Summary of the invention
The invention provides a kind of glass kiln flue gas desulfurization and denitrification system and technique, first flue gas denitration is that denitrfying agent completes in glass kiln burner regenerator with ammonia, the follow-up ammonia process of desulfurization can realize secondary denitration simultaneously, utilize desulfurization product ammonium sulfate and flue gas heat exchange to decompose and obtain ammonia, ammonia can be used as a denitration absorbent.Therefore the present invention's denitrification process supplies ammonia without the need to outer, remain NOx in flue gas to be removed by secondary in follow-up ammonia process of desulfurization process, solve in prior art with ammonia be denitrfying agent method of denitration in ammonia source need outer for and ammonia consumption is large, and the problem such as denitration effect difference in ammonia process of desulfurization process.
Object of the present invention is achieved through the following technical solutions:
The invention provides a kind of glass kiln flue gas desulfurization and denitrification system and technique.
Described glass kiln flue gas desulfurization and denitrification system comprises glass kiln burner regenerator denitration unit, fume dust remover, decomposition ammonia-preparing device and flue gas desulfurization and secondary denitration unit;
Wherein, flue gas is successively by glass kiln burner regenerator denitration unit, fume dust remover, decomposition ammonia-preparing device and flue gas desulfurization and secondary denitration unit;
Glass kiln burner regenerator denitration unit comprises heat accumulating sections and denitration section, and be provided with ammonia spraying system in denitration section, ammonia spraying system is connected with ammoniacal liquor storage device;
The ammonia decomposing ammonia-preparing device generation enters described ammoniacal liquor storage device;
Flue gas desulfurization and secondary denitration unit are provided with ammonium sulfite spray system, and the ammonium sulfate outlet of flue gas desulfurization and secondary denitration unit is connected with the solution inlet decomposing ammonia-preparing device.
Further, described glass kiln flue gas desulfurization and denitrification system also comprises oxidant preparation facilities, the ammonium bisulfate solution that described decomposition ammonia-preparing device is discharged is connected through the entrance of pipeline with described oxidant preparation facilities, the decomposition exhanst gas outlet of ammonia-preparing device and the oxidant outlet of oxidant preparation facilities are connected respectively on oxidation reactor, and the exhanst gas outlet on oxidation reactor is connected with the smoke inlet of flue gas desulfurization and secondary denitration unit.
Further, in glass kiln burner regenerator denitration unit, described heat accumulating sections comprises the first heat accumulating sections and the second heat accumulating sections, and flue gas is successively through the first heat accumulating sections, denitration section and the second heat accumulating sections.
Further, flue gas desulfurization and secondary denitration unit comprise desulphurization denitration tower and tower external oxidation district, and the taphole of desulphurization denitration tower is connected with tower external oxidation district, and the ammonium sulfate outlet in tower external oxidation district is connected with the solution inlet decomposing ammonia-preparing device.
Further, tower external oxidation district is provided with air intake.
More specifically, described fume dust remover air inlet and glass kiln burner regenerator denitration unit smoke discharge tube road is connected, and dust arrester exhanst gas outlet is connected with decomposition ammonia-preparing device.Described decomposition ammonia-preparing device is provided with gas approach and exhanst gas outlet, and the gas approach decomposing ammonia-preparing device is connected with dust arrester exhanst gas outlet by pipeline.Described decomposition ammonia-preparing device is also provided with ammonium sulfate entrance and ammonium hydrogen sulfate outlet, wherein, ammonium sulfate entrance is connected with tower external oxidation district, ammonium hydrogen sulfate outlet is connected with oxidant preparation facilities entrance, the ammonia decomposing generation after ammonium sulfate and flue gas heat exchange enters ammoniacal liquor storage device through pipeline, decomposes the ammonium hydrogen sulfate that ammonia-preparing device discharges and enters oxidant preparation facilities through pipeline.Oxidant preparation facilities production oxidant hydrogen peroxide, raffinate ammonium bisulfate solution is back to device portal and recycles.The hydrogen peroxide of being discharged by oxidant preparation facilities and the flue gas of discharging through decomposing ammonia-preparing device are connected on oxidation reactor, and the exhanst gas outlet of oxidation reactor is connected with flue gas desulfurization and secondary denitration unit.Flue gas desulfurization and secondary denitration unit comprise desulphurization denitration tower and tower external oxidation district.Described desulphurization denitration tower is provided with smoke inlet, and the smoke inlet of desulphurization denitration tower is connected with the exhanst gas outlet of oxidation reactor.Be provided with ammonium sulfite spray system at desulphurization denitration tower flue gas entrance top, arrange demister above spray system, top of tower arranges exhanst gas outlet.Tower bottom connects neutralization reaction district and zoneofoxidation.Arrange ammoniacal liquor in neutralization reaction district and add entrance, the solution ammonium sulfite after neutralization reaction, as desulfurization absorption cycle liquid, is connected to spray system by absorbing liquid circulating pump.Tower external oxidation district is provided with air intake, and the ammonium sulfate that tower external oxidation district discharges is connected with decomposition ammonia-preparing device entrance.
Heat smoke after glass kiln burning transfers heat to heat storage by during burner regenerator, the section being 900-1100 DEG C in flue-gas temperature arranges ammonia spraying system, carry out denitration reaction, after denitration, flue gas leaves glass kiln and carries out electric precipitation, then with the heat exchange of desulfurization product ammonium sulfate, flue gas after cooling mixes with oxidant hydrogen peroxide, and the NO in flue gas is oxidized to NO
2, enter ammonia process of desulfurization denitrating tower, desulfurization absorbent ammonium sulfite in desulfurization simultaneously, also can by part NO
2remove, achieve secondary denitration, after desulfur denitrate dust collecting, flue gas discharges after the demist of desulphurization denitration tower top.The solvent portions neutralization of discharging at the bottom of desulphurization denitration tower, partial oxidation, be ammonium sulfate after oxidation, after ammonium sulfate and flue gas heat exchange, decomposition reaction occur, generate ammonia and ammonium hydrogen sulfate.Ammonia obtains ammoniacal liquor and can be used as glass kiln burner regenerator denitration absorbent, and ammonium bisulfate solution electrolysis obtains hydrogen peroxide, and as NOx oxidant in flue gas, raffinate is ammonium hydrogen sulfate reusable edible.
Glass kiln flue gas desulfurization and denitration technique according to the present invention adopts above-mentioned glass kiln flue gas desulfurization and denitrification system, comprising:
(1) heat smoke after glass kiln burning is after heat accumulating sections is once lowered the temperature, enter denitration section, ammoniacal liquor is supplied to ammonia spraying system by ammoniacal liquor storage device, ammonia spraying system sprays ammonia spirit to carry out a denitration to the heat smoke after described once cooling, leaves glass kiln after the smoke secondary cooling after a described denitration;
(2) flue gas leaving glass kiln enters fume dust remover, removes the dust in flue gas;
(3) after dedusting, flue gas enters decomposition ammonia-preparing device, enters flue gas desulfurization and secondary denitration unit with after the ammonium sulfate heat exchange of decomposing in ammonia-preparing device; Decomposing the ammonium sulfate generation decomposition reaction in ammonia-preparing device after heat exchange, obtain ammonia and ammonium bisulfate solution, described ammonia enters described ammoniacal liquor storage device and obtains described ammonia spirit;
(4) flue gas entering flue gas desulfurization and secondary denitration unit contacts with ammonium sulfite solution, carries out desulphurization denitration, eventually passes the fume emission after process; The ammonium sulfate that flue gas desulfurization and secondary denitration unit are discharged enters decomposition ammonia-preparing device.
Wherein, in described step (1), before flue gas enters denitration section, temperature is 900-1100 DEG C, adopts the denitration of SNCR method.
In described step (1), glass kiln burner regenerator denitration unit comprises the first heat accumulating sections, denitration section and the second heat accumulating sections, flue gas is first after the first heat accumulating sections cooling, enter denitration section, the flue gas after a denitration continues to be cooled to about 200-280 DEG C through the second heat accumulating sections again and leaves glass kiln.
In described step (3), the described ammonium bisulfate solution obtained enters oxidant preparation facilities and produces oxidant, the oxidant that oxidant preparation facilities is discharged and the flue gas that decomposition ammonia-preparing device is discharged enter in oxidation reactor respectively, and the NO in flue gas is oxidized to NO
2, the flue gas leaving oxidation reactor enters flue gas desulfurization and secondary denitration unit.
In described step (4), the ammonium sulfite solution absorbing SO2 and NOx is discharged by the bottom of the tower of desulphurization denitration tower, and part enters tower external oxidation district; At tower external oxidation, district passes into air, and be ammonium sulfate by the sulfite oxidation in solution, described ammonium sulfate enters decomposition ammonia-preparing device.
More specifically, described glass kiln flue gas desulfurization and denitration technique comprises:
(1) glass kiln burning after heat smoke by burner regenerator time first through the first heat accumulating sections, flue-gas temperature reduction transfers heat to heat storage, time in the scope that flue-gas temperature is down to 900-1100 DEG C, reach SNCR method denitration effecting reaction temperature, enter denitration section, ammonia spraying system is set in denitration section, using ammoniacal liquor as denitration absorbent, carries out a denitration.After denitration, flue gas leaves glass kiln after continuing through the second heat accumulating sections cooling.Denitration reaction formula is:
4NH
3+4NO+O
2→4N
2+6H
2O
(2) flue gas leaving glass kiln, by electric precipitation, removes dust that is tiny in glass kiln flue gas and tool viscosity.
(3) after electric precipitation, flue-gas temperature 160-240 DEG C, enters decomposition ammonia-preparing device, with the heat exchange of desulfurization product ammonium sulfate, the flue gas being cooled to 130-150 DEG C mixes with hydrogen peroxide, and the mol ratio keeping NO in hydrogen peroxide and flue gas is 1-1.5, and the NO in flue gas is oxidized to NO
2, then enter desulfurization unit.Reaction equation is:
NO is oxidized: NO+H
2o
2→ NO
2+ H
2o
(4) flue gas enters desulphurization denitration tower by air inlet, upwards flows through spray system, and with absorbing liquid counter current contacting, desulfurization absorbent is ammonium sulfite, the SO in flue gas
2be recycled absorbing liquid to absorb.Because the NO in flue gas is oxidized to NO
2, NO
2soluble in water, strengthen the extent of reaction with liquid absorbent, therefore in desulfurization simultaneously, remainder NOx (NO, NO in flue gas
2) react with ammonium sulfite solution, generate ammonium sulfate and nitrogen, achieve secondary denitration.After desulfur denitrate dust collecting, flue gas discharges after the demist of desulphurization denitration tower top.
Absorb SO
2discharge by the bottom of tower with the solution of NOx, part enters neutralization reaction district, and part enters tower external oxidation district.In neutralization reaction, district adds ammoniacal liquor, is the absorbent ammonium sulfite of tool, delivers to spray system, as desulfurization absorption cycle liquid by absorbing liquid circulating pump by the ammonium bisulfite neutralization in solution.Inject air in tower external oxidation district, solution sulfite ammonium is oxidized to ammonium sulfate, enters decomposition ammonia-preparing device.
This partial reaction formula is:
Desulfurization absorbs: SO
2+ H
2o=H
2sO
3
(NH
4)
2SO
3+SO
2=NH
4HSO
3
Secondary denitration: 4 (NH
4)
2sO
3+ 2NO
2=4 (NH
4)
2sO
4+ N
2
2(NH
4)
2SO
3+2NO=2(NH
4)
2SO
4+N
2
Neutralization: NH
4hSO
3+ NH
3=(NH
4)
2sO
3
Oxidation: (NH
4)
2sO
3+ 1/2O
2=(NH
4)
2sO
4
(5) ammonium sulfate of being discharged by tower external oxidation district enters decomposition ammonia-preparing device, and in device, after ammonium sulfate and dedusting, flue gas carries out heat exchange generation decomposition reaction, and reaction temperature is 100-120 DEG C, generation ammonia and ammonium hydrogen sulfate.Reaction equation is:
(NH
4)
2SO
4=NH
3+NH
4HSO
4
Ammonia obtains ammoniacal liquor and can be used as glass kiln burner regenerator denitration absorbent, and ammonium bisulfate solution enters oxidant preparation facilities, obtains hydrogen peroxide through electrolysis, and as NOx oxidant in flue gas, raffinate is ammonium hydrogen sulfate reusable edible.
(6) a kind of glass kiln flue gas desulfurization and denitrification system provided by the invention and technique, ammonia and NOx oxidant hydrogen peroxide can be obtained by internal system flow process, ammonia need not be supplied outward, can denitration be carried out, and can secondary denitration in sweetening process, system produces without raffinate, belong to pollution-free recycle utilization, have ammonia consumption little, denitration efficiency is high, and process system is simple and invest the advantages such as little.
(7) glass kiln flue gas desulfurization and denitrification system of the present invention and technique, desulfurization degree is greater than 95%, denitration rate 70-90%.
Beneficial effect of the present invention
(1) the present invention utilizes desulphurization denitration product ammonium sulfate preparing ammonia and ammonium hydrogen sulfate, ammonia can be used as a denitration absorbent, ammonia need not be supplied outward, reduce the ammonia consumption of whole system for desulfuration and denitration, ammonium hydrogen sulfate obtains hydrogen peroxide further as NOx oxidant in flue gas, avoid consuming a large amount of outer oxidant that supplies to improve denitration rate, raffinate ammonium hydrogen sulfate reusable edible.
(2) first flue gas denitration of the present invention adopts SNCR method, before flue gas discharges glass kiln, a denitration is carried out in burner regenerator, in follow-up ammonia process of desulfurization process, in flue gas, some residual NOx is removed by secondary, relative to the denitration of SNCR method, this technique adds the removal efficiency of NOx in flue gas, and denitration rate is 70-90%.
(3) the present invention adopts ammonia desulfurizing process, and desulfurization degree is greater than 95%.Carry out outside tower owing to mending ammonia, avoid ammonia and directly contact with flue gas, avoid in flue gas and carry ammonia secretly and produce aerosol.
(4) first flue gas denitration of the present invention completes in glass kiln regenerator, the follow-up ammonia process of desulfurization can realize secondary denitration simultaneously, desulfurization product ammonium sulfate aftertreatment systems can obtain a denitration absorbent ammonia and NOx oxidant hydrogen peroxide, and produce without raffinate, whole system for desulfuration and denitration and technique simple, invest little, denitrification efficiency is high.
Detailed description of the invention
Composition graphs 1 describes specific embodiment of the invention scheme further.
Embodiment 1
The invention provides a kind of glass kiln flue gas desulfurization and denitrification system and technique, described system comprises glass kiln burner regenerator denitration unit, fume dust remover, decomposition ammonia-preparing device, oxidant preparation facilities and flue gas desulfurization and secondary denitration unit.
Wherein, flue gas is successively by glass kiln burner regenerator denitration unit, fume dust remover, decomposition ammonia-preparing device and flue gas desulfurization and secondary denitration unit.
Glass kiln burner regenerator denitration unit comprises the first heat accumulating sections, denitration section and the second heat accumulating sections, and denitration section is arranged between the first heat accumulating sections and the second heat accumulating sections, is provided with ammonia spraying system in denitration section, and ammoniacal liquor storage device is connected with ammonia spraying system.
Described decomposition ammonia-preparing device is provided with gas approach and exhanst gas outlet, the gas approach decomposing ammonia-preparing device is connected with dust arrester exhanst gas outlet by pipeline, described decomposition ammonia-preparing device is also provided with ammonium sulfate entrance and ammonium bisulfate solution outlet, wherein, the ammonium sulfate of ammonium sulfate entrance and flue gas desulfurization and secondary denitration unit exports and is connected, ammonium hydrogen sulfate outlet is connected with oxidant preparation facilities entrance, the ammonia decomposing generation after ammonium sulfate and flue gas heat exchange enters ammoniacal liquor storage device through pipeline, the ammonium hydrogen sulfate decomposing ammonia-preparing device discharge enters oxidant preparation facilities through pipeline, oxidant preparation facilities produces hydrogen peroxide, and raffinate ammonium bisulfate solution is back to device portal and recycles, the hydrogen peroxide of being discharged by oxidant preparation facilities and the flue gas of discharging through decomposing ammonia-preparing device are connected on oxidation reactor, and the exhanst gas outlet of oxidation reactor is connected with the smoke inlet of flue gas desulfurization and secondary denitration unit.
Flue gas desulfurization and secondary denitration unit comprise desulphurization denitration tower, absorbing liquid circulating pump, Ta Wai neutralization reaction district and tower external oxidation district.Ammonium sulfite spray system is provided with in desulphurization denitration tower.Desulphurization denitration tower taphole is connected to Ta Wai neutralization reaction district and tower external oxidation district.The ammonium sulfate outlet in tower external oxidation district is connected with the solution inlet decomposing ammonia-preparing device.
Its technique is as follows:
A denitration: first through the first heat accumulating sections when the heat smoke in glass kiln flows through burner regenerator, flue-gas temperature reduces and transfers heat to heat storage.When flue-gas temperature reduces to 900 DEG C, enter denitration section, ammonia spraying system is arranged on denitration section, adopts ammoniacal liquor as denitration absorbent, carries out a denitration to flue gas.After denitration, flue gas continues through the second heat accumulating sections cooling, reduces to-200 DEG C leave glass kiln when temperature.One time denitration reaction formula is:
4NH
3+4NO+O
2→4N
2+6H
2O
Dedusting: glass kiln exhaust gas dust particle diameter is less, viscosity is comparatively strong, adopts electric cleaner can obtain preferably removal effect.
Desulfurization and secondary denitration: after electric precipitation, flue-gas temperature-160 DEG C, enter Decomposition of ammonium sulfate ammonia-preparing device, flue gas and the heat exchange of desulfurization product ammonium sulfate, the flue gas being cooled to 130 DEG C mixes at oxidation reactor with oxidant hydrogen peroxide prepared by oxidant preparation facilities, the mol ratio making NO in hydrogen peroxide and flue gas is 1.1, and the NO in flue gas is oxidized to NO
2, then enter desulphurization denitration tower.Flue gas enter desulphurization denitration tower backward on flow through spray system, with absorbing liquid counter current contacting, desulfurization absorbing liquid is ammonium sulfite, the SO in flue gas
2be recycled absorbing liquid to absorb, absorbing liquid pH value remains on about 5.In desulfurization simultaneously, remainder NO, NO in flue gas
2react with ammonium sulfite solution, generate ammonium sulfate and nitrogen, achieve secondary denitration.After desulfur denitrate dust collecting, flue gas discharges after the demist of desulfurization tower top.Reaction equation is:
NO is oxidized: NO+H
2o
2→ NO
2+ H
2o
Desulfurization absorbs: SO
2+ H
2o=`H
2sO
3
(NH
4)
2SO
3+SO
2=NH
4HSO
3
Secondary denitration: 4 (NH
4)
2sO
3+ 2NO
2=4 (NH
4)
2sO
4+ N
2
2(NH
4)
2SO
3+2NO=2(NH
4)
2SO
4+N
2
Absorb SO
2discharge by the bottom of tower with the solution of NOx, part enters neutralization reaction district, and part enters tower external oxidation district.In neutralization reaction, district adds ammoniacal liquor, is the absorbent ammonium sulfite of tool, delivers to spray system, as desulfurization absorption cycle liquid by absorbing liquid circulating pump by the ammonium bisulfite neutralization in solution.Inject air in zoneofoxidation, solution sulfite ammonium is oxidized to ammonium sulfate, enters decomposition ammonia-preparing device.Reaction equation is:
Neutralization: NH
4hSO
3+ NH
3=(NH
4)
2sO
3
Oxidation: (NH
4)
2sO
3+ 1/2O
2=(NH
4)
2sO
4
Ammonium sulfate process: at 100-120 DEG C, decomposition reaction occurs after flue gas heat exchange after ammonium sulfate and the dedusting of being discharged by tower external oxidation district, generation ammonia and ammonium hydrogen sulfate.Reaction equation is:
(NH
4)
2SO
4=NH
3+NH
4HSO
4
Ammonia obtains ammoniacal liquor and can be used as glass kiln burner regenerator denitration absorbent, and ammonium bisulfate solution electrolysis obtains hydrogen peroxide, and as NOx oxidant in flue gas, raffinate is ammonium hydrogen sulfate reusable edible.
The present invention makes glass kiln flue gas desulphuization rate be greater than 95%, denitration rate 70%.
Embodiment 2:
Adopt the system for desulfuration and denitration identical with embodiment 1 and technique.When flue-gas temperature reduces to 1100 DEG C in glass kiln burner regenerator, carry out a denitration, when flue gas leaves glass kiln, temperature is-280 DEG C.After electric precipitation, flue-gas temperature-240 DEG C, enter Decomposition of ammonium sulfate ammonia-preparing device, flue gas and the heat exchange of desulfurization product ammonium sulfate, be cooled to the flue gas of 150 DEG C to mix with the oxidant hydrogen peroxide of preparation, the mol ratio making NO in hydrogen peroxide and flue gas is 1.35, and the NO in flue gas is oxidized to NO
2, then enter desulphurization denitration tower.Desulfurization absorbing liquid pH value remains on about 6, completes desulfurization and secondary denitrification process.
Flue gas desulphuization rate is greater than 95%, denitration rate 85%.