CN102658016B - Method for ammonia method desulfurization of flue gas and high-purity ammonium hydrogen sulfite by-producing - Google Patents

Method for ammonia method desulfurization of flue gas and high-purity ammonium hydrogen sulfite by-producing Download PDF

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CN102658016B
CN102658016B CN201210131357.4A CN201210131357A CN102658016B CN 102658016 B CN102658016 B CN 102658016B CN 201210131357 A CN201210131357 A CN 201210131357A CN 102658016 B CN102658016 B CN 102658016B
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flue gas
solution
tower
absorption tower
washing
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CN102658016A (en
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郭翠翠
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Shuize Festival (Shandong) Environmental Protection Technology Co.,Ltd.
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SHANDONG TIANTAI STEEL PLASTIC Co Ltd
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Abstract

The invention discloses a method for ammonia method desulfurization of flue gas and high-purity ammonium hydrogen sulfite by-producing. The method comprises the following steps that: solid substances rich in sulfur are firstly burnt to generate the flue gas rich in high concentration sulfur dioxide gas; the flue gas enters into a cyclone separator for dedusting, and the dedusted flue gas enters into a heat exchanger for temperature reduction; then the flue gas enters into a washing and purifying tower to be washed; the flue gas respectively enters into a primary absorption tower, a secondary absorption tower and a third absorption tower for absorption, the high concentration ammonium hydrogen sulfite solution generated through reaction is taken out from a bottom groove of the primary absorption tower as a finished product for package; and the flue gas enters into a washing tower to discharge after washing. By the method, SO2 and other harmful acidic gas are highly purified; the utilization ratio of an ammonia absorption agent is effectively improved; high-purity ammonium hydrogen sulfite solution can be obtained; and the ammonium hydrogen sulfite solution has excellent special industrial use and prospect.

Description

A kind of method of flue gas ammonia method desulfurizing by-product high-purity ammonium bisulfite
Technical field
The present invention relates to the gas generation ammonium bisulfite technical field of utilizing rich sulfur material burning to produce, the particularly a kind of method of flue gas ammonia method desulfurizing by-product high-purity ammonium bisulfite.
Background technology
Ammonium bisulfite (NH 4hSO 3) solution is a kind of important raw material of industry, is the raw material of producing liquid sulfur dioxide, sodium hydrosulfite and sodium formaldehyde sulfoxylate, is used as reducing agent in pharmaceuticals industry.Conventional preparation method is with ammonia absorption relieving haperacidity tail gas, obtains bisulfite ammonium salt solution.Its chemical reaction formula is:
2NH 3+SO 2+H 2O→(NH 4) 2SO 3 (1) ;
(NH 4) 2SO 3+SO 2+H 2O→2NH 4HSO 3 (2) 。
The tail gas of discharge contains sulfur dioxide, in the waste gas of the tail gas of gas washing in SA production and sulfur-bearing raw ore sintering, also contains sulfur dioxide, and these sulfurous gas absorb with ammoniacal liquor conventionally, and ammonium sulfite is the byproduct of its desulfurization.Because content of sulfur dioxide in these gases is conventionally lower, therefore conventionally can react (1), it is incomplete that reaction (2) is carried out.If impurity is more in gas, or SO 2gas concentration is inadequate, and its product purity of producing is inadequate, has affected its industrial use.
Publication number is the ammonia type flue gas desulfurizing apparatus that the patent of CN201609633U discloses a kind of by-product ammonium bisulfite and ammonium sulfite, comprise two-step desulfurization tower, be specially first grade desulfurizing tower and two-grade desulfurizing tower, feed liquid in first grade desulfurizing tower and two-grade desulfurizing tower all by circulated sprinkling to absorb the sour gas in flue gas, first grade desulfurizing tower bottom is provided with slurry pool, is mainly ammonium bisulfite feed liquid in slurry pool.Can find out from the 15th section of this patent specification, the gas of the method desulfurization be plant tail gas from flue gas, conventionally sulfur dioxide in flue gas concentration is lower.When the burning such as gangue, containing sulfur minerals, SO in flue gas 2content is conventionally lower, and conventionally at 300-5000ppm, therefore the desulfurizer of secondary just can meet absorption, and discharge flue gas can meet the requirement of environmental protection.But this device is not suitable for the high concentration sulfur dioxide gas that the secondary sulfur material of burning produces.The concentration of SO 2 gas that the secondary sulfur material that burns produces is very high.For example sulfur burning, if sufficient combustion, without remaining O 2, SO in burning gases 2the ratio that gas accounts for volume of gas can reach 21%, certainly exists excess air in Actual combustion, nonetheless, and the SO of generation 2the volume ratio of gas also can reach 10% to 15%; If burning is troilite, the SO of generation 2the volume ratio of gas also can reach 7%; In activated carbon desulfurization, form the active carbon that is rich in sulphur, its sulfur content is also very high, SO in the gas producing after burning 2content is also very high.The high concentration sulfur dioxide gas that the secondary sulfur material that burns produces is by after first grade absorption tower, the sulfur dioxide concentration of residual gas is still very high, after two-level absorption tower absorbs, the concentration of SO 2 gas of discharge is difficult to reach emission request, if strengthen the concentration of the ammonia of two-level absorption tower, although sulfur dioxide can absorb completely, may have the escaping of ammonia.
Summary of the invention
The object of the present invention is to provide a kind of flue gas that is rich in high concentration sulfur dioxide that secondary sulfur material burning is produced to carry out the method for the ammonia process of desulfurization production high-purity bisulfite ammonium salt solution, make it in having compared with high desulfurization efficiency, ammonia in cleaning of off-gas, loss reduces, and reduces production costs.
For achieving the above object, the present invention proposes technical scheme and is: a kind of method of flue gas ammonia method desulfurizing by-product high-purity ammonium bisulfite, is characterized in that: the solid matter that is rich in sulphur is burnt, produce the flue gas that is rich in high concentration sulfur dioxide gas; Flue gas enters cyclone separator and carries out dedusting, and the flue gas after dedusting enters heat exchanger, cools the temperature to 60~70 DEG C; Flue gas enters washing, purifying tower, and washing, purifying tower structure and cyclone separator are similar, is just provided with shower nozzle on top, by shower nozzle ejection atomization water, the solid matter in flue gas is washed; Flue gas enters first grade absorption tower subsequently, first grade absorption tower inside at least comprises shower nozzle, several clean room and kerve from top to bottom, tower outside is provided with circulating pump, solution in kerve is constantly transported in shower nozzle by pipeline, the base plate of described clean room is with some apertures, by shower nozzle ejection atomization solution, this solution is by ammoniacal liquor and (NH 4) 2sO 3composition, the pH value of solution is controlled at 5~6, and the bisulfite ammonium salt solution of the high concentration that reaction generates falls into the kerve of first grade absorption tower, after concentration reaches requirement, from kerve, takes out and packs as finished product; Flue gas enters two-level absorption tower subsequently, and the structure of two-level absorption tower is identical with first grade absorption tower, by shower nozzle ejection atomization solution, this solution is by ammoniacal liquor and (NH 4) 2sO 3composition, the pH value of solution is controlled at 6~7; Flue gas enters three grades of absorption towers subsequently, and the structure on three grades of absorption towers is identical with first grade absorption tower, by shower nozzle ejection atomization solution, this solution is by ammoniacal liquor and (NH 4) 2sO 3composition, the pH value of solution is controlled at 6~7; Three grades of flue gas discharges after water scrubber washing that discharge on absorption tower, water scrubber structure is identical with washing, purifying tower structure.
Further, can in water scrubber, set up net demister, carry out foam removal.
Further, the solution of flue gas being washed to rear generation in washing, purifying tower enters degassing tower and carries out degassedly, and degassing tower is void tower structure, and top is provided with gas vent; The degassed solution completing enters wash cycle pond and precipitates, and again burns being rich in after solids of sedimentations such as thering is no the biochemical sulphur of completing combustion separates, and recycles; The gas that degassing tower produces is admitted to first grade absorption tower.
Further, the solution of the participation reaction in three grades of absorption towers can be transported in two-level absorption tower and react, and the solution of the participation reaction in two-level absorption tower can be transported to first grade absorption tower and react.
The invention has the beneficial effects as follows: through cyclone separator, flue gas has been carried out to dedusting, through cooling system, gas has been lowered the temperature; If when the secondary sulfur material such as sulphur can not fully burn, wherein may contain the solid impurities such as certain biochemical sulphur, through washing, purifying tower, rich sulphur gas is washed, impurity such as thering is no clean-burning biochemical sulphur can be washed out, in slag liquid accumulator tank, reclaim.The solution producing after the washing of washing, purifying tower contains certain SO 2, can in degassing tower, carry out further degassedly, reclaim SO wherein 2.With carrying out SO in three absorption towers 2absorption, wherein first grade absorption tower is mainly used to high concentration SO 2concentrating of the absorption of gas and ammonium bisulfite, due to SO 2gas concentration is very high, and participates in the ammoniacal liquor of reaction and generally lower (pure ammonia concn is 25%-33%) of concentration of ammonium sulfite solution, and the bisulfite ammonium salt solution purity therefore producing is very high.Generally at first grade absorption tower, through constantly circulation, nearly 75% SO in gas 2be absorbed.Two-level absorption tower is mainly used to absorb SO 2and for first grade desulfurizing tower provides ammonium sulfite absorption liquid, now, SO in gas 2concentration significantly reduces, and in product, main component is ammonium sulfite.Generally at two-level absorption tower, through constantly circulation, nearly 75% SO in gas 2be absorbed.In three grades of absorption towers, sulfur dioxide concentration is very low, and now the ammonia concentration in absorption liquid is also very low, reacts remaining ammonia also little; Gas after absorption is again through washing, SO in gas 2very low with the discharge capacity of ammonia, in gas, the removal efficiency of main acid contaminant can reach: SO 2:>=98%; SO 3:>=95%, can reach emission request completely.Desulfurizing tower is provided with multilayer clean room, has solved in prior art gas and has contacted insufficiently with circulation fluid, easily has dead angle, the problem that desulfuration efficiency is low.Therefore the present invention has high purification SO 2and other harmful sour gas, effectively improve the features such as ammonia absorbent utilization rate, and can obtain high concentration bisulfite ammonium salt solution, there is good special industry purposes and prospect.
Brief description of the drawings
Fig. 1 is the method for application a kind of flue gas ammonia method desulfurizing of the present invention by-product high-purity ammonium bisulfite.
Wherein: 1-sulfur furnace; 2-cyclone separating tower; 3-heat exchanger; 4-washing, purifying tower; 5-first grade absorption tower; 6-two-level absorption tower; Tri-grades of absorption towers of 7-; 8-water scrubber; 9-circulating pump; 10-shower nozzle; 11-clean room; 12-base plate; 13-kerve; 14-one-level circulating tank; 15-secondary circulation pipe; Tri-grades of circulation pipes of 16-; 17-tank; 18-ammonia water tank; 19-wash cycle pond; 20-degassing tower.
Detailed description of the invention
Experiment Introduction: at when experiment simulated flue gas of being made up of mixed air of flue gas, experiment flow is identical with Fig. 1, but flow process is from first grade absorption tower, and simulated flue gas be preheating to 60 DEG C laggard enter flow process.
Embodiment 1: simulated flue gas composition: 78% N 2, 3% O 2, 15% SO 2, 3% CO 2and steam.Flue gas flow: 1m 3/ min.In first grade absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 5~6; In two-level absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 6~7; In three grades of absorption towers, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 6~7.Result is as follows:
Flue gas flow (m 3/min) SO after purifying 2Content (ppm) NH after purifying 3Content (ppm) NH 4HSO 3Solution concentration
1 58 32 75%
Embodiment 2: simulated flue gas composition: 78% N 2, 3% O 2, 12% SO 2, 7% CO 2and steam.Flue gas flow: 1m 3/ min.In first grade absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 5~6; In two-level absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 6~7; In three grades of absorption towers, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 6~7.Result is as follows:
Flue gas flow (m 3/min) SO after purifying 2Content (ppm) NH after purifying 3Content (ppm) NH 4HSO 3Solution concentration
1 65 28 70%
Embodiment 3: simulated flue gas is formed: 78% N 2, 8 O 2sO %, 8% 2, 5% CO 2and steam.Flue gas flow: 1m 3/ min.In first grade absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 5~6; In two-level absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 6~7; In three grades of absorption towers, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 5~6.Result is as follows:
Flue gas flow (m 3/min) SO after purifying 2Content (ppm) NH after purifying 3Content (ppm) NH 4HSO 3Solution concentration
1 58 62 72%
Embodiment 4: simulated flue gas is formed: 78% N 2, 3% O 2sO %, 10% 2, 8% CO 2and steam.Flue gas flow: 1m 3/ min.In first grade absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 5~6; In two-level absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 6~7; In three grades of absorption towers, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 6~7.Result is as follows:
Flue gas flow (m 3/min) SO after purifying 2Content (ppm) NH after purifying 3Content (ppm) NH 4HSO 3Solution concentration
1 62 27 73%
Embodiment 5: simulated flue gas is formed: 78% N 2, 3% O 2sO %, 12% 2, 6% CO 2and steam.Flue gas flow: 1m 3/ min.In first grade absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 5~6; In two-level absorption tower, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 6~7; In three grades of absorption towers, participate in the ammoniacal liquor and (NH of circulation 4) 2sO 3the pH value of solution is 6~7.Result is as follows:
Flue gas flow (m 3/min) SO after purifying 2Content (ppm) NH after purifying 3Content (ppm) NH 4HSO 3Solution concentration
1 65 26 72%

Claims (2)

1. the method for a flue gas ammonia method desulfurizing by-product high-purity ammonium bisulfite, it is characterized in that: the solid matter that is rich in sulphur is burnt, the flue gas of high concentration sulfur dioxide gas is rich in generation, and in described high concentration sulfur dioxide gas, the concentration of sulfur dioxide is more than 7%; Flue gas enters cyclone separator and carries out dedusting, and the flue gas after dedusting enters heat exchanger, cools the temperature to 60~70 DEG C; Flue gas enters washing, purifying tower, and washing, purifying tower structure and cyclone separator are similar, is just provided with shower nozzle on top, by shower nozzle ejection atomization water, the solid matter in flue gas is washed; Flue gas enters first grade absorption tower subsequently, first grade absorption tower inside at least comprises shower nozzle, several clean room and kerve from top to bottom, tower outside is provided with circulating pump, solution in kerve is constantly transported in shower nozzle by pipeline, the base plate of described clean room is with some apertures, by shower nozzle ejection atomization solution, this solution is by ammoniacal liquor and (NH 4) 2sO 3composition, the pH value of solution is controlled at 5~6, and the bisulfite ammonium salt solution of the high concentration that reaction generates falls into the kerve of first grade absorption tower, after concentration reaches requirement, from kerve, takes out and packs as finished product; Flue gas enters two-level absorption tower subsequently, and the structure of two-level absorption tower is identical with first grade absorption tower, by shower nozzle ejection atomization solution, this solution is by ammoniacal liquor and (NH 4) 2sO 3composition, the pH value of solution is controlled at 6~7; Flue gas enters three grades of absorption towers subsequently, and the structure on three grades of absorption towers is identical with first grade absorption tower, by shower nozzle ejection atomization solution, this solution is by ammoniacal liquor and (NH 4) 2sO 3composition, the pH value of solution is controlled at 6~7; Three grades of flue gas discharges after water scrubber washing that discharge on absorption tower, water scrubber structure is identical with washing, purifying tower structure;
The solution of flue gas being washed to rear generation in described washing, purifying tower enters degassing tower and carries out degassedly, and degassing tower is void tower structure, and top is provided with gas vent; The degassed solution completing enters wash cycle pond and precipitates, and again burns being rich in after solids of sedimentations such as thering is no the biochemical sulphur of completing combustion is collected, and recycles; The gas that degassing tower produces is admitted to first grade absorption tower.
2. the method for a kind of flue gas ammonia method desulfurizing as claimed in claim 1 by-product high-purity ammonium bisulfite, it is characterized in that: the solution of the participation reaction in three grades of absorption towers can be transported in two-level absorption tower and react, the solution of the participation reaction in two-level absorption tower can be transported to first grade absorption tower and react.
CN201210131357.4A 2012-05-02 2012-05-02 Method for ammonia method desulfurization of flue gas and high-purity ammonium hydrogen sulfite by-producing Active CN102658016B (en)

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CN103908883B (en) * 2014-04-18 2016-01-20 中石化南京工程有限公司 A kind of ammonia of sulfur recovery facility absorbs exhaust gas treating method
CN104208993A (en) * 2014-07-31 2014-12-17 仙桃市中星电子材料有限公司 Device and method for treatment of calcination tail gas
CN104474849B (en) * 2014-12-04 2017-01-04 中国钢研科技集团有限公司 Acid regeneration acid gas absorbs and tail gas emission system and Application way thereof
CN110002472A (en) * 2019-02-21 2019-07-12 武汉青江化工黄冈有限公司 The industrial method of by-product sodium sulphate continuous production sodium hydrogensulfite

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CN101934192B (en) * 2010-09-16 2012-01-25 江苏和亿昌环保工程科技有限公司 Double-tower ammonia-method desulfurization process

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US6773555B1 (en) * 1999-08-12 2004-08-10 Ebara Corporation Method for treating exhaust gas
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