CN1259122C - 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 PDFInfo
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- CN1259122C CN1259122C CN 200410021942 CN200410021942A CN1259122C CN 1259122 C CN1259122 C CN 1259122C CN 200410021942 CN200410021942 CN 200410021942 CN 200410021942 A CN200410021942 A CN 200410021942A CN 1259122 C CN1259122 C CN 1259122C
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- mother liquor
- dynamic wave
- gas
- tail gas
- pipe
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 title 1
- 238000010521 absorption reaction Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000012452 mother liquor Substances 0.000 claims abstract description 29
- 239000007921 spray Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims description 41
- 239000006260 foam Substances 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 238000005507 spraying Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract 2
- 238000005187 foaming Methods 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The present invention provides a technology for applying a dynamic wave washing device to absorb tail gas by an ammonia-acid method. The tail gas with SO2 is led into a reverse spraying pipe of the dynamic wave washing device and flows from top to bottom, circulating liquid is transferred into the reverse spraying pipe through a liquid feeding pipe by a mother liquor circulating pump, and sprayed from a spray head from the bottom to top in a reverse direction of the airflow direction, the gas and the liquid reversely crash to form a foaming region, the tail gas is discharged from an outlet pipe of the dynamic wave washing device after the mother liquor absorbs the SO2 of the tail gas, and the circulating liquid is discharged from a mother liquor outflow pipe. The technology has the advantages that the operation flexibility is high because the gas flow can fluctuate within a range of 50 to 120% and the change of the foaming region is small, the SO2 absorption rate can reach more than 95%, the processes of mixed decomposition and neutralization can be cancelled because of the adoption of the dynamic wave washing device, the process flow is simplified, and the investment is saved.
Description
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 that the solution is easy to form crystals when the operation fluctuates and the specific gravity is increased, and the solution has certain corrosivity.
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 is complicated, 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 applied for the first timeIn the ammonia-acid process SO2Tail 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 efficient reverse-spraying scrubber adopts a large-opening form, so that blockage caused by crystallization can be avoided, the drying gas such as the target sulfuric acid tail gas has special adaptability, no measures need to be taken under the condition of failure of the circulating pump, and the problems of blockage of a liquid separation hole caused by crystallization and the like can be avoided. 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 SO2Flue gas enters a reverse spray pipe 4 of the dynamic wave scrubber from top to bottom from an inlet of the dynamic wave scrubber, circulating liquid is sent into the reverse spray pipe through an upper liquid pipe 6 by a mother liquid circulating pump 8 and is reversely sprayed out from a spray head 5 from bottom to top along with the direction of air flow, the gas and the liquid collide reversely to form a foam area, the gas and the liquid surface in the foam area are continuously and violently updated, the foam area moves up and down along with the fluctuation of the air flow, and SO in the gas phase is generated after the gas passes through the2The 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 (2)
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 mother liquor is sent into the reverse spray pipe through a liquor feeding pipe by a mother liquor circulating pump and is reversely sprayed out from a spray head from bottom to top along the direction of the air flow, the gas and the liquor 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 liquor2Then the water is discharged from an outlet pipe of the dynamic wave scrubber,the mother liquid falls down from the reverse spray pipe, and is discharged from a mother liquid output pipe through a mother liquid circulating pump outlet after being circularly absorbed in the scrubber cylinder body.
2. The absorption process according to claim 1, wherein: two stages of spray heads are arranged in the reverse spray pipe, two dynamic wave washers are connected in series for two-stage absorption, and when the two-stage absorption is carried out, the specific gravity of one section of mother liquor is as follows: 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, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410021942 CN1259122C (en) | 2004-02-27 | 2004-02-27 | Ammonia-acid method SO2 tail gas adsorption process using dynamic wave washer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410021942 CN1259122C (en) | 2004-02-27 | 2004-02-27 | Ammonia-acid method SO2 tail gas adsorption process using dynamic wave washer |
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| CN1559652A CN1559652A (en) | 2005-01-05 |
| CN1259122C true CN1259122C (en) | 2006-06-14 |
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| CN 200410021942 Expired - Lifetime CN1259122C (en) | 2004-02-27 | 2004-02-27 | Ammonia-acid method SO2 tail gas adsorption process using dynamic wave washer |
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Families Citing this family (8)
| 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 |
| 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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- 2004-02-27 CN CN 200410021942 patent/CN1259122C/en not_active Expired - Lifetime
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| CN1559652A (en) | 2005-01-05 |
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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 |