WO2004056449A2 - Process for removal of so2 from off-gases by reaction with h202 - Google Patents
Process for removal of so2 from off-gases by reaction with h202 Download PDFInfo
- Publication number
- WO2004056449A2 WO2004056449A2 PCT/EP2003/013699 EP0313699W WO2004056449A2 WO 2004056449 A2 WO2004056449 A2 WO 2004056449A2 EP 0313699 W EP0313699 W EP 0313699W WO 2004056449 A2 WO2004056449 A2 WO 2004056449A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- removal
- gases
- reaction
- filter
- Prior art date
Links
- 239000007789 gas Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 title description 11
- 239000000443 aerosol Substances 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 7
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 7
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims 1
- 229910003556 H2 SO4 Inorganic materials 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 12
- 239000003595 mist Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000012719 wet electrostatic precipitator Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2215/00—Preventing emissions
- F23J2215/20—Sulfur; Compounds thereof
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2217/00—Intercepting solids
- F23J2217/10—Intercepting solids by filters
- F23J2217/102—Intercepting solids by filters electrostatic
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2219/00—Treatment devices
- F23J2219/40—Sorption with wet devices, e.g. scrubbers
Definitions
- the present invention relates to a process for removal of S0 2 from off-gases by reaction with H 2 0 2 .
- H 2 0 2 0.1-0.5% H 2 0 2 .
- the absorption is typically carried out at a temperature of 50-80°C of the circulating solution.
- H 2 0 2 is added either as a concentrated aqueous solution of H 2 0 2 to the circulating acid, or it is produced by electrolysis of a side stream of the circulating acid. The produced acid is drawn off from the circulating acid.
- the known process usually requires installation of a low velocity aerosol filter downstream of the absorption tower to remove sulphuric acid aerosol (acid mist) in order to meet acid mist emission regulations requiring less than about 5 mol ppm HS0 4 in the stack gas.
- Fine acid mist (aerosol) that may be present in the off-gas is not removed efficiently in the absorption tower. Fine acid mist is also formed in the absorption tower itself by reaction between S0 and H 2 0 2 vaporised from the absorbing liquid.
- FIG. 1 A preferred embodiment of the invention is shown in Fig. 1.
- a solution of 0.1-30% H 2 0 2 in line 1 is sprayed by the spray nozzles 3 into a stream of off-gas in line 2 containing typically between 100-1000 ppm S0 2 and having a temperature typically in the range of 50-120°C.
- the nozzles are placed in duct 4, so that the spray is evenly distributed in the gas stream upstream of the mist filter 5 in which the gas is passed in parallel through a number of low velocity filter candles 6.
- Even distribution of the droplets in the gas is desirable for the process and the most even distribution of the droplets is achieved by using air- atomising nozzles producing very small droplets.
- the H 2 S0 formed in the process accumulates in the filter elements or candles from which it is drained off through line 7. Most or all of the mass of the droplets evaporate before the gas enters the filter candles, whereby most of the H 2 0 evaporates and reacts in the gas phase under formation of sul- phuric acid aerosol. However, it is not necessary that the droplets are completely evaporated before the gas enters the filter elements. The reaction between S0 2 and H 2 0 will be completed and the thermal equilibrium will be established in the mist filter elements without decreasing the efficiency of the S0-removal. Thus, the injection of the aqueous solution H 2 0 2 serves two purposes :
- the water comprised in the solution cools off the off-gas in line 2 by evaporation of the droplets, whereby the off-gas is cooled off to a desired temperature of the filter elements or candles typically to a temperature between 50°C and 70°C.
- the concentration of H 2 S0 4 in the produced acid will be the equilibrium concentration of H 2 S0 4 at the actual temperature and H 2 0 partial pressure in the gas phase.
- An off-gas stream of 1000 Nm 3 /h at 100°C contains 200 ppm S0 2 + 10% H 2 0 and has a temperature of 100°C. 96% S0 2 removal is desired.
- the aerosol filter is designed for opera- tion at maximum 70°C. Operation at 67-70°C is chosen in order to achieve the highest possible acid strength and low content of remaining H 2 0 2 in the produced acid.
- the process is conducted as follows : 15.7 kg/h water con- taining 2.0 wt% H 2 0 2 is injected into the off-gas, whereby the off-gas is cooled to 65-70°C in thermal equilibrium.
- the mist filter is 75 mm thick and has a flow area of 2.5 m 2 .
- the diameter of the fibres is about 8 ⁇ m.
- Experiments carried out under these conditions show that about 96% of the S0 2 is removed under production of 1.7 kg/h 50% H 2 S0 4 with about 500 ppm H 2 0 2 .
- the treated gas contains less than 2 ppm H 2 S0 4 and the content of H 2 0 2 is below the detection limit .
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0317462-0A BR0317462B1 (en) | 2002-12-21 | 2003-12-04 | process for the removal of so2 in outlet gases by reaction with h2o2. |
US10/539,604 US7776299B2 (en) | 2002-12-21 | 2003-12-04 | Process for removal of SO2 from off-gases by reaction with H2O2 |
AU2003288228A AU2003288228B2 (en) | 2002-12-21 | 2003-12-04 | Process for removal of SO2 from off-gases by reaction with H202 |
DE60319738T DE60319738T2 (en) | 2002-12-21 | 2003-12-04 | PROCESS FOR REMOVING SO2 FROM EXHAUST GASES BY MITH2O2 REACTION |
CA2511311A CA2511311C (en) | 2002-12-21 | 2003-12-04 | Process for removal of so2 from off-gases by reaction with h2o2 |
EP03780121A EP1578517B1 (en) | 2002-12-21 | 2003-12-04 | Process for removal of so2 from off-gases by reaction with h202 |
JP2004561212A JP2006512190A (en) | 2002-12-21 | 2003-12-04 | Method for removing SO2 from off-gases by reaction with H2O2 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DKPA200201992 | 2002-12-21 | ||
DKPA200201992 | 2002-12-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2004056449A2 true WO2004056449A2 (en) | 2004-07-08 |
WO2004056449A3 WO2004056449A3 (en) | 2004-09-30 |
Family
ID=32668631
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/013699 WO2004056449A2 (en) | 2002-12-21 | 2003-12-04 | Process for removal of so2 from off-gases by reaction with h202 |
Country Status (13)
Country | Link |
---|---|
US (1) | US7776299B2 (en) |
EP (1) | EP1578517B1 (en) |
JP (1) | JP2006512190A (en) |
KR (1) | KR20050084454A (en) |
CN (1) | CN100354028C (en) |
AT (1) | ATE388751T1 (en) |
AU (1) | AU2003288228B2 (en) |
BR (1) | BR0317462B1 (en) |
CA (1) | CA2511311C (en) |
DE (1) | DE60319738T2 (en) |
ES (1) | ES2300632T3 (en) |
RU (1) | RU2346731C2 (en) |
WO (1) | WO2004056449A2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007025948A1 (en) * | 2005-09-02 | 2007-03-08 | Basf Se | Method and device for removing sulphur dioxide from a dry gas stream |
CN107970911A (en) * | 2017-12-01 | 2018-05-01 | 南京云高新型材料有限公司 | A kind of environmental protection and energy saving high conversion rare earth catalyst and preparation method thereof |
US10675585B2 (en) | 2016-05-24 | 2020-06-09 | Haldor Topsoe A/S | Method for the removal of oxygen from an industrial gas |
US10933372B2 (en) | 2017-02-16 | 2021-03-02 | Haldor Topsoe A/S | Method for the removal of oxygen from an industrial gas feed |
Families Citing this family (13)
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US7404938B2 (en) * | 2004-05-11 | 2008-07-29 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Emission control system |
CN100393393C (en) * | 2006-03-30 | 2008-06-11 | 国电科技环保集团有限公司 | Arrangement for sprinkling and pre-washing flue gas in entrance of flue gas-desulfurizing absorption tower |
CN100463847C (en) * | 2006-06-23 | 2009-02-25 | 李开春 | Method for preparing vitriol from flue gas |
DE102007020141A1 (en) * | 2007-04-26 | 2008-10-30 | Bayer Materialscience Ag | Recycle gas scrubber for the removal of SOx and sulfuric acid aerosols from chlorine-containing process gases |
DE102007039926B4 (en) * | 2007-08-23 | 2012-03-22 | Götaverken Miljö AB | Method and device for exhaust gas purification |
KR101039715B1 (en) * | 2009-01-23 | 2011-06-13 | 엘에스니꼬동제련 주식회사 | Method of Treating a By-product Gas from Copper Smelting |
KR101341967B1 (en) * | 2012-06-22 | 2013-12-16 | 한국에너지기술연구원 | Method for producing hydrogen and sulfuric acid from sulfur dioxide using electrochemical process |
US8877152B2 (en) * | 2013-02-27 | 2014-11-04 | Alstom Technology Ltd | Oxidation system and method for cleaning waste combustion flue gas |
CN103657375B (en) * | 2014-01-07 | 2015-07-08 | 上海科洋科技股份有限公司 | Method and system for removing trace SO2 in tail gas by gas phase oxidation |
EP3592449A1 (en) * | 2017-03-08 | 2020-01-15 | Shell Internationale Research Maatschappij B.V. | Process for removing so2 from gas with so2 content that is temporarily very high |
CN110407181A (en) * | 2019-08-19 | 2019-11-05 | 广东新生环保科技股份有限公司 | A kind of tail gas sulphur dioxide relieving haperacidity recovery system |
US11071947B2 (en) | 2019-10-30 | 2021-07-27 | W. L. Gore & Associates, Inc. | Catalytic efficiency of flue gas filtration |
US10940471B1 (en) | 2019-10-30 | 2021-03-09 | W. L. Gore & Associates, Inc. | Catalytic efficiency of flue gas filtration |
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US3733393A (en) * | 1970-09-30 | 1973-05-15 | Air Liquide | Purification of combustion products before discharge into the atmosphere |
US3953578A (en) * | 1972-02-04 | 1976-04-27 | Oxysynthese | Method for purification of industrial flue gases |
DE4036899A1 (en) * | 1990-11-20 | 1992-05-21 | Degussa | Sulphuric acid prodn. by oxidn. of sulphur di:oxide mixt. - using hydrogen peroxide for desulphurisation of gases arising from sulphite-treated grape juice |
DE4424367A1 (en) * | 1994-07-11 | 1996-01-18 | Siemens Ag | Process and appts. to purify flue gas |
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DE436899C (en) | 1926-11-09 | August Henze | Freischaeler for beet harvesters | |
US3503704A (en) | 1966-10-03 | 1970-03-31 | Alvin M Marks | Method and apparatus for suppressing fumes with charged aerosols |
US3760061A (en) * | 1971-03-02 | 1973-09-18 | Du Pont | High-strength acid containing h2o2 to scrub so2 |
CA1069273A (en) | 1974-05-23 | 1980-01-08 | Fmc Corporation | Purification of sulfur-containing waste gases with hydrogen peroxide |
JPS53135878A (en) | 1977-04-30 | 1978-11-27 | Ishikawajima Harima Heavy Ind Co Ltd | Wet denitrating or wet denitrating and desulurizing method |
DE3237699A1 (en) | 1982-10-12 | 1984-04-12 | Toschi Produktions-Gesellschaft mbH, 2800 Bremen | METHOD FOR SEPARATING AIR POLLUTANTS FROM EXHAUST GAS, IN PARTICULAR FROM FLUE GAS, BY CONDENSATION |
CA1159773A (en) * | 1981-09-30 | 1984-01-03 | George Drzewiecki | Wet electrostatic precipitator having removable nested hexagonal collector plates and magnetic aligning and rapping means |
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US5017350A (en) * | 1989-06-02 | 1991-05-21 | Union Carbide Canada Limited | Gas scrubbing process |
CN2133353Y (en) * | 1992-09-17 | 1993-05-19 | 王明环 | Smoke sweetening duster for coal boiler |
JPH06142440A (en) | 1992-11-13 | 1994-05-24 | Nippon Steel Corp | Oxidation treatment of gas containing harmful gas and device for the same |
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-
2003
- 2003-12-04 EP EP03780121A patent/EP1578517B1/en not_active Expired - Lifetime
- 2003-12-04 WO PCT/EP2003/013699 patent/WO2004056449A2/en active IP Right Grant
- 2003-12-04 BR BRPI0317462-0A patent/BR0317462B1/en active IP Right Grant
- 2003-12-04 ES ES03780121T patent/ES2300632T3/en not_active Expired - Lifetime
- 2003-12-04 CN CNB2003801067013A patent/CN100354028C/en not_active Ceased
- 2003-12-04 JP JP2004561212A patent/JP2006512190A/en active Pending
- 2003-12-04 US US10/539,604 patent/US7776299B2/en active Active
- 2003-12-04 AU AU2003288228A patent/AU2003288228B2/en not_active Expired
- 2003-12-04 CA CA2511311A patent/CA2511311C/en not_active Expired - Lifetime
- 2003-12-04 RU RU2005123041/15A patent/RU2346731C2/en active
- 2003-12-04 KR KR1020057011703A patent/KR20050084454A/en active Search and Examination
- 2003-12-04 DE DE60319738T patent/DE60319738T2/en not_active Expired - Lifetime
- 2003-12-04 AT AT03780121T patent/ATE388751T1/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US3733393A (en) * | 1970-09-30 | 1973-05-15 | Air Liquide | Purification of combustion products before discharge into the atmosphere |
US3953578A (en) * | 1972-02-04 | 1976-04-27 | Oxysynthese | Method for purification of industrial flue gases |
DE4036899A1 (en) * | 1990-11-20 | 1992-05-21 | Degussa | Sulphuric acid prodn. by oxidn. of sulphur di:oxide mixt. - using hydrogen peroxide for desulphurisation of gases arising from sulphite-treated grape juice |
DE4424367A1 (en) * | 1994-07-11 | 1996-01-18 | Siemens Ag | Process and appts. to purify flue gas |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007025948A1 (en) * | 2005-09-02 | 2007-03-08 | Basf Se | Method and device for removing sulphur dioxide from a dry gas stream |
US10675585B2 (en) | 2016-05-24 | 2020-06-09 | Haldor Topsoe A/S | Method for the removal of oxygen from an industrial gas |
US10933372B2 (en) | 2017-02-16 | 2021-03-02 | Haldor Topsoe A/S | Method for the removal of oxygen from an industrial gas feed |
CN107970911A (en) * | 2017-12-01 | 2018-05-01 | 南京云高新型材料有限公司 | A kind of environmental protection and energy saving high conversion rare earth catalyst and preparation method thereof |
CN107970911B (en) * | 2017-12-01 | 2020-10-13 | 南京云高新型材料有限公司 | Environment-friendly energy-saving high-conversion-rate rare earth catalyst and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
EP1578517B1 (en) | 2008-03-12 |
AU2003288228A1 (en) | 2004-07-14 |
RU2346731C2 (en) | 2009-02-20 |
AU2003288228B2 (en) | 2009-08-06 |
RU2005123041A (en) | 2006-01-27 |
DE60319738T2 (en) | 2009-04-02 |
BR0317462A (en) | 2005-11-16 |
BR0317462B1 (en) | 2013-02-05 |
US7776299B2 (en) | 2010-08-17 |
ATE388751T1 (en) | 2008-03-15 |
CN1729039A (en) | 2006-02-01 |
CA2511311C (en) | 2011-09-20 |
ES2300632T3 (en) | 2008-06-16 |
DE60319738D1 (en) | 2008-04-24 |
JP2006512190A (en) | 2006-04-13 |
CA2511311A1 (en) | 2004-07-08 |
WO2004056449A3 (en) | 2004-09-30 |
US20060057047A1 (en) | 2006-03-16 |
KR20050084454A (en) | 2005-08-26 |
EP1578517A2 (en) | 2005-09-28 |
CN100354028C (en) | 2007-12-12 |
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