CN102228777B - Double-oxidation ammonia desulfurization process and device - Google Patents
Double-oxidation ammonia desulfurization process and device Download PDFInfo
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- CN102228777B CN102228777B CN 201110132854 CN201110132854A CN102228777B CN 102228777 B CN102228777 B CN 102228777B CN 201110132854 CN201110132854 CN 201110132854 CN 201110132854 A CN201110132854 A CN 201110132854A CN 102228777 B CN102228777 B CN 102228777B
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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 Double-oxidation ammonia desulfurization process and device adopt liquefied ammonia to remove sulfur dioxide in the flue gas, 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, day by day comes into one's own.
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, EA-FGD, impulse electric corona ammonia process, simple and easy ammonia process etc.
The wet ammonia process desulfurizing technology system is mainly by compositions such as desulfurization washing system, flue gas system, ammonia storage system, ammonium sulfate production systems (if not ammonia-ammonium sulfate method, then being the accessory substance manufacturing system corresponding with its technique).Nucleus equipment is desulfurization washing tower.Usually adopt ammoniacal liquor as desulfurizing agent, absorption liquid usually adopt 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 of absorption liquid spray-absorption in most of ammonia desulfurizing process, the mode of this spray-absorption mainly can cause the outlet flue gas in ammonia-spillage amount large, 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, only have by adding excess ammonia and absorb sulfide in the flue gas, so just cause the absorbent consumption large, uneconomical, the outlet ammonia-spillage amount is also large, 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 flue gas by the reaction time of absorption liquid on column plate and the column plate, so the pitch-row of tray designs is little, resistance is large, energy consumption is high, and when flue gas passed from the column plate liquid film, drop was carried secretly more serious.
Yet by oxidation in the absorbing tower, 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 is unstable, 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 equally the absorption efficiency reduction, be difficult to output ammonium sulfate.
A kind of integral desulfurization, dust removal tower of ammonia process is provided in the Chinese patent 200310115523.2, this desulfurized dust collection column 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 processing large exhaust gas volumn, and the solution on the column plate is difficult to evenly distribute when the tower diameter of desulfurizing tower is larger.
Void tower type ammonia desulfurizing process and device are provided in the Chinese patent application 200510040800.7, have used this technique and device to carry out desulfurization and can when guaranteeing desulfuration efficiency, can reduce investment outlay.But this technique and device can affect the desulfurization degree of whole desulphurization system like this owing to having 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 Double-oxidation ammonia desulfurization 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 carrying out dual oxide on absorption tower and buffer oxide case, reach effective reduction amount of ammonia slip, reduce the purpose that ammonium sulfate loses.
Technical scheme of the present invention is:
Double-oxidation ammonia desulfurization 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 respectively two liquid ammonia gasification heat-exchanger rigs, the ammoniacal liquor gasification is the endothermic reaction, can be with the circulating water cooling that passes into, the ammoniacal liquor cooling that will discharge simultaneously, ammoniacal liquor gas mixture after the gasification enters spraying ammonia absorption device, the recirculated water that passes into is mixed with preparation water, preparation quality concentration 20% ammoniacal liquor, ammoniacal liquor is tentatively lowered the temperature by ammonia water cooling device and the recirculated water that cooled off from the liquid ammonia gasification heat-exchanger rig, temperature is down to below 50 ℃, again by another liquid ammonia gasification heat-exchanger rig by with the heat exchange of liquid ammonia gasification process, obtain temperature less than 25 ℃ ammoniacal liquor.The ammoniacal liquor preparation process is utilized the liquid ammonia vaporization endothermic reaction, cooling circulating water, and then the ammoniacal liquor of cooling preparation reduces cooling water amount, reduces operating cost, except 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 slurry pool 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 arranges one deck spray, supplies with spray liquid by circulating pump, and the absorption tower arranges 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 a small amount of ammonia aerosols, 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 slurry pool, also contain sulfurous acid ammonia and ammonium bisulfite, slurry pool is according to the height of prewashing tower liquid level, by circulating pump the ammonium sulfate in the slurry pool 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 arranges exhaust scrubber, finishes the byproduct packing by sack filling machine after the drying bed oven dry; Drying bed is dried to ammonium sulfate moisture 1.0%, drains at last packing machine, the packing outward transport; The liquid containing ammonium sulfate dust tail gas that drying bed is discharged enters exhaust scrubber, washs rear 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 produces without waste water, waste gas.
A kind of device for above-mentioned Double-oxidation ammonia desulfurization 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 successively demister, rotating plate convection current ammonia absorption plant, spraying layer and porous plate in the described absorption tower from top to bottom, the bottom on described absorption tower is slurry pool; 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: liquid ammonia vaporization heat-exchanger rig, spraying ammoniacal liquor mixing arrangement, ammoniacal liquor cooling heat exchange device; Described liquid ammonia vaporization heat-exchanger rig has two, described two liquid ammonia vaporization heat-exchanger rigs are 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 exchange device, and described ammoniacal liquor cooling heat exchange device is connected with described two liquid ammonia vaporization heat-exchanger rigs respectively.
Described porous plate is 1/2 porous plate.
Described buffer oxide case and slurry pool 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 slurry pool, prewashing tower and buffer oxide case all are connected with a slurry tank, and described slurry tank is connected with a melt pit.
1/2 perforated plate construction on absorption tower has increased flue gas flow rate, in the situation that the absorption tower height is constant, does not affect 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 arranges 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 dual oxide device is absorption tower and buffer oxide 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
3SO in the solution absorption flue gas
2, and generate NH
4HSO
3, (NH
4)
2SO
3And NH
4HSO
3Oxidized airborne dioxygen oxidation becomes (NH respectively
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 Double-oxidation ammonia desulphurization device;
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-slurry pool, 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-liquid ammonia vaporization heat-exchanger rig, 103-spraying ammoniacal liquor mixing arrangement, 104-ammoniacal liquor cooling heat exchange 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, is not intended to limit the present invention.
Embodiment 1
A kind of Double-oxidation ammonia desulfurization 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 respectively two liquid ammonia gasification heat-exchanger rigs, the ammoniacal liquor gasification is the endothermic reaction, can be with the circulating water cooling that passes into, the ammoniacal liquor cooling that will discharge simultaneously, ammoniacal liquor gas mixture after the gasification enters spraying ammonia absorption device, the recirculated water that passes into is mixed with preparation water, preparation quality concentration 20% ammoniacal liquor, ammoniacal liquor is tentatively lowered the temperature by ammonia water cooling device and the recirculated water that cooled off from the liquid ammonia gasification heat-exchanger rig, temperature is down to below 50 ℃, again by another liquid ammonia gasification heat-exchanger rig by with the heat exchange of liquid ammonia gasification process, obtain temperature less than 25 ℃ ammoniacal liquor.The ammoniacal liquor preparation process is utilized the liquid ammonia vaporization endothermic reaction, cooling circulating water, and then the ammoniacal liquor of cooling preparation reduces cooling water amount, reduces operating cost, except 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 slurry pool 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 arranges one deck spray, supplies with spray liquid by circulating pump, and the absorption tower arranges three layers of spray, respectively corresponding three circulating pumps;
(4) flue gas after the desulfurization contains a small amount of ammonia aerosols, remove most of ammonia of escaping by rotating plate convection current ammonia absorption plant, and then by demister dehydration, demist, remove the water smoke in the flue gas, the flue gas that is purified, the flue gas of purification enters clean flue to smoke stack emission from the absorption tower jacking;
(5) be mainly saturated ammonium sulfate solution in the slurry pool, also contain sulfurous acid ammonia and ammonium bisulfite, slurry pool 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 slurry pool 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, then by circulating pump ammonium sulfate is entered centrifuge;
(8) by centrifuge solution is carried out Separation of Solid and Liquid, obtain moisturely less than 5% ammonium sulfate solids, when namely solid content reaches weight fraction 95%, be delivered to drying bed (such as the vibrations fluidized bed dryer) by conveying worm;
(9) drying bed arranges exhaust scrubber, finishes the byproduct packing by sack filling machine after the drying bed oven dry; Drying bed is dried to ammonium sulfate moisture 1.0%, drains at last packing machine, the packing outward transport; The liquid containing ammonium sulfate dust tail gas that drying bed is discharged enters exhaust scrubber, washs rear discharging, and whole process ammonium sulfate yield can reach more than 96%.
The result: by dual oxide technique of the present invention, sulfur dioxide in tail gas content is less than 150mg/ Nm
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 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 down to below the 8mg/m3.
Embodiment 2
As depicted in figs. 1 and 2, a kind of Double-oxidation ammonia desulphurization device 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 successively 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, the bottom on described absorption tower 4 is slurry pool 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 slurry pool 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 slurry pool 42, prewashing tower 5 and buffer oxide case 6 all are connected with a slurry tank, and described slurry tank is connected with a melt pit, and in the time of can preventing that liquid level in slurry pool 42, prewashing tower 5 and the buffer oxide case 6 is higher, slurries overflow.
The ammoniacal liquor preparation facilities comprises: liquid ammonia vaporization heat-exchanger rig 102, spraying ammoniacal liquor mixing arrangement 103, ammoniacal liquor cooling heat exchange device 104; Described liquid ammonia vaporization heat-exchanger rig 102 has two, described two liquid ammonia vaporization heat-exchanger rigs 102 are 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 exchange device 104, and described ammoniacal liquor cooling heat exchange device 104 is connected with described two liquid ammonia vaporization heat-exchanger rigs 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 arranges 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 arranges through a reflux line.
Whole process is carried out blanking from top to bottom, does not increase any lifting means, and whole system produces without waste water, waste gas.
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 with reference to previous embodiment the present invention is had been described in detail, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment puts 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 doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. Double-oxidation ammonia desulfurization 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, ammonium sulfite and ammonium bisulfite, absorbed SO in the flue gas
2Spray liquid fall into the slurry pool of absorption tower bottom;
(4) contain a small amount of ammonia aerosols through the flue gas after above-mentioned steps (3) desulfurization, remove most of ammonia of escaping by rotating plate convection current ammonia absorption plant, and then by demister dehydration, demist, remove the water smoke in the flue gas, the flue gas that is purified;
(5) fall into the mixed solution of slurry pool 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, ammonium sulfate solid content in the buffer oxide case reaches weight fraction 15%, by the circulating pump of buffer oxide case ammonium sulfate 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, then by circulating pump ammonium sulfate is entered centrifuge;
(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 dry with ammonium sulfate, obtains water content less than 1.0% ammonia sulfate crystal; Drying bed arranges exhaust scrubber, and the liquid containing ammonium sulfate dust tail gas of discharging from drying bed enters exhaust scrubber, washs rear discharging.
2. Double-oxidation ammonia desulfurization process according to claim 1, it is characterized in that: the process of described ammoniacal liquor preparation is: liquefied ammonia enters respectively two liquid ammonia vaporization heat-exchanger rigs, vaporize, ammoniacal liquor gas mixture after the vaporization enters spraying ammonia absorption device, the recirculated water that passes into is mixed with preparation water, preparation quality concentration 20% ammoniacal liquor, ammoniacal liquor is tentatively lowered the temperature by ammonia water cooling device and the recirculated water that cooled off from the liquid ammonia vaporization heat-exchanger rig, temperature is down to below 50 ℃, again by another liquid ammonia vaporization heat-exchanger rig by with the heat exchange of liquid ammonia vaporization process, obtain temperature less than 25 ℃ ammoniacal liquor.
3. Double-oxidation ammonia desulfurization 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 Double-oxidation ammonia desulfurization process claimed in 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 successively demister, rotating plate convection current ammonia absorption plant, spraying layer and porous plate in the described absorption tower from top to bottom, the bottom on described absorption tower is slurry pool; 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 for Double-oxidation ammonia desulfurization process according to claim 4, it is characterized in that: described ammoniacal liquor preparation facilities comprises: liquid ammonia vaporization heat-exchanger rig, spraying ammoniacal liquor mixing arrangement, ammoniacal liquor cooling heat exchange device; Described liquid ammonia vaporization heat-exchanger rig has two, described two liquid ammonia vaporization heat-exchanger rigs are 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 exchange device, and described ammoniacal liquor cooling heat exchange device is connected with described two liquid ammonia vaporization heat-exchanger rigs respectively.
6. the device for Double-oxidation ammonia desulfurization process according to claim 4, it is characterized in that: described buffer oxide case and slurry pool are equipped with oxidation fan.
7. the device for Double-oxidation ammonia desulfurization 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.
8. the device for Double-oxidation ammonia desulfurization 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.
9. the device for Double-oxidation ammonia desulfurization process according to claim 4, it is characterized in that: described slurry pool, prewashing tower and buffer oxide case all are connected with a slurry tank, and described slurry tank is connected with a melt pit.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110132854 CN102228777B (en) | 2011-05-23 | 2011-05-23 | Double-oxidation ammonia desulfurization process and device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110132854 CN102228777B (en) | 2011-05-23 | 2011-05-23 | Double-oxidation ammonia desulfurization process and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10207220B2 (en) | 2017-03-15 | 2019-02-19 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
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| CN102693451B (en) * | 2012-06-14 | 2014-11-19 | 东北电力大学 | Method for predicting ammonia process flue gas desulphurization efficiency based on multiple parameters |
| US8884024B1 (en) * | 2013-09-25 | 2014-11-11 | Titan Chemicals Limited | Process for preparing benzisothiazolinones |
| CN103553078B (en) * | 2013-11-22 | 2015-07-22 | 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 |
| CN107213769B (en) * | 2017-05-25 | 2019-09-20 | 江苏新世纪江南环保股份有限公司 | A kind of ammonia method desulfurizing method and device of locellus ammonification |
| CN107684812A (en) * | 2017-09-19 | 2018-02-13 | 于维礼 | Oxidizing process in low-pressure oxidized slurries system and liquid |
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| CN116510513A (en) * | 2018-04-13 | 2023-08-01 | 江苏新世纪江南环保股份有限公司 | Oxidation method and device for ammonia desulfurization solution |
| CN109647163B (en) * | 2018-12-21 | 2021-10-19 | 大田县伊鑫新型材料有限公司 | Ammonia process and semi-dry process desulfurization device for dry-process cement kiln |
| CN114159941A (en) * | 2021-11-29 | 2022-03-11 | 启东亚太药业有限公司 | Method and equipment for synthesizing ammonium bisulfite |
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