CN1559652A - Ammonia-acid method SO2 tail gas adsorption process using dynamic wave washer - Google Patents

Ammonia-acid method SO2 tail gas adsorption process using dynamic wave washer Download PDF

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Publication number
CN1559652A
CN1559652A CNA2004100219424A CN200410021942A CN1559652A CN 1559652 A CN1559652 A CN 1559652A CN A2004100219424 A CNA2004100219424 A CN A2004100219424A CN 200410021942 A CN200410021942 A CN 200410021942A CN 1559652 A CN1559652 A CN 1559652A
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liquid
gas
mother liquor
dynamic wave
stage
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CN1259122C (en
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严雪峰
刘利民
徐毅敏
冉峻南
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Fumin Xinye Industry And Trade Co ltd
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YUNNAN COPPER INDUSTRY Co Ltd
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Abstract

An application of power wave washer in absorbing CO2 from the tail gas generated by ammona-acid method is disclosed. In said power wave washer, the fume containing CO2 flows downward and the circulating liquid is prayed up ward. They are collided to generate a foam region, wheremore than 95% of CO2 in absorbed by said circulating liquid.

Description

Dynamic wave scrubber forammonia-acid method SO2Tail gas absorption process
Technical Field
The invention relates to low-concentration SO produced in industries such as sulfuric acid production, non-ferrous metal smelting, thermal power plants and the like2A tail gas absorption treatment method and equipment, in particular to a method for applying a dynamic wave scrubber to SO by an ammonia-acid method for the first time2And (5) tail gas absorption process.
Background
Ammonia-acid process SO2The tail gas absorption process utilizes (NH)4)2SO3-NH4HSO3-(NH4)2SO4The mixed solution is absorption mother liquor for absorbing SO in the flue gas2And recovering low concentration SO2The process comprises the following four steps: absorption, absorbent regeneration, decomposition and neutralization. The main chemical reactions are as follows:
1. absorbent for SO2The chemical reaction of the absorption is as follows:
2. absorb SO2The latter solution is made to contain the main absorbent (NH) in solution by adding ammonia4)2SO3Regenerated, the chemical reaction formula is as follows:
3. the mother liquor obtained after absorption is decomposed by using excessive concentrated sulfuric acid, and the chemical reaction formula is as follows:
4. the acidic decomposition liquid is neutralized by ammonia, and the chemical reaction formula is as follows:
ammonia-acid process SO2The circulating mother liquor adopted by the tail gas absorption process is mainly (NH)4)2SO3-NH3HSO3-(NH4)2SO4The mixed solution of (1), the solution components are: the total sub-salt concentration is about 450g/l, S/C is 0.85, the alkalinity is 3-10 titer, the specific gravity is 1.2, and the pH value is 5-6. The solution under the condition has high salt content, and the sulfuric acid tail gas contains no moisture, so the solution is easy to be subjected to operation fluctuation and specific gravity increaseCrystals are formed and the solution is somewhat corrosive.
Ammonia-acid process SO2The tail gas absorption process is realized by circulating main absorbent ammonium sulfite in mother liquor and SO in flue gas2Reacting to form ammonium bisulfite and reacting SO2A process for the desulfurization of flue gases, since the flue gases treated contain SO2The concentration is low, so the absorption effect is determined by the contact area between the smoke and the absorbent and the contact surface renewal speed.
Currently ammonia-acid process SO2The absorption equipment that the tail gas absorption adopted is mostly the foam tower, and this equipment efficiency is high, but equipment structure iscomplicated, the investment is big, easily form the crystallization in the production process and block up the column plate sieve mesh, uses and has certain limitation. The dynamic wave scrubber is a novel gas-liquid mass transfer device appearing in the late stage of the nineties of the twenty-century, has simple structure, low investment, difficult blockage and high operation elasticity, and is a high-efficiency gas-liquid mass transfer device.
Disclosure of Invention
The invention provides a dynamic wave scrubber applied to SO (SO) in an ammonia-acid method2The tail gas absorption process is characterized by that it utilizes the characteristics of dynamic wave scrubber and ammonia-acid method SO2The characteristics of the tail gas absorption process are combined, and the dynamic wave scrubber is firstly applied to SO by the ammonia-acid method2Tail gas absorption process as SO2The tail gas absorption equipment obtains satisfactory effect and success in production practice, the method has low investment and simple operation, and can effectively and reliably ensure SO2The tail gas reaches the standard and is discharged.
The dynamic wave washer is simple in structure, can be made of corrosion-resistant materials such as glass fiber reinforced plastics and the like, has no special precision requirement in manufacturing, and is corrosion-resistant, so that the pH value of mother liquor fluctuates in a large range and corrosion does not exist in actual operation, and stainless steel materials such as 1Cr18Ni9Ti can corrode after the pH value is less than 3, so that the final product is discolored. The spray head of the high-efficiency reverse-spraying scrubber adopts a large-opening form, can not be blocked due to crystallization, and dry gas such as target sulfuric acid tail gas has special adaptability and is circulatedNo measures are needed under the condition of pump-out failure, and the problems of blocking the liquid separation hole by crystallization and the like can not occur. The dynamic wave scrubber can form a stable foam area due to the unique gas-liquid reverse collision principle, the gas-liquid contact is sufficient, the gas-liquid surface updating speed is high, and the mass transfer process is particularly facilitated. To SO2The absorption rate can reach more than 95 percent. The method has high operation flexibility, the air quantity can fluctuate within the range of 50-120%, and the change of the foam area is small, so the method has high operation flexibility, is easy to operate and is easy to realize self-control operation. Meanwhile, as the gas-liquid contact in the inverse pipe of the dynamic wave washer is sufficient, the gas-liquid surface is updated quickly, the oxidation and decomposition speed of the sulfite is accelerated, the mixed decomposition and neutralization processes in the ammonia-acid process can be cancelled under the condition of ensuring the absorption rate by controlling reasonable process indexes, and the absorption mother liquor is directly evaporated, crystallized and dried to prepare ammonium sulfate, thereby reducing the processes and equipment and simplifying the process.
This invention is at low concentration SO2The tail gas absorption process for preparing ammonium sulfate can directly replace a foam tower as absorption equipment.
Description of the drawings: FIG. 1 is a schematic flow diagram of a dynamic wave scrubber.
FIG. 2 is a schematic diagram of a dynamic wave scrubber.
The specific implementation mode is as follows:
as shown in FIG. 1: for sulfuric acid tail gas SO2The last SO of the sulfuric acid process is used in the acid making system which does not reach the standard3SO-containing gas from the absorption column 12The tail gas is connected into a reverse spray pipe 3 of the dynamic wave scrubber 2. The flue gas flows from top to bottom and absorbs SO by the mother liquor2Then, the exhaust gas is discharged from an outlet pipe of the dynamic wave scrubber and is discharged into the atmosphere through an exhaust gas evacuation chimney 3.
The operation of the dynamic wave scrubber is illustrated by fig. 2: containing SO2The flue gas enters a reverse spray pipe 4 of the dynamic wave washer from top to bottom from an inlet of the dynamic wave washer, and circulating liquid is sent into the reverse spray pipe 4 of the dynamic wave washer from a mother liquid circulating pump 8 through a liquid feeding pipe 6The spray pipe is reversely sprayed from the spray head 5 from bottom to top along the direction of the air flow, the gas and the liquid collide reversely to form a foam area, the surface of the gas and the liquid in the foam area is continuously and violently updated, the foam area moves up and down along with the fluctuation of the air flow, and the SO in the gas phase is generated after the gas passes through the foam area2The tail gas is absorbed by ammonium sulfite in a liquid phase, and the tail gas is discharged from an outlet of the dynamic wave scrubber after being defoamed. The circulating liquid falls down from the reverse spray pipe and then is in a storage tank at the lower part of the scrubber cylinder 9, the liquid is circularly absorbed, and is discharged from the mother liquid output pipe 7 through the outlet of the circulating pump after meeting the process requirements, and the liquid level dropsThe liquid level is kept stable through make-up water, the ammonia water is added through an ammonia adding pipe 10, automatic regulating valves are installed on a water adding pipe 11, the ammonia adding pipe 10 and an ammonium sulfate mother liquor production pipe 7, and the automatic control of the process can be realized by controlling the PH value, the liquid level and the specific gravity. The flushing water pipe 12 is used for periodically flushing the mist eliminator 13.
In fig. 2: 4. the device comprises a back spray pipe, 5, a spray head, 6, a liquid feeding pipe, 7, an ammonium sulfate mother liquor production pipe, 8, a mother liquor circulating pump, 9, a cylinder, 10, an ammonia feeding pipe, 11, a water feeding pipe, 12, washing water, 13, a foam catching device, 14 and an air outlet pipe.
At the low concentration SO required2Tail gas absorption or SO absorption by ammonia process2The size of the dynamic wave scrubber can be determined according to the respective process conditions, and the liquid-gas ratio is generally 0.005m3/Nm3 Gas (es)The air speed of the reverse spray pipe is 20m/s, the pressure of the spray head is 15-20 kPa, and each dynamic wave scrubber can be provided with a first-stage or a second-stage spray head, such as an inlet SO2When the concentration is 1.5-2%, in order to ensure that the tail gas reaches the standard and is discharged, a method of connecting two dynamic wave washers in series and separating the two dynamic wave washers into two sections for absorption can be adopted. The control indexes of the circulating mother liquor process are as follows: during first-stage absorption: specific gravity of mother liquor: 1.2-1.24, pH value of mother liquor: 4-6, alkalinity of mother liquor: 5-8 titer, total sub-salt content: 10-40 g/L;
during two-stage absorption, the specific gravity of one-stage mother liquid is as follows: 1.2-1.24, pH: 4-6, alkalinity: 5-8 titer, total sub-salt content: 10-40 g/L, specific gravity of the second-stage mother liquid: 1.1-1.15, pH value of mother liquor: 5-6, alkalinity of mother liquor: 1-3 titer, total sub-salt content: 10-20 g/L.
The applicant firstly used a dynamic wave scrubber as tail gas SO in his own sulfuric acid two-series tail gas absorption process2Absorption apparatus, inspection by production practice, SO2The absorption rate can reach 95%, the operation is simple and convenient, the equipment maintenance cost is low, and the investment is lower than that of a stainless steel foam tower. Because the dynamic wave scrubber has reverse gas-liquid contact, the gas flow velocity is large, the gas-liquid agitation is violent, the contact is full, the sulfite in the mother liquor can be directly oxidized by the oxygen in the air, if the byproduct of the tail absorption process is ammonium sulfate, the subsequent mixing decomposition and neutralization processes of the sulfite can be reduced, the mother liquor can be directly evaporated and crystallized to prepare the ammonium sulfate, and the purposes of simplifying the process and saving the investment are achieved.

Claims (3)

1. Dynamic wave scrubber for ammonia-acid method SO2The tail gas absorption process is characterized in that: will contain SO2The tail gas is connected into a reverse spray pipe of a dynamic wave scrubber, the flue gas flows from top to bottom, the circulating liquid is sent into the reverse spray pipe from a mother liquid circulating pump through a liquid feeding pipe and is reversely sprayed out from a spray head from bottom to top along the direction of the air flow, the gas and the liquid collide reversely to form a foam area, the liquid-gas ratio is 0.005m3/Nm3 Gas (es)The gas velocity of the reverse spray pipe is 20m/s, the pressure of a spray head is 15-20 kPa, and the tail gas absorbs SO through mother liquor2And then the circulating liquid is discharged from an outlet pipe of the dynamic wave washer, the circulating liquid falls down from the reverse spray pipe, and the liquid is circularly absorbed in the washer cylinder and then is discharged from a mother liquid output pipe through a circulating pump outlet.
2. The absorption process according to claim 1, wherein: the reverse spray pipe is internally provided with a first-stage or a second-stage spray head; two dynamic wave washers can be connected in series for two-stage absorption.
3. Absorption process according to claims 1 and 2, characterized in that: during first-stage absorption: specific gravity of mother liquor: 1.2-1.24, pH value of mother liquor: 4-6, alkalinity of mother liquor: 5-8 titer, total sub-salt content: 10-40 g/L; during two-stage absorption, the specific gravity of one-stage mother liquid is as follows: 1.2-1.24, pH: 4-6, alkalinity: 5-8 titer, total sub-salt content: 10-40 g/L, specific gravity of the second-stage mother liquid: 1.1-1.15, pH value of mother liquor: 5-6, alkalinity of mother liquor: 1-3 titer, total sub-salt content: 10-20 g/L.
CN 200410021942 2004-02-27 2004-02-27 Ammonia-acid method SO2 tail gas adsorption process using dynamic wave washer Expired - Lifetime CN1259122C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101961589A (en) * 2010-08-31 2011-02-02 华东理工大学 Dynamic wave liquid seal tail gas absorption method and device
CN102350174A (en) * 2011-07-11 2012-02-15 中国石油化工集团公司 Method for selective removal of H2S by dynamic wave scrubber
CN102527214A (en) * 2011-12-23 2012-07-04 中国石油化工股份有限公司 Method for removing hydrogen sulfide from gas
CN103157347A (en) * 2013-04-01 2013-06-19 普辉(漳州)轻烃科技发展有限公司 Method for absorbing maleic-anhydride-containing gas by employing dynamic wave absorption tower
CN103506001A (en) * 2013-08-19 2014-01-15 云南云铜锌业股份有限公司 Desulfurization method for fume gas containing low-concentration sulfur dioxide
CN104258722A (en) * 2014-09-25 2015-01-07 昆明理工大学 Method for removing SO2 in tail gas
CN106178906A (en) * 2016-09-23 2016-12-07 杭州东日节能技术有限公司 Sulfur-containing tail gas dedusting and chlorine fluorine removing process device
CN107824035A (en) * 2017-12-01 2018-03-23 中冶焦耐(大连)工程技术有限公司 A kind of coking relieving haperacidity exhaust gas cleaner and method

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101961589A (en) * 2010-08-31 2011-02-02 华东理工大学 Dynamic wave liquid seal tail gas absorption method and device
CN102350174A (en) * 2011-07-11 2012-02-15 中国石油化工集团公司 Method for selective removal of H2S by dynamic wave scrubber
CN102527214A (en) * 2011-12-23 2012-07-04 中国石油化工股份有限公司 Method for removing hydrogen sulfide from gas
CN103157347A (en) * 2013-04-01 2013-06-19 普辉(漳州)轻烃科技发展有限公司 Method for absorbing maleic-anhydride-containing gas by employing dynamic wave absorption tower
CN103506001A (en) * 2013-08-19 2014-01-15 云南云铜锌业股份有限公司 Desulfurization method for fume gas containing low-concentration sulfur dioxide
CN103506001B (en) * 2013-08-19 2016-03-30 云南云铜锌业股份有限公司 A kind of sulfur method containing low concentration sulphur dioxide flue gas
CN104258722A (en) * 2014-09-25 2015-01-07 昆明理工大学 Method for removing SO2 in tail gas
CN106178906A (en) * 2016-09-23 2016-12-07 杭州东日节能技术有限公司 Sulfur-containing tail gas dedusting and chlorine fluorine removing process device
CN107824035A (en) * 2017-12-01 2018-03-23 中冶焦耐(大连)工程技术有限公司 A kind of coking relieving haperacidity exhaust gas cleaner and method

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Effective date of registration: 20170515

Address after: 650000 Baisha street, Yongding Subdistrict Office, Fumin County, Yunnan, Kunming

Patentee after: FUMIN XINYE INDUSTRY AND TRADE CO.,LTD.

Address before: 650102 Wang Jia Qiao, Xishan District, Yunnan, Kunming

Patentee before: Yunnan Copper Co.,Ltd.

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Granted publication date: 20060614