US4044101A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Method of treating exhaust gases containing nitrogen oxides and sulfurous acid gas
Assignee: Asahi Kasei Corp
•
Filing: 1975-12-17
•
Granted: 1977-08-23
•
Expires: 1995-12-17
Abstract
Abstract A method of removing NO x and SO 2 from an exhaust gas containing NO x and SO 2 which comprises contacting an exhaust gas containing NO x and SO 2 with an aqueous solution containing M 2 SO 3 , an iron ion and an aminopolycarboxylic acid to absorb NO x and SO 2 in the aqueous solution and treating the resulting absorbing solution while preventing a contact of the solution with the exhaust gas, thereby to form M 2 S 2 O 6 in the absorbing solution and reducing NO x to N 2 . The M 2 S 2 O 6 formed in the absorbing solution can be easily removed by crystallization separation. With such method, NO x and SO 2 can be removed from exhaust gases at high rates and the absorbing solution can be easily regenerated and recycled to the absorbing zone.
Inventors
- 👤 Tokuichi Hisamatsu
- 👤 Taketsugu Kitamura
- 👤 Takeshiro Saito
- 👤 Hitoshi Takagi
- 👤 Takuzo Sekiya
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 01:02
CPC Classifications
B; B01; B01D; B01D53/00; B01D53/34
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
162 words
A method of treating exhaust gases containing nitrogen oxides and sulfurous acid gas which comprises contacting an exhaust gas containing nitrogen oxides and sulfurous acid gas with an aqueous solution containing a sulfite in a concentration of 0.05 to 1.0 mole/liter, an iron ion in a concentration of 0.01 to 0.7 g-ion/liter and an aminopolycarboxylic acid in a concentration of 0.005 to 2.0 moles/liter at 40° to 100° C. and a pH of 4 to 9 in an absorbing zone, so as to remove nitrogen oxides and sulfurous acid gas from said exhaust gas and form a dithionate in the absorbing solution and treating the absorbing solution from the absorbing zone at 40° to 100° C. for 1 to 30 minutes in a reducing zone while insulating the absorbing solution from contact with the exhaust gas, so as to reduce at least a portion of the absorbed nitrogen oxides to N 2 , iron ion to ferrous ion and form further dithionate.
Claim 2
Independent Claim
162 words
A method of treating exhaust gases containing nitrogen oxides and sulfurous acid gas which comprises contacting an exhaust gas containing nitrogen oxides and sulfurous acid gas with an aqueous solution containing a sulfite in a concentration of 0.05 to 1.0 mole/liter, an iron ion in a concentration of 0.01 to 0.7 g-ion/liter and an aminopolycarboxylic acid in a concentration of 0.005 to 2.0 moles/liter at 40° to 100° C. and a pH of 4 to 9 in an absorbing zone, so as to remove nitrogen oxides and sulfurous acid gas from said exhaust gas and form a dithionate in the absorbing solution and treating the absorbing solution from the absorbing zone at 40° to 100° C. for 1 to 30 minutes in a reducing zone while insulating the absorbing solution from contact with the exhaust gas, so as to reduce at least a portion of the absorbed nitrogen oxides to N 2 , iron ion to ferrous ion and form further dithionate.
Claim 3
Dependent Claim
29 words
A method according to claim 1 wherein the absorbing solution coming from the reducing zone is recycled to the absorbing zone and it is used for the absorption treatment.
Claim 4
Dependent Claim
37 words
A method according to claim 1 wherein the amount of the absorbing solution resident in either the absorbing zone or the reducing zone is 0.5 to 5 liters per Nm 3 of the exhaust gas per hour.
Claim 5
Dependent Claim
31 words
A method according to claim 1 wherein the amount of the aminopolycarboxylic acid or its salt in the absorbing solution is 0.5 to 2 moles per gram-ion of the iron ion.
Claim 6
Dependent Claim
20 words
A method according to claim 1 wherein the sulfate concentration in the absorbing solution is not higher than 1.0 mole/liter.
Claim 7
Dependent Claim
40 words
A method according to claim 1 wherein the aminopolycarboxylic acid in the absorbing solution is at least one member selected from the group consisting of nitrilotriacetic acid, nitrilotripropionic acid, N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid, ethylenediamine-tetraacetic acid, ethylenediamine-tetrapropionic acid, 1,2-propylenediamine-tetraacetic acid and diethylenetriamine-N,N,N',N",N"-pentaacetic acid.
Claim 8
Dependent Claim
49 words
A method according to claim 1 wherein a part or all of the absorbing solution is withdrawn from the absorbing zone or reducing zone, and sulfuric acid is added to the withdrawn absorbing solution to decompose the dithionate formed in the absorbing solution to a sulfate or a hydrogensulfate.
Claim 9
Dependent Claim
115 words
A method according to claim 7 wherein the sulfite contained in the initial aqueous solution is at least one member selected from the group consisting of potassium, sodium and ammonium sulfite whereby the dithionate formed and to be reacted with sulfuric acid is at least one member selected from the group consisting of potassium dithionate, sodium dithionate and ammonium dithionate, the absorbing solution treated with sulfuric acid is then treated with calcium sulfite, calcium hydroxide or calcium carbonate to convert the dithionate to the sulfite, gypsum formed by this treatment is separated from residual liquid containing the sulfite and the residual liquid is recycled and used as the absorbing solution for the exhaust gas treatment.
Claim 10
Dependent Claim
27 words
A method according to claim 1 wherein the sulfite is at least one member selected from the group consisting of potassium and sodium ortho-sulfites and acidic sulfite.
Claim 11
Dependent Claim
53 words
A method according to claim 9 wherein a part or all of the absorbing solution is withdrawn from the absorbing zone or reducing zone, the withdrawn absorbing solution is cooled or concentrated by evaporation to crystallize the dithionate accumulated in the absorbing solution, and the precipitated dithionate is separated from the absorbing solution.
Claim 12
Dependent Claim
24 words
A method according to claim 10 wherein the withdrawn absorbing solution is cooled at 0 to 50° C. to effect crystallization of the dithionate.
Claim 13
Dependent Claim
30 words
A method according to claim 10 wherein the crystallized and separated dithionate is heated at 200 to 800° C. to decompose it to an alkali sulfate and sulfurous acid gas.
Claim 14
Dependent Claim
70 words
A method according to claim 10 wherein at least one member selected from the group consisting of alkali hydroxides, alkali carbonates and alkali sulfites is added to a part or all of the absorbing solution from which the dithionate has been separated and removed, to adjust the sulfite concentration in the absorbing solution to the desired level, and the absorbing solution is recycled and used for the exhaust gas treatment.
Claim 15
Dependent Claim
60 words
A method according to claim 10 wherein sulfurous acid gas or calcium sulfite is reacted with a part or all of the absorbing solution from which the dithionate has been separated and removed, to convert the alkali sulfate in the absorbing solution to an acidic alkali sulfite and gypsum, and the so formed gypsum is removed from the absorbing solution.
Claim 16
Dependent Claim
72 words
A method according to claim 14 wherein the acidic alkali sulfite-containing solution left after separation of the gypsum is reacted with calcium hydroxide or calcium carbonate, after recovering sulfurous acid gas by stripping, to decompose the acidic alkali sulfite to an alkali sulfite and calcium sulfite, and the calcium sulfite is removed from the reaction mixture liquid and the residual liquid is recycled as the absorbing solution for the exhaust gas treatment.
Claim 17
Dependent Claim
102 words
A method according to claim 12, 13 wherein a part or all of said alkali sulfate and a part or all of the sulfurous acid gas which are both obtained by decomposition of the crystallized and separated dithionate are added to the absorbing solution from which the dithionate has been separated and removed; to the resulting solution is added a part or all of the calcium sulfite obtained by decomposition of the acidic alkali sulfite-containing solution left after separation of the gypsum thereby to convert the alkali sulfate to an acidic alkali sulfite and gypsum; and the gypsum is separated and removed.
Claim 18
Dependent Claim
51 words
A method according to claim 8, wherein the adsorbing solution treated with sulfuric acid is treated with calcium sulfite, and the residual liquid prior to recycling is treated with calcium hydroxide or calcium carbonate to form calcium sulfite and a sulfite corresponding to the dithionate, and the calcium sulfite is separated.
References Cited (Backward Citations)
DE1251900B
Cited
FR1454723A
Cited
GB1245854A
Cited
US3923954A
Cited
US3932585A
Cited
US3984522A
Cited
US3991161A
Cited
US3992508A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-08-22 | 1981-02-21 | 1981-08-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-08-22 | 1985-02-21 | 1985-08-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-08-22 | 1989-02-21 | 1989-08-23 | $7700.00 | Window Closed / Lapsed |