CN1226459A - Process for purifying and recovering waste SOx gas from coal boiler - Google Patents
Process for purifying and recovering waste SOx gas from coal boiler Download PDFInfo
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- CN1226459A CN1226459A CN 99113403 CN99113403A CN1226459A CN 1226459 A CN1226459 A CN 1226459A CN 99113403 CN99113403 CN 99113403 CN 99113403 A CN99113403 A CN 99113403A CN 1226459 A CN1226459 A CN 1226459A
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Abstract
A process for purifying and recovering SO2 in the waste gas from coal-burning boiler includes such technological steps as dusting flue, cooling, absorbing SO2 with ammonia, neutralization with solution of ammonium sulfite, preparing sulfuric acid and preparing ammonium sulfate. A combined absorption tower integrating washing, dusting, cooling and absorbing functions is disclosed. Its advantages include low cost of operation, low energy consumption,compact structure, and less investment.
Description
The invention belongs to the field of environmental protection, and relates to SO in coal-fired boiler waste gas2The purification and recovery process.
As is well known, the flue gas pollution of coal-fired boilers is one of the most main sources of air pollution and is always the main object of the environmental management work. SO in exhaust gas produced by burning coal2The content of (A) is generally over 1000ppm, some is even as high as 3000-4000 ppm, and coal is used as coal for thermal power plants, nonferrous metal smelting plants and the likeDepartment of fuel. The flue gas amount is huge, if the flue gas amount is not treated, the flue gas amount can bring serious harm to the environment, and the flue gas amount has attracted high attention of relevant departments. At present, SO in coal-fired boiler exhaust gas2The following methods are mainly used for processing:
(1) the abandoning method comprises the following steps: absorbing SO in waste gas by limestone slurry as absorbent2And the calcium sulfate is generated and then discarded. The method has large equipment investment and high running cost, so the method is difficult to be accepted by related factories;
(2) sodium sulfite thermal concentration method: this process is a typical recovery process, but the side reactions are severe, SO2The loss can be as high as 15%, corresponding to 1 ton SO recovered2The loss of NaOH of (2) is 220kg, so the loss of the absorbent is quite high and the operation cost is very high; secondly, the steam consumption of the process is also large, with 1 ton of SO recovered2The steam consumption can reach more than 10 tons, and the equipment investment is also large;
(3) U.S. patent No. 3,843,789(1974) discloses a method for direct oxidation of ammonium sulfate by ammonia absorption, which is also a typical recovery method, and has the main disadvantages of high ammonia loss, high energy consumption, low oxidation rate, complex equipment and great operation difficulty;
(4) U.S. patent No. 4,519,994(1985) discloses a phosphate process which reduces the oxidation loss to below 1% and recovers 1 ton of SO2Alkali consumption of less than 10kg, but desorption of SO2The steam consumption of (2) is still large.
In addition, there are other methods, such as electron beam method and plasma method, which have the disadvantages of high energy consumption, difficult equipment manufacture, etc. Therefore, the SO in the exhaust gas of a new coal-fired boiler is developed and researched2The treatment method of (2) has become an urgent need for industrial sector and environmental protection.
The invention aims to: 1. discloses SO in coal-fired boiler exhaust gas with ammonia as an absorbent and sulfuric acid and ammonium sulfate as final products2The purification and recovery process overcomes the defects of high energy consumption and operation cost and single recovered product in the prior art(ii) a 2. Discloses a method for collecting washing, dust removal, temperature reduction and SO absorption2The absorption tower is an integrated combined type device, so as to improve the absorption efficiency and reduce the equipment investment.
The idea of the invention is that:
1. by using ammonia as SO2Absorbing SO in flue gas2Generating a mixture of ammonium bisulfite and ammonium sulfite, ammonium sulfite for short, and neutralizing the generated ammonium sulfite and sulfuric acid to release gaseous SO2The concentration of the compound can reach 50 percent (V)0V is more than V0Is SO2V is the volume of the gas mixture, the same applies hereinafter) while producing an ammonium sulfate solution. The large amount of reaction heat released during this neutralization reaction will contribute to the SO2Thereby reducing the steam consumption of the ammonium sulfate evaporation concentration. SO (SO)2The sulfuric acid is prepared by oxidation and absorption by a conventional method, part of the sulfuric acid is recycled, and part of the sulfuric acid can be used as a product. Due to SO2The concentration is higher, so that the investment of a sulfuric acid preparation device can be reduced, steam can be byproduct, and the energy consumption is reduced; the generated ammonium sulfate solution can be prepared into ammonium sulfate by adopting a conventional method;
2. because SO is removed from the waste gas of the coal-fired boiler2Besides, there is a lot of smoke and dust, and the temperature is also higher, the invention will wash, remove dust, lower the temperature, absorb, NH in the tail gas3The six functions of washing and demisting are integrated, and an absorption tower which occupies a small area and adopts a sieve plate with large aperture and high aperture ratio and regular packing as an inner member of the tower is designed to improve the mass transfer efficiency, reduce entrainment and pressure drop and reduce equipment investment.
Based on the above conception, the invention designs a new technological process for SO in flue gas2The process mainly comprises 4 processes of ① dedusting and cooling of flue gas and SO 2② neutralization of the ammonium sulfite solution, ③ sulfuric acid production, ④ ammonium sulfate production, fig. 1 is a block diagram of the process:
1- -dedusting, Cooling and SO of flue gases2Absorption process of
2- -neutralization of ammonium sulfite solution
3- -sulfuric acid preparation process
4- -Process for preparing ammonium sulfate
The waste gas of the coal-fired boiler is firstly subjected to dust removal, temperature reduction and SO of the flue gas2The absorption process 1, the smoke dust is removed by water washing, the temperature is reduced, and the SO in the ammonia water solution is absorbed2Generating ammonium sulfite, exhausting the purified flue gas through a chimney, and discharging the sewage out of the system. The absorption temperature is 40-60 ℃, the total ammonium content in the absorption liquid is 0.2-10 mol/L, the gas-liquid ratio is 1,000-10,000 (volume ratio, the same below), and the washing gas-liquid ratio is 1,000-5,000 (volume ratio, the same below). The reaction formula of the process is as follows:
The generated ammonium sulfite solution is neutralized with sulfuric acid in the neutralization process 2, and gaseous ammonium sulfite solution with concentration higher than 50 percent is desorbedSO2And generating ammonium sulfate solution with the concentration of 50-75% (wt%). The total ammonium ratio of the added sulfuric acid to the ammonium sulfite solution is 0.4 to 0.5 (molar ratio). The process is exothermic, and can release large amount of heat to help SO2And the ammonium sulfate solution is evaporated and concentrated, thereby reducing the steam consumption of the ammonium sulfate evaporation and concentration. The reaction formula of the process is as follows:
Relieving the SO2Sending to sulfuric acid preparation process 3, introducing part of the prepared sulfuric acid into neutralization process 2 for recycling, and using the rest as product;
the ammonium sulfate solution generated in the neutralization process 2 is sent to an ammonium sulfate preparation process 4 to prepare the ammonium sulfate product.
Figure 2 is a flow diagram of the process. In the figure:
5-reheater 6-absorption tower
7-neutralization tank 8-sulfuric acid preparation device
9- - -ammonium sulfate preparation facilities
The temperature of the coal-fired boiler is 120-200 ℃ and the SO is contained2The temperature of the flue gas is reduced to 90-120 ℃ through a reheater 5, the flue gas enters a cooling and dedusting section at the lower part of an absorption tower 6, the temperature of the flue gas is reduced to 40-60 ℃ and then enters an absorption section at the middle part, and an ammonia-containing water solution enters the tower from the upper part. In order to maintain a certain concentration of the absorption liquid on each section of the absorption section, the absorption liquid can enter the absorption tower in sections to supplement ammonia in sections, and the absorption liquid circulates in the sections; the washing water enters the tower from the cooling and dedusting section at the lower part of the tower 6. In the absorption tower, SO2The absorption rate of the gas can reach more than 95 percent, the dust removal rate can reach more than 99 percent, the temperature of the absorbed gas is reduced to 40-60 ℃, and the SO of the gas is2The content of the (D) can be reduced to be below 100ppm, and the (D) is discharged from a chimney after passing through a reheater 5; absorb SO2The ammonia water solutionreacts to generate ammonium sulfite, enters a neutralization tank 7, is neutralized with sulfuric acid from a sulfuric acid preparation device 9, and SO is desorbed2The concentration of the sulfuric acid is generally 50-70%, and the sulfuric acid is sent to a sulfuric acid preparation device 9 and used for preparing sulfuric acid with the concentration of 98%. To SO2Or introducing air into the neutralizing tank 7 in an amount of SO 25 to 10 times of the volume of the mixture, and adding SO2Diluting to 10-12%; the ammonium sulfate flowing out of the bottom of the neutralization tank 7 enters an ammonium sulfate preparation device 9 for preparing finished ammonium sulfate; the sewage is discharged from the bottom of the absorption tower 6.
As can be seen from the above process, the process of the invention has the following significant advantages: 1. SO in flue gas absorbed by ammonia water solution2Almost totally concentrated to SO with a concentration of more than 50%2Gas ensures that 30-40% of the total amount of the gas can be prepared into 98% industrial sulfuric acid, and 60-70% of the gas is ammonium sulfate; 2. the operation cost is relatively highLow, 1 ton SO per recovery2The ammonia dosage is 350-380 kg, and is reduced by 30-40% compared with the traditional process.
The process of the present invention may employ a conventional absorption tower, or preferably a combined absorption tower, and fig. 3 is a schematic diagram of the absorption tower. In the figure:
10-flue gas inlet 11-washing plate
12-partition plate 13-absorption plate
14-corrugated plate structured packing 15-lift cap
16-demister 17-flue gas outlet
18- -absorption liquid inlet 19- -circulating absorption liquid outlet
20- -absorbing liquid outlet 21- -washing water inlet
22-sewage drain 23-gas distributor
24-tower body
Fig. 4 is a schematic view of direction a-a in fig. 3.
The combined absorption tower is a combination body and is provided with a cylindrical tower body 24, the bottom of the tower body 24 is provided with a gas distributor 23 which can be a ring distributor generally and can ensure that gas uniformly enters the absorption tower, and a gas inlet 10 and a sewage outlet 22 are arranged at the lower part of the tower body 24;
1-3 washing plates 11 are arranged above the tower bottom gas distributor 23. The washing plate 11 is a large-hole sieve plate with the hole diameter of 10-30 mm and the opening rate of 10-30%, and other types such as a double-hole sieve plate, a grating plate and the like can also be adopted;
the middle part of the tower body 24 is provided with 1-5 absorption plates 13 and 1-5 partition plates 12, and each absorption plate 13 and partition plate 12 form an absorption section. Each partition plate 12 is provided with 10-40 air lifting caps 15, and the air lifting caps have the functions of enabling air to smoothly enter the upper layer and blocking absorption liquid from flowing into the lower layer; corrugated plate structured packing 14 is arranged below the partition plate 12, so that air flow can be uniformly distributed, the mass transfer efficiency is improved, liquid drop coalescence can be realized, and entrainment under high air speed is reduced; each absorption section is provided with an absorption liquid inlet 18 and a circulating absorption liquid outlet 19, and the circulating absorption liquid outlet 19 is arranged below the gas lifting cap 15 so as to be beneficial to the rising of gas; the absorption liquid outlet 20 is arranged atthe last partition plate; the absorption plate 13 is a large-hole sieve plate with the hole diameter of 10-30 mm and the opening rate of 10-30%, and other types such as a double-hole-diameter sieve plate, a grating plate and the like can also be adopted;
a demister 16 is provided in the upper part of the tower body 24. The demister 16 may be a conventional demister such as a wire mesh demister, a filler demister, or the like;
the gas outlet 17 is arranged at the top of the column 24.
In operation, flue gas enters a tower body 24 from a gas inlet 10 at the bottom of the tower through a gas distributor 23, is washed by washing water entering from a washing water inlet 21, and then sequentially passes through a partition plate 12, an absorption plate 13 and a demister 16 and then leaves the absorption tower through a gas outlet 17; the absorption liquid enters the tower through an absorption liquid inlet 18, is then led out through a circulating absorption liquid outlet 19, is partially recycled, enters the next absorption section, is finally led out of the tower through an absorption liquid outlet 20, and enters the next procedure.
In order to prevent the high-temperature flue gas from damaging the absorption tower, the high-temperature flue gas may be washed and cooled before entering the absorption tower, and fig. 5 shows the absorption tower with a washing pipe. In the figure:
25-washing pipe 26-water tank
27- -baffle
The high-temperature flue gas is firstly cooled by washing water in a washing pipe 25 and then enters an absorption tower.
The combined absorption tower has the following remarkable advantages:
1. washing, dedusting, cooling, absorbing and NH in tail gas3The six functions of washing, recovering and defoaming are integrated, the process and the equipment are compact, and the occupied area is small;
2. the tower internals compounded by the sieve plates and the fillers are adopted, so that the mass transfer efficiency is obviously improved, and the entrainment is less;
3. the sieve plate with large aperture and high aperture ratio is adopted, the pressure drop is small, the energy consumption is low, and the flux is high;
the present invention will be further illustrated by the following examples.
Example 1
The smoke gas amount of a coal-fired boiler of a certain 25MW unit is 10 ten thousand standard m3Hour, SO2The content is 3000ppm, the temperature is 80 ℃, three sections are adoptedAnd (4) absorbing.
The operating process parameters are as follows:
ammonium concentration in the absorption liquid:
0.5-9 mol/L, wherein the concentration of each section from top to bottom is respectively as follows: 0.5mol/L,2.4 mol/L,9.0mol/L
Circulation amount of absorption liquid: 50 m3Hour/hour
Amount of washing water: 80 m3Hour/hour
Amount of liquid absorbed into the neutralization tank: 2207 kg/h, wherein:
NH4HSO340％(wt％),(NH4)2SO317.5％(wt％),(NH4)2SO44％(wt％)
the dosage of the neutralized sulfuric acid: 780 kg/h
The ammonia dosage is as follows: 280 kg/h
Water usage in the absorption section: 850 kg/h
SO in tail gas2The content is as follows: ammonia content in 157ppm tail gas: 34ppm of
The yield of sulfuric acid (98%) is 440 kg/h yield of ammonium sulfate: 1050 kg/h
The structural parameters of the combined absorption tower are as follows:
tower internal diameter: 3.35 m tower height: 5m
Number of washing plates: 1, mesh diameter: the aperture ratio of 15mm is 25 percent
Number of absorbing plates: 3, mesh diameter: the aperture ratio of 15mm is 25 percent
Number of partition plates: 3 liters of air caps: 36
Height of the filler: 3 × 200 filler type: 170X
Containing 3000ppm SO2The temperature of the high-temperature flue gas at 80 ℃ is reduced to 68 ℃ after passing through a washing pipe 25, the flue gas enters a tower, the temperature is reduced to 50 ℃ after washing, and the flue gas is discharged from a chimney after absorption and defoaming; the neutralization temperature of the absorption liquid and sulfuric acid fed into the neutralization tank 7 was 90 ℃ and the amount of air blown was 1350 kg/hr.
Example 2
The same technological parameters and structural parameters of the combined absorption tower as those of the embodiment 1 are adopted, but the absorption section is changed from three sections to four sections, the concentration of ammonium in the absorption liquid is changed to 0.2-9 mol/L, and the concentrations of the sections from top to bottom are respectively as follows: 0.23mol/L,1.7mol/L,3.7mol/L,9.0mol/L, the results are as follows:
SO in tail gas2The content is as follows: ammonia content in 53ppmtail gas: 7.1ppm of
The yield of sulfuric acid (98%) is 460 kg/h yield of ammonium sulfate: 1080 kg/h
Claims (6)
1. SO in coal-fired boiler waste gas2The purification and recovery process is characterized by mainly comprising 4 processes:
① dust removal, temperature reduction and SO of flue gas2The absorption process of (2): the waste gas of the coal-fired boiler is firstly subjected to dust removal, temperature reduction and SO of the flue gas2The absorption process (1) is carried out at the absorption temperature of 40-60 ℃, the total ammonium content in the absorption liquid is 0.2-10 mol/L, the gas-liquid ratio is 1,000-10,000 (volume ratio), and the gas-liquid ratio of the washing water is 1,000-5,000 (volume ratio);
② neutralization of the solution of ammonium sulfite the ammonium sulfite formed in process ① is neutralized with sulfuric acid in neutralization process (2) and desorbed as gaseous SO2Generating ammonium sulfate solution;
③ Process for preparing sulfuric acid by desorbing SO2Sending to sulfuric acid preparation process (3), introducing part of the prepared sulfuric acid and recycling in process (2), wherein part of the prepared sulfuric acid can be used as a product;
④ ammonium sulfate preparation process, the ammonium sulfate solution generated in the neutralization process (2) is sent to the ammonium sulfate preparation process (4) to prepare the ammonium sulfate product.
2. The process as claimed in claim 1, wherein the absorption liquid is introduced into the absorption process (1) in stages
3. The process as claimed in claims 1-2, wherein air is blown in during the neutralization (2), the air being blown in an amount SO21-10 times of the volume.
4. The process of claim 1, wherein the flue gas is dedusted, cooled and SO cooled2The absorption process (1) is carried out in a combined absorption tower, the combined absorption tower is a combination body and is provided with a cylindrical tower body (24), the bottom of the tower body 24 is provided with a gas distributor 23, and a gas inlet 10 and a sewage outlet 22 are arranged at the lower part of the tower body 24;
1-3 washing plates (11) are arranged above the tower bottom gas distributor (23);
the middle part of the tower body (24) is provided with 1-5 absorption plates (13) and 1-5 partition plates (12), each absorption plate (13) and partition plate (12) form an absorption section, each partition plate (12) is provided with an air lifting cap (15), corrugated plate structured packing (14) is arranged below each partition plate (12), each absorption section is provided with an absorption liquid inlet (18) and a circulating absorption liquid outlet (19), the circulating absorption liquid outlet (19) is arranged below the air lifting cap (15), and the absorption liquid outlet (20) is arranged at the last partition plate;
a demister (16) is arranged at the upper part of the tower body (24);
the gas outlet (17) is arranged at the top of the tower body (24).
5. The process as claimed in claim 4, characterized in that a wash pipe (25) is arranged outside the combined absorption column.
6. The process as claimed in claims 4 to 5, wherein the washing plate (11) is a large-pore sieve plate with a pore diameter of 10 to 30mm and an aperture ratio of 10 to 30%; the absorption plate (13) is a large-hole sieve plate, the hole diameter is 10-30 mm, and the opening rate is 10-30%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN99113403A CN1087180C (en) | 1999-01-07 | 1999-01-07 | Process for purifying and recovering waste SOx gas from coal boiler |
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| CN99113403A CN1087180C (en) | 1999-01-07 | 1999-01-07 | Process for purifying and recovering waste SOx gas from coal boiler |
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| CN1226459A true CN1226459A (en) | 1999-08-25 |
| CN1087180C CN1087180C (en) | 2002-07-10 |
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| CN99113403A Expired - Fee Related CN1087180C (en) | 1999-01-07 | 1999-01-07 | Process for purifying and recovering waste SOx gas from coal boiler |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368061C (en) * | 2003-09-24 | 2008-02-13 | 郑州海天电力环保实业有限公司 | Integration method for ammonia process of desulfurizing flue gas and multiple utilizing desulfurized products and equipment |
| CN1919419B (en) * | 2006-08-11 | 2011-04-13 | 李湘忠 | Ammonia sulfur process art |
| CN102309920A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for removing NOx and SOx from fluid catalytic cracking (FCC) flue gas |
| CN101698134B (en) * | 2009-10-27 | 2012-05-02 | 德阳市南邡再生资源有限公司 | Method for treating sulfur dioxide high temperature tail gas |
| CN102989187A (en) * | 2011-09-19 | 2013-03-27 | 中国石油化工股份有限公司 | Reaction distillation equipment |
| CN107321167A (en) * | 2017-08-05 | 2017-11-07 | 山东新龙集团有限公司 | A kind of boiler fired coal flue gas desulfurization and the method for producing sulfur dioxide |
| CN109737766A (en) * | 2019-01-09 | 2019-05-10 | 刘童童 | A kind of metal smelt waste gas treatment process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4519994A (en) * | 1984-02-27 | 1985-05-28 | Stauffer Chemical Company | Process for absorption of SO2 into phosphate absorbent |
-
1999
- 1999-01-07 CN CN99113403A patent/CN1087180C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368061C (en) * | 2003-09-24 | 2008-02-13 | 郑州海天电力环保实业有限公司 | Integration method for ammonia process of desulfurizing flue gas and multiple utilizing desulfurized products and equipment |
| CN1919419B (en) * | 2006-08-11 | 2011-04-13 | 李湘忠 | Ammonia sulfur process art |
| CN101698134B (en) * | 2009-10-27 | 2012-05-02 | 德阳市南邡再生资源有限公司 | Method for treating sulfur dioxide high temperature tail gas |
| CN102309920A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for removing NOx and SOx from fluid catalytic cracking (FCC) flue gas |
| CN102309920B (en) * | 2010-07-07 | 2014-01-01 | 中国石油化工股份有限公司 | Method for removing NOx and SOx from fluid catalytic cracking (FCC) flue gas |
| CN102989187A (en) * | 2011-09-19 | 2013-03-27 | 中国石油化工股份有限公司 | Reaction distillation equipment |
| CN102989187B (en) * | 2011-09-19 | 2015-02-11 | 中国石油化工股份有限公司 | Reaction distillation equipment |
| CN107321167A (en) * | 2017-08-05 | 2017-11-07 | 山东新龙集团有限公司 | A kind of boiler fired coal flue gas desulfurization and the method for producing sulfur dioxide |
| CN109737766A (en) * | 2019-01-09 | 2019-05-10 | 刘童童 | A kind of metal smelt waste gas treatment process |
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