CA1305848C - Process for oxidizing hydrogen sulfide contained in mineral acid - Google Patents
Process for oxidizing hydrogen sulfide contained in mineral acidInfo
- Publication number
- CA1305848C CA1305848C CA000541409A CA541409A CA1305848C CA 1305848 C CA1305848 C CA 1305848C CA 000541409 A CA000541409 A CA 000541409A CA 541409 A CA541409 A CA 541409A CA 1305848 C CA1305848 C CA 1305848C
- Authority
- CA
- Canada
- Prior art keywords
- mineral acid
- ppm
- hydrogen sulfide
- acid
- sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/2372—Anionic impurities, e.g. silica or boron compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
PROCESS FOR OXIDIZING HYDROGEN SULFIDE CONTAINED IN
MINERAL ACID
ABSTRACT OF THE DISCLOSURE
Hydrogen sulfide contained in mineral acid is oxidized. To this end, a vanadium content of at least 10 ppm is established in the mineral acid prior to adding hydrogen peroxide.
MINERAL ACID
ABSTRACT OF THE DISCLOSURE
Hydrogen sulfide contained in mineral acid is oxidized. To this end, a vanadium content of at least 10 ppm is established in the mineral acid prior to adding hydrogen peroxide.
Description
130S8~
This invention relates to a process for oxidizing hy-drogen sulfide contained in mineral acid by means of hy-drogen peroxide.
It has been described that hydrogen sulfide can be reacted in a neutral or alkaline solution with hydrogen peroxide with formation of sulfate and thiosulfate ions (cf. KIRK-OTHMER: "Encyclopedia of Chemical Technology", 3rd edition, volume 22, 1933, page 116). It has also been described that the oxidation behaviour of hydrogen per-oxide with respect to hydrogen sulfide in a mineral acid,such as hydrochloric acid, sulfuric acid or phosphoric acid, is not uniform; depending on the particular acid and its concentration, the reaction occurs but incompletely, at low reaction velocity or even fails to take place (cf.
"Gmelins Handbuch der Anorganischen Chemie", 8th edition, system number 9, "Schwefe].", part 3, issue 1, 1953, page 94; VDI-Richtlinie No. 3486, sheet 1, 1979, page 3).
It is also possible for hydrogen sulfide contained in mineral acid to be expelled by evaporating the mineral acid or blowing out with air (cf. WINNACKER-KUCHLER:
"Chemische Technologie", volume 2, Anorganische Technolo-gie I, 4th edition, 1982, page 219; "Ullmanns Enzyklopadie der technischen Chemie", 4th edition, volume 18, 1979, page 313). In this case, however vaporous matter and off gas containing hydrogen sulfide are obtained for which it is invariably necessary to be worked up.
~305848 It is therefore highly desirable to have a procass for oxidizing hydrogen sulfide contained in mineral acid with the aid of hydrogen peroxide, permitting the hydrogen sulfide to be oxidized quantitatively within short reac-tion periods, independently from the concentration of themineral acid and the mineral acid to be freed from it. To this end, the invention provides for a vanadium content of at least 10 ppm to be established in the mineral acid prior to admixing it with hydrogen peroxide.
Further preferred and optional features of the inven-tion provide:
a) for a vanadium content of up to 200 ppm, preferably of up to 100 ppm, to be established;
b) for the reaction mixture to be allowed to stand over a period of 10 to 30 minutes;
c) for the mineral acid to be admixed with 4 to 20, preferably 5 to 10 mols H202 per mol H2S.
In the process of this invention, sulfate ions and elementary sulfur are obtained as the oxidation products of the sulfide ion. Despite the fact that the sulfur is obtained in the form of fine-particulate material, it is possible for it to be separated from the mineral acid by pressure or suction filtration.
The process of this invention occurs at a satisfacto-ry velocity already at room temperature; it is however advantageous for it to be carried out at a temperature of from 30 - 60C.
The following Examples illustrate the invention which is naturally not limited thereto:
~3~1t58~3 Example 1 (comparative Example) Chemically pure phosphoric acid (40 % H3P04) contain-ing 350 ppm sulfide was admixed at room temperature with 6 mols H202 per mol sulfide, while stirring. Stirring was continued for a period of 20 minutes, and 21 % of the hy-drogen sulfide contained in the phosphoric acid was found to have been oxidized.
Example Z (invention) The procedure of Example 1 was repeated with that mo-dification however that a vanadium content of 10 ppm wasestablished in the phosphoric acid prior to admixing it with H202. Aftar a reaction period of 15 minutes, the phosphoric acid was odorless. Analysis indicateq that 100 % of the sulfide had been oxidized.
Example 3 (invention) Wet-process phosphoric acid (40 % H3P04) containing 630 ppm sulfide and 100 ppm vanadium was admixed at 40C
with 10 mol Hz02 per mol sulfide, and the whole was stirred for 20 minutes. After that time, 100 % of the hy-drogen sulfide contained in the wet-process phosphoric acid was found to have been oxidized.
Example 4 ~invention) Wet-process phosphoric acid (70 % H3Pû4) containing 85 pprn sulfide and 30 ppm vanadium was admixed with 8 mol H202 per mol sulfide, and the whole was stirred for 15 mi-nutes at 60C. After that time, 100 % of the hydrogen sul-fide contained in the phosphoric acid was found to have been oxidized.
~305848 Example 5 (comparative Example) Sulfuric acid (10 % strength) containing 290 ppm sul-fide was admixed with 10 mols H202 per mol sulfide and the whole was stirred for 20 minutes at room temperature.
After that time, the sulfuric acid still had the distinct smell of hydrogen sulfide; only 9 % of the hydrogen sul-fide contained in it was found to have been oxidized.
Example 6 (invention) The procedure of Example 5 was repeated with that mo-dification however that a vanadium content of 100 ppm wasestablished in the sulfuric acid prior to admixing it with H202. After a reaction period of 15 minutes, the sulfuric acid was odorless. Analysis indicated that 100 % of the sulfide had been oxidized.
Example 7 (comparative Example) Hydrochloric acid (5 % strength) containing 340 ppm sulfide was admixed with 10 mol H202 per mol sulfide and stirred for 20 minutes at room te~lperature. After that time, 48 % of the hydrogen sulfide contained in the hydro-chloric acid was found to have been oxidized.
Example 8 (invention) The procedure of Example 7 was repeated with thatmodification however that a vanadium content of 10 ppm was established in the hydrochloric acid prior to admixing it with H202. After stirring for 20 minutes at room tempera-ture, 100 % of the hydrogen sulfide contained in the hy-drochloric acid was found to have been oxidized.
The results of the above Examples are summarized in the following Table.
o ~ ~ ~ O o o ~ o a~ o r/ ~ ~I O O O O ~ O
o C~l ._ ,, ~
C~l O Sr) ~ r-l O O(D CD O CO O O O O
r S ~1 ~-1 ~1 ~1 rl ~1 r-l 'OO O
1:1 N j~
E
~rl E O O O O O O O O
O. ~ O ~ O ~
~ .. ._ ~
LLI ~ ~ ~
C ~rl E~ O O O L~l O O O O
O r-l O. ~ ~ t.O C~l N t'l o r ;~
c ~ o o o o ~ o ul ~n o _ ~
r ~ ~ rl ~ r n~
~l a~
r~ C
cl: Y f~ Q O h O t-l o o o oo o E CL E
o~ ~ tn c~ I tn I u~ O o o r O ~ ~ O Y O ~ C/) r-l r-l c ~ c ~ c ~ c _ . _ _.__ .
~ .~
This invention relates to a process for oxidizing hy-drogen sulfide contained in mineral acid by means of hy-drogen peroxide.
It has been described that hydrogen sulfide can be reacted in a neutral or alkaline solution with hydrogen peroxide with formation of sulfate and thiosulfate ions (cf. KIRK-OTHMER: "Encyclopedia of Chemical Technology", 3rd edition, volume 22, 1933, page 116). It has also been described that the oxidation behaviour of hydrogen per-oxide with respect to hydrogen sulfide in a mineral acid,such as hydrochloric acid, sulfuric acid or phosphoric acid, is not uniform; depending on the particular acid and its concentration, the reaction occurs but incompletely, at low reaction velocity or even fails to take place (cf.
"Gmelins Handbuch der Anorganischen Chemie", 8th edition, system number 9, "Schwefe].", part 3, issue 1, 1953, page 94; VDI-Richtlinie No. 3486, sheet 1, 1979, page 3).
It is also possible for hydrogen sulfide contained in mineral acid to be expelled by evaporating the mineral acid or blowing out with air (cf. WINNACKER-KUCHLER:
"Chemische Technologie", volume 2, Anorganische Technolo-gie I, 4th edition, 1982, page 219; "Ullmanns Enzyklopadie der technischen Chemie", 4th edition, volume 18, 1979, page 313). In this case, however vaporous matter and off gas containing hydrogen sulfide are obtained for which it is invariably necessary to be worked up.
~305848 It is therefore highly desirable to have a procass for oxidizing hydrogen sulfide contained in mineral acid with the aid of hydrogen peroxide, permitting the hydrogen sulfide to be oxidized quantitatively within short reac-tion periods, independently from the concentration of themineral acid and the mineral acid to be freed from it. To this end, the invention provides for a vanadium content of at least 10 ppm to be established in the mineral acid prior to admixing it with hydrogen peroxide.
Further preferred and optional features of the inven-tion provide:
a) for a vanadium content of up to 200 ppm, preferably of up to 100 ppm, to be established;
b) for the reaction mixture to be allowed to stand over a period of 10 to 30 minutes;
c) for the mineral acid to be admixed with 4 to 20, preferably 5 to 10 mols H202 per mol H2S.
In the process of this invention, sulfate ions and elementary sulfur are obtained as the oxidation products of the sulfide ion. Despite the fact that the sulfur is obtained in the form of fine-particulate material, it is possible for it to be separated from the mineral acid by pressure or suction filtration.
The process of this invention occurs at a satisfacto-ry velocity already at room temperature; it is however advantageous for it to be carried out at a temperature of from 30 - 60C.
The following Examples illustrate the invention which is naturally not limited thereto:
~3~1t58~3 Example 1 (comparative Example) Chemically pure phosphoric acid (40 % H3P04) contain-ing 350 ppm sulfide was admixed at room temperature with 6 mols H202 per mol sulfide, while stirring. Stirring was continued for a period of 20 minutes, and 21 % of the hy-drogen sulfide contained in the phosphoric acid was found to have been oxidized.
Example Z (invention) The procedure of Example 1 was repeated with that mo-dification however that a vanadium content of 10 ppm wasestablished in the phosphoric acid prior to admixing it with H202. Aftar a reaction period of 15 minutes, the phosphoric acid was odorless. Analysis indicateq that 100 % of the sulfide had been oxidized.
Example 3 (invention) Wet-process phosphoric acid (40 % H3P04) containing 630 ppm sulfide and 100 ppm vanadium was admixed at 40C
with 10 mol Hz02 per mol sulfide, and the whole was stirred for 20 minutes. After that time, 100 % of the hy-drogen sulfide contained in the wet-process phosphoric acid was found to have been oxidized.
Example 4 ~invention) Wet-process phosphoric acid (70 % H3Pû4) containing 85 pprn sulfide and 30 ppm vanadium was admixed with 8 mol H202 per mol sulfide, and the whole was stirred for 15 mi-nutes at 60C. After that time, 100 % of the hydrogen sul-fide contained in the phosphoric acid was found to have been oxidized.
~305848 Example 5 (comparative Example) Sulfuric acid (10 % strength) containing 290 ppm sul-fide was admixed with 10 mols H202 per mol sulfide and the whole was stirred for 20 minutes at room temperature.
After that time, the sulfuric acid still had the distinct smell of hydrogen sulfide; only 9 % of the hydrogen sul-fide contained in it was found to have been oxidized.
Example 6 (invention) The procedure of Example 5 was repeated with that mo-dification however that a vanadium content of 100 ppm wasestablished in the sulfuric acid prior to admixing it with H202. After a reaction period of 15 minutes, the sulfuric acid was odorless. Analysis indicated that 100 % of the sulfide had been oxidized.
Example 7 (comparative Example) Hydrochloric acid (5 % strength) containing 340 ppm sulfide was admixed with 10 mol H202 per mol sulfide and stirred for 20 minutes at room te~lperature. After that time, 48 % of the hydrogen sulfide contained in the hydro-chloric acid was found to have been oxidized.
Example 8 (invention) The procedure of Example 7 was repeated with thatmodification however that a vanadium content of 10 ppm was established in the hydrochloric acid prior to admixing it with H202. After stirring for 20 minutes at room tempera-ture, 100 % of the hydrogen sulfide contained in the hy-drochloric acid was found to have been oxidized.
The results of the above Examples are summarized in the following Table.
o ~ ~ ~ O o o ~ o a~ o r/ ~ ~I O O O O ~ O
o C~l ._ ,, ~
C~l O Sr) ~ r-l O O(D CD O CO O O O O
r S ~1 ~-1 ~1 ~1 rl ~1 r-l 'OO O
1:1 N j~
E
~rl E O O O O O O O O
O. ~ O ~ O ~
~ .. ._ ~
LLI ~ ~ ~
C ~rl E~ O O O L~l O O O O
O r-l O. ~ ~ t.O C~l N t'l o r ;~
c ~ o o o o ~ o ul ~n o _ ~
r ~ ~ rl ~ r n~
~l a~
r~ C
cl: Y f~ Q O h O t-l o o o oo o E CL E
o~ ~ tn c~ I tn I u~ O o o r O ~ ~ O Y O ~ C/) r-l r-l c ~ c ~ c ~ c _ . _ _.__ .
~ .~
Claims (6)
1. A process for oxidizing hydrogen sulfide contained in mineral acid by means of hydrogen peroxide which com-prises initially establishing in the mineral acid a vanadium content of at least 10 ppm and then adding the hydrogen peroxide.
2. The process as claimed in claim 1, wherein a vanadium content of up to 100 ppm is established.
3. The process as claimed in claim 1, wherein a vanadium content of up to 200 ppm is established.
4. The process as claimed in claim 1, wherein the reac-tion mixture is allowed to stand over a period of 10 to 30 minutes.
5. The process as claimed in claim 1, wherein the mine-ral acid is admixed with 4 to 20 mols H2O2 per mol H2S.
6. The process as claimed in claim 5, wherein the mine-ral acid is admixed with 5 to 10 mols H2O2 per mol H2S.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863623134 DE3623134A1 (en) | 1986-07-09 | 1986-07-09 | METHOD FOR THE OXIDATION OF HYDROGEN SULFUR CONTAINED IN MINERAL ACIDS |
| DEP3623134.7 | 1986-07-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1305848C true CA1305848C (en) | 1992-08-04 |
Family
ID=6304778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000541409A Expired - Fee Related CA1305848C (en) | 1986-07-09 | 1987-07-07 | Process for oxidizing hydrogen sulfide contained in mineral acid |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0253137B1 (en) |
| CA (1) | CA1305848C (en) |
| DE (2) | DE3623134A1 (en) |
| ES (1) | ES2032777T3 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2700450A1 (en) * | 1977-01-07 | 1978-07-13 | Isega Ind Studien | Removing odorous sulphur cpds. from waste gases or water - esp. in cellulose mfr. or in petrochemistry |
| DE2942545A1 (en) * | 1979-10-20 | 1981-06-04 | Riedel-De Haen Ag, 3016 Seelze | METHOD FOR PRODUCING A CLEANED OXIDATION-RESISTANT INORGANIC ACID AND AFTER-OBTAINED ACID |
-
1986
- 1986-07-09 DE DE19863623134 patent/DE3623134A1/en not_active Withdrawn
-
1987
- 1987-06-12 DE DE8787108529T patent/DE3779197D1/en not_active Expired - Fee Related
- 1987-06-12 EP EP87108529A patent/EP0253137B1/en not_active Expired - Lifetime
- 1987-06-12 ES ES198787108529T patent/ES2032777T3/en not_active Expired - Lifetime
- 1987-07-07 CA CA000541409A patent/CA1305848C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0253137B1 (en) | 1992-05-20 |
| DE3623134A1 (en) | 1988-01-21 |
| ES2032777T3 (en) | 1993-03-01 |
| EP0253137A3 (en) | 1988-12-21 |
| DE3779197D1 (en) | 1992-06-25 |
| EP0253137A2 (en) | 1988-01-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |