide case, the pH value transfers to 4～6 in the buffer oxide case, fully oxidation sulfurous acid ammonia obtains purer ammonium sulfate, sulfate of ammoniac solution solid content in the buffer oxide case reaches weight fraction 15%, by the circulating pump of buffer oxide case sulfate of ammoniac solution is delivered to cyclone and carries out liquid-solid separation;
Preferred pH value 5.5 in the described buffer oxide case.
(7) solution further is concentrated into solid content at weight fraction 35% in cyclone, by circulating pump ammonium sulfate is entered centrifuge;
(8) by centrifuge solution is carried out Separation of Solid and Liquid, when solid content reaches weight fraction 95%, be delivered to drying bed;
(9) drying bed is provided with exhaust scrubber, finishes the byproduct packing in drying bed oven dry back by sack filling machine; Drying bed is dried to ammonium sulfate moisture 1.0%, drains into packing machine at last, the packing outward transport; The sulfur acid ammonium dust tail gas that drying bed is discharged enters exhaust scrubber, washs the back discharging, and whole process ammonium sulfate yield can reach more than 96%.
Flue gas carries out blanking from top to bottom through the whole process on absorption tower, does not increase any lifting means, has reduced the use of circulating pump, has promoted utilization rate of equipment and installations, and whole system does not have waste water, waste gas produces.
A kind of device that is used for above-mentioned dioxygen ammonia desulfurizing process comprises ammoniacal liquor preparation facilities, absorption tower, prewashing tower, buffer oxide case, cyclone, centrifuge, drying bed, exhaust scrubber, packing machine, ammoniacal liquor storage tank; Be provided with demister, rotating plate convection current ammonia absorption plant, spraying layer and porous plate in the described absorption tower from top to bottom successively, the bottom on described absorption tower is the slurries pond; Described ammoniacal liquor preparation facilities links to each other with the ammoniacal liquor storage tank, and the ammoniacal liquor storage tank links to each other with the buffer oxide case, and described prewashing tower links to each other with the bottom on absorption tower, and top, described absorption tower links to each other with chimney; Described prewashing tower is connected with the buffer oxide case, and described buffer oxide case, cyclone, centrifuge, drying bed link to each other successively, and described drying bed links to each other with exhaust scrubber with packing machine respectively.
Described ammoniacal liquor preparation facilities comprises: liquefied ammonia vaporization heat-exchanger rig, spraying ammoniacal liquor mixing arrangement, ammoniacal liquor cooling heat transferring device; Described liquefied ammonia vaporization heat-exchanger rig has two, described two liquefied ammonia vaporization heat-exchanger rig is in parallel, and be connected with spraying ammoniacal liquor mixing arrangement, described spraying ammoniacal liquor mixing arrangement is connected with described ammoniacal liquor cooling heat transferring device, and described ammoniacal liquor cooling heat transferring device is connected with described two liquefied ammonia vaporization heat-exchanger rig respectively.
Described porous plate is 1/2 porous plate.
Described buffer oxide case and slurries pond are equipped with oxidation fan.
Be provided with circulating pump between described absorption tower and the prewashing tower; Be provided with circulating pump between prewashing tower and the buffer oxide case; Be provided with slush pump between buffer oxide case and the cyclone; Be provided with slush pump between ammoniacal liquor storage tank and the buffer oxide case.
Described cyclone, exhaust scrubber and centrifuge are equipped with overfall, and the overflowing liquid of cyclone, exhaust scrubber and centrifuge is back to the buffer oxide case by the reflux line that is arranged on overfall.
Described slurries pond, prewashing tower and buffering oxidation case all are connected with a slurries case, and described slurries case is connected with a melt pit.
1/2 perforated plate construction on absorption tower has increased flue gas flow rate, under the constant situation of absorption tower height, does not influence the reaction time, forms the contact area that strong convection has increased flue gas and spray liquid with spray liquid simultaneously, has reduced the slurries internal circulating load.
Rotating plate convection current ammonia absorption plant can be removed 90% ammonia and the ammonia salt aerosol of escaping, thereby reduces amount of ammonia slip.
Cyclone, exhaust scrubber and centrifuge are equipped with overfall, and the overflowing liquid of cyclone, exhaust scrubber and centrifuge is back to the buffer oxide case by the reflux line that is arranged on overfall.
Drying bed is provided with exhaust scrubber, and the gas that the drying bed air-introduced machine is discharged reclaims the ammonium sulfate dust of being taken away by air-flow through exhaust scrubber washing, dehumidifying, thereby reduces the ammonium sulfate loss, purifies and discharges air.
The dioxygen makeup is changed to absorption tower and buffering oxidation case, has increased the ammonium sulfate oxidization time, guarantees the absorption tower ion concentration of inferior sulfate radical, lasting oxidation by the buffer oxide case, guarantee the oxidization time of sulfite ion, thereby reduced sulfite ion, improved the yield of ammonium sulfate.
The ammonia absorption liquid becomes (NH gradually in the cyclic process that absorbs flue gas
4)
2SO
3And NH
4HSO
3Mixed solution, by (NH
4)
2SO
3Solution absorbs the SO in the flue gas
2, and generate NH
4HSO
3, (NH
4)
2SO
3And NH
4HSO
3Oxidized respectively airborne dioxygen oxidation becomes (NH
4)
2SO
4And NH
4HSO
4Reaction equation is as follows:
(NH
4?)
2SO
3?+?SO
2?+?H
2O?=?2NH
4HSO
3
NH
4HSO
3?+?NH
3?=?(NH
4?)
2SO
3
2(NH
4?)
2SO
3?+?O
2?=?2?(NH
4?)
2SO
4
2NH
4?HSO
3?+?O
2?=?2NH
4?HSO
4
The invention has the advantages that: compare with existing apparatus, reduce existing ammonia process of desulfurization cost, improved absorption efficiency, desulfuration efficiency has improved output more than 95%, obtain purity at the ammonia sulfate crystal more than 99%, turn waste into wealth, increased economic benefit, the ammonium sulfate yield reaches more than 96%, reduced amount of ammonia slip, amount of ammonia slip is less than 8mg/m
3
The invention will be further described with enforcement below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 is the connection diagram of embodiment of the invention dioxygen ammonia desulfuration equipment;
Fig. 2 is the connection diagram of embodiment of the invention ammoniacal liquor preparation facilities;
Among the figure: 1-demister, 2-rotating plate convection current ammonia absorption plant, 3-spraying layer, 4-absorption tower, 41-1/2 porous plate, 42-slurries pond, 5-prewashing tower, 6-buffer oxide case, 7-cyclone, 8-centrifuge, 9-drying bed, 10-ammoniacal liquor preparation facilities, 101-ammoniacal liquor storage tank, 11-exhaust scrubber, 12-packing machine, 102-liquefied ammonia vaporization heat-exchanger rig, 103-spraying ammoniacal liquor mixing arrangement, 104-ammoniacal liquor cooling heat transferring device.
The specific embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, and be not used in qualification the present invention.
Embodiment 1
A kind of dioxygen ammonia desulfurizing process may further comprise the steps:
(1) preparation desulfurizing agent ammoniacal liquor, ammoniacal liquor is prepared by liquefied ammonia by the ammoniacal liquor preparation facilities, and the ammoniacal liquor mass fraction for preparing is 20%, is stored in the ammoniacal liquor storage tank, squeezes into absorption tower bottom circulating line by circulating pump during use;
Described ammoniacal liquor preparation process is: liquefied ammonia enters two liquefied ammonia gasification heat-exchanger rigs respectively, the ammoniacal liquor gasification is the endothermic reaction, can be with the circulating water cooling that feeds, the ammoniacal liquor cooling that will discharge simultaneously, ammoniacal liquor gas mixture after the gasification enters spraying ammoniacal liquor absorption plant, the recirculated water that feeds is mixed with preparation water, preparation quality concentration 20% ammoniacal liquor, ammoniacal liquor is tentatively lowered the temperature by ammoniacal liquor cooling device and the recirculated water that cooled off from liquefied ammonia gasification heat-exchanger rig, temperature is reduced to below 50 ℃, again by another liquefied ammonia gasification heat-exchanger rig by with the heat exchange of liquefied ammonia gasification, obtain temperature less than 25 ℃ ammoniacal liquor.The ammoniacal liquor preparation process is utilized the liquefied ammonia vaporization endothermic reaction, cooling circulating water, and the ammoniacal liquor of cooling preparation reduces cooling water amount then, reduces operating cost, removes recirculated water, equipment support that whole process is unpowered;
(2) boiler smoke enters flue after dedusting, after flue gas under the effect of air-introduced machine enters from the top of prewashing tower, in the prewashing tower, cool to about 60 ℃, and spray desulfurization, spray liquid is the mixed liquor of ammoniacal liquor, ammonium sulfate and sulfurous acid ammonia, and flue gas enters the absorption tower through the bottom from the prewashing tower after the elementary desulfurization;
(3) flue gas that enters the absorption tower at first through 1/2 porous plate (be percent opening uniform be 50% orifice plate, and plate hole evenly distributes), flow velocity is 6-10m/s, flue gas evenly distributes, and forming strong convection with the vaporific spray liquid (mixed solution of sulfurous acid ammonia and ammonium bisulfite) of squeezing into spraying layer ejection by circulating pump, the liquid gas volume ratio of flue gas and spray liquid is controlled between 3 to 5, thereby has increased the contact area of flue gas and spray liquid, further carry out desulfurization, SO in the flue gas
2With the spray liquid reaction that contains ammonium sulfate, sulfurous acid ammonia and ammonium bisulfite that discharge on the absorption tower, finish removing of sulfur dioxide, absorbed SO in the flue gas
2Spray liquid fall into the slurries pond of absorption tower bottom;
The prewashing tower is used for to flue gas cool-down, simultaneously by the SO in the flue gas
2Come the concentrated vitriol ammonium salt solution, the prewashing tower is provided with one deck spray, supplies with spray liquid by circulating pump, and the absorption tower is provided with three layers of spray, respectively corresponding three circulating pumps;
(4) flue gas after the desulfurization contains small amount of ammonia gas colloidal sol, remove most of ammonia of escaping by rotating plate convection current ammonia absorption plant, and then, remove the water smoke in the flue gas by demister dehydration, demist, the flue gas that is purified, the flue gas of purification is gone into clean flue to smoke stack emission from the absorption tower jacking;
(5) be mainly saturated ammonium sulfate solution in the slurries pond, also contain sulfurous acid ammonia and ammonium bisulfite, slurries pond at the bottom of the absorption tower is according to the height of prewashing tower liquid level, by circulating pump the ammonium sulfate in the slurries pond is drained into the prewashing tower, in the prewashing tower, ammonium sulfate is concentrated, mixed solution in the prewashing tower enters the buffer oxide case through being concentrated into solid content weight fraction 10% when above by circulating pump;
(6) oxidation sulfurous acid ammonia and ammonium bisulfite in the buffer oxide case, the pH value transfers to 4～6 in the buffer oxide case, optimum oxidation pH value is 5.5, fully oxidation sulfurous acid ammonia obtains purer ammonium sulfate, when the sulfate of ammoniac solution solid content in the buffer oxide case reaches mass fraction 15%, by the circulating pump of buffer oxide case sulfate of ammoniac solution is delivered to cyclone and carry out liquid-solid separation;
(7) solution further is concentrated into the solid content weight fraction more than 35% in cyclone, by circulating pump ammonium sulfate is entered centrifuge then;
(8) by centrifuge solution is carried out Separation of Solid and Liquid, obtain moisturely, when promptly solid content reaches weight fraction 95%, be delivered to drying bed (as the vibrations fluidized bed dryer) by conveying worm less than 5% ammonium sulfate solids;
(9) drying bed is provided with exhaust scrubber, finishes the byproduct packing in drying bed oven dry back by sack filling machine; Drying bed is dried to ammonium sulfate moisture 1.0%, drains into packing machine at last, the packing outward transport; The sulfur acid ammonium dust tail gas that drying bed is discharged enters exhaust scrubber, washs the back discharging, and whole process ammonium sulfate yield can reach more than 96%.
The result: by dioxygen metallization processes of the present invention, content of sulfur dioxide is less than 150mg/ Nm in the tail gas
3, the content of ammonia is less than 8mg/ Nm in the tail gas
3Desulfurizer total pressure drop 800Pa, by-product meets DLT 808-2002 producing ammonium sulfate byproduct, and steam consumption (drier vapour) is a 100kg/t ammonium sulfate, power consumption is less than 200KW/t ammonium sulfate, existing ammonia process is compared and is reduced desulphurization cost 30%, and absorption efficiency mentions 98%, and amount of ammonia slip is reduced to below the 8mg/m3.
As depicted in figs. 1 and 2, a kind of dioxygen ammonia desulfuration equipment comprises ammoniacal liquor preparation facilities 10, absorption tower 4, prewashing tower 5, buffer oxide case 6, cyclone 7, centrifuge 8, drying bed 9, exhaust scrubber 11, packing machine 12, ammoniacal liquor storage tank 101; Be provided with demister 1, rotating plate convection current ammonia absorption plant 2, spraying layer 3 and 1/2 porous plate 41 in the described absorption tower 4 from top to bottom successively, the bottom on described absorption tower 4 is slurries pond 42; Described ammoniacal liquor preparation facilities 10 links to each other with ammoniacal liquor storage tank 101, and ammoniacal liquor storage tank 101 links to each other with buffer oxide case 6, and described prewashing tower 5 links to each other with the bottom on absorption tower 4, and 4 tops, described absorption tower link to each other with chimney; Described prewashing tower 5 is connected with buffer oxide case 6, and described buffer oxide case 6, cyclone 7, centrifuge 8, drying bed 9 link to each other successively, and described drying bed 9 links to each other with exhaust scrubber 11 with packing machine 12 respectively.
Described buffer oxide case 6 and slurries pond 42 are equipped with oxidation fan;
Be provided with circulating pump between described absorption tower 4 and the prewashing tower 5; Be provided with circulating pump between prewashing tower 5 and the buffer oxide case 6; Be provided with slush pump between buffer oxide case 6 and the cyclone 7; Be provided with slush pump between ammoniacal liquor storage tank 101 and the buffer oxide case 6.
Described slurries pond 42, prewashing tower 5 and buffering oxidation case 6 all are connected with a slurries case, and described slurries case is connected with a melt pit, can prevent slurries pond 42, prewashing tower 5 and cushion the interior liquid level of oxidation case 6 when higher, and slurries overflow.
The ammoniacal liquor preparation facilities comprises: liquefied ammonia vaporization heat-exchanger rig 102, spraying ammoniacal liquor mixing arrangement 103, ammoniacal liquor cooling heat transferring device 104; Described liquefied ammonia vaporization heat-exchanger rig 102 has two, described two liquefied ammonia vaporization heat-exchanger rig 102 is in parallel, and be connected with spraying ammoniacal liquor mixing arrangement 103, described spraying ammoniacal liquor mixing arrangement 103 is connected with described ammoniacal liquor cooling heat transferring device 104, and described ammoniacal liquor cooling heat transferring device 104 is connected with described two liquefied ammonia vaporization heat-exchanger rig 102 respectively.
The prewashing tower is used for to flue gas cool-down and concentrated vitriol ammonium salt solution, and one deck spray is set, and supplies with spray liquid by circulating pump, and the absorption tower is provided with the respectively corresponding three layers of spray of three circulating pumps.
Cyclone overflowing liquid, exhaust scrubber overflowing liquid and centrifuge overflowing liquid are back to the buffer oxide case by the overfall that is provided with through a reflux line.
Whole process is carried out blanking from top to bottom, does not increase any lifting means, and whole system does not have waste water, waste gas produces.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. dioxygen ammonia desulfurizing process is characterized in that: may further comprise the steps:
(1) preparation desulfurizing agent ammoniacal liquor, ammoniacal liquor is prepared by liquefied ammonia by the ammoniacal liquor preparation facilities, and the ammoniacal liquor mass fraction for preparing is 20%, is stored in the ammoniacal liquor storage tank, squeezes into the absorption tower by circulating pump;
(2) after flue gas enters from the top of prewashing tower, cool to 60 ℃ in the prewashing tower, and spray desulfurization, flue gas enters the absorption tower through the bottom from the prewashing tower after the desulfurization;
(3) flue gas that enters the absorption tower at first passes through porous plate, and the flue gas flow rate by porous plate is 6～10m/s, forms convection current with the spray liquid of spraying layer, and the liquid gas volume ratio of flue gas and spray liquid is controlled at 3～5 ﹕ 1, SO in the flue gas
2Spray liquid reaction with discharge on the absorption tower has absorbed SO in the flue gas
2Spray liquid be the mixed solution that contains ammonium sulfate, sulfurous acid ammonia and ammonium bisulfite, absorbed SO in the flue gas
2Spray liquid fall into the slurries pond of absorption tower bottom;
(4) contain small amount of ammonia gas colloidal sol through the flue gas after above-mentioned steps (3) desulfurization, remove most of ammonia of escaping, and then, remove the water smoke in the flue gas, the flue gas that is purified by demister dehydration, demist by rotating plate convection current ammonia absorption plant;
(5) fall into the mixed solution in slurries pond in the above-mentioned steps (3), drain into the prewashing tower by circulating pump, in the prewashing tower, mixed solution is concentrated, when the mixed solution in the prewashing tower reaches weight fraction 10% through being concentrated into solid content, enter the buffer oxide case by circulating pump;
(6) in the buffer oxide case, the mixed solution that obtains in the above-mentioned steps (5) is carried out oxidation, the pH value transfers to 4～6 in the buffer oxide case, obtain ammonium sulfate, sulfate of ammoniac solution solid content in the buffer oxide case reaches weight fraction 15%, by the circulating pump of buffer oxide case sulfate of ammoniac solution is delivered to cyclone;
(7) solution that obtains of above-mentioned steps (6) further is concentrated into solid content and reaches weight fraction 35% in cyclone, by circulating pump ammonium sulfate is entered centrifuge then;
(8) by centrifuge the solution that above-mentioned steps (7) obtains is carried out Separation of Solid and Liquid, when solid content reaches weight fraction 95%, be delivered to drying bed;
(9) drying bed is the ammonium sulfate drying, obtains water content less than 1.0% ammonia sulfate crystal; Drying bed is provided with exhaust scrubber, and the sulfur acid ammonium dust tail gas of discharging from drying bed enters exhaust scrubber, washs the back discharging.
2. dioxygen ammonia desulfurizing process according to claim 1, it is characterized in that: the process of described ammoniacal liquor preparation is: liquefied ammonia enters two liquefied ammonia gasification heat-exchanger rigs respectively, gasify, ammoniacal liquor gas mixture after the gasification enters spraying ammoniacal liquor absorption plant, the recirculated water that feeds is mixed with preparation water, preparation quality concentration 20% ammoniacal liquor, ammoniacal liquor is tentatively lowered the temperature by ammoniacal liquor cooling device and the recirculated water that cooled off from liquefied ammonia gasification heat-exchanger rig, temperature is reduced to below 50 ℃, again by another liquefied ammonia gasification heat-exchanger rig by with the heat exchange of liquefied ammonia gasification, obtain temperature less than 25 ℃ ammoniacal liquor.
3. dioxygen ammonia desulfurizing process according to claim 1 is characterized in that: the pH value 5.5 in the described buffer oxide case.
4. a device that is used for the described dioxygen ammonia desulfurizing process of claim 1 is characterized in that: comprise ammoniacal liquor preparation facilities, absorption tower, prewashing tower, buffer oxide case, cyclone, centrifuge, drying bed, exhaust scrubber, packing machine, ammoniacal liquor storage tank;
Be provided with demister, rotating plate convection current ammonia absorption plant, spraying layer and porous plate in the described absorption tower from top to bottom successively, the bottom on described absorption tower is the slurries pond; Described ammoniacal liquor preparation facilities links to each other with the ammoniacal liquor storage tank, and described ammoniacal liquor storage tank links to each other with the buffer oxide case, and described prewashing tower links to each other with the bottom on absorption tower, and top, described absorption tower links to each other with chimney; Described prewashing tower is connected with the buffer oxide case, and described buffer oxide case, cyclone, centrifuge, drying bed link to each other successively, and described drying bed links to each other with exhaust scrubber with packing machine respectively.
5. the device that is used for the dioxygen ammonia desulfurizing process according to claim 4 is characterized in that: described ammoniacal liquor preparation facilities comprises: liquefied ammonia vaporization heat-exchanger rig, spraying ammoniacal liquor mixing arrangement, ammoniacal liquor cooling heat transferring device; Described liquefied ammonia vaporization heat-exchanger rig has two, described two liquefied ammonia vaporization heat-exchanger rig is in parallel, and be connected with spraying ammoniacal liquor mixing arrangement, described spraying ammoniacal liquor mixing arrangement is connected with described ammoniacal liquor cooling heat transferring device, and described ammoniacal liquor cooling heat transferring device is connected with described two liquefied ammonia vaporization heat-exchanger rig respectively.
6. the device that is used for the dioxygen ammonia desulfurizing process according to claim 4 is characterized in that: described porous plate is 1/2 porous plate.
7. the device that is used for the dioxygen ammonia desulfurizing process according to claim 4 is characterized in that: described buffer oxide case and slurries pond are equipped with oxidation fan.
8. the device that is used for the dioxygen ammonia desulfurizing process according to claim 4 is characterized in that: be provided with circulating pump between described absorption tower and the prewashing tower; Be provided with circulating pump between prewashing tower and the buffer oxide case; Be provided with slush pump between buffer oxide case and the cyclone; Be provided with slush pump between ammoniacal liquor storage tank and the buffer oxide case.
9. the device that is used for the dioxygen ammonia desulfurizing process according to claim 4, it is characterized in that: described cyclone, exhaust scrubber and centrifuge are equipped with overfall, and the overflowing liquid of cyclone, exhaust scrubber and centrifuge is back to the buffer oxide case by the reflux line that is arranged on overfall.
10. the device that is used for the dioxygen ammonia desulfurizing process according to claim 4 is characterized in that: described slurries pond, prewashing tower and buffering oxidation case all are connected with a slurries case, and described slurries case is connected with a melt pit.
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| CN103553078A (en) * | 2013-11-22 | 2014-02-05 | 云南云铝涌鑫铝业有限公司 | Technology for preparing ammonium sulfate by high-efficiency ammonia desulphurization and crystallization |
| CN104043328A (en) * | 2014-06-19 | 2014-09-17 | 山东黑石环保科技有限公司 | Regenerated flue gas desulfurizing device and method by alkaline process catalytic cracking |
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| PH12018000127A1 (en) * | 2017-05-25 | 2019-03-18 | Jiangnan Environmental Prot Group Inc | Ammonia-based desulfurization process and apparatus through ammonia-adding in different chambers |
| CN109647163A (en) * | 2018-12-21 | 2019-04-19 | 大田县伊鑫新型材料有限公司 | A kind of dry-process cement rotary kiln ammonia process semidry process desulfurizer |
| US10406477B2 (en) | 2017-03-15 | 2019-09-10 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
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| CN109647163A (en) * | 2018-12-21 | 2019-04-19 | 大田县伊鑫新型材料有限公司 | A kind of dry-process cement rotary kiln ammonia process semidry process desulfurizer |
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