WO1995004588A1 - Method for removing hydrogen sulphide from mixture gas containing hydrogen sulphide and excessive amounts of steam and ammonia - Google Patents
Method for removing hydrogen sulphide from mixture gas containing hydrogen sulphide and excessive amounts of steam and ammonia Download PDFInfo
- Publication number
- WO1995004588A1 WO1995004588A1 PCT/KR1994/000107 KR9400107W WO9504588A1 WO 1995004588 A1 WO1995004588 A1 WO 1995004588A1 KR 9400107 W KR9400107 W KR 9400107W WO 9504588 A1 WO9504588 A1 WO 9504588A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen sulphide
- ammonia
- mixture gas
- vol
- steam
- Prior art date
Links
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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- 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
- B01D53/002—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 by condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
-
- 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
- C01B17/64—Thiosulfates; Dithionites; Polythionates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
Definitions
- the present invention relates to a method for removing hydrogen sulphide (H2S) from a mixture gas containing hydrogen sulphide and containing steam (H2O) and ammonia (NH3). More specifically, the present invention relates to a method for removing hydrogen sulphide from a mixture gas, in which the mixture gas containing less than 70 vol % of steam, less than 30 vol % of ammonia, below 10 vol % of hydrogen sulphide and other inert gases such as CO and CO2 is oxidized on a non-uniform catalyst by means of air or oxygen so as to convert the hydrogen sulphide (H2S) into ammonium thiosulfate ((NH4)2S2 ⁇ 3) and element sulphur (S), thereby completely removing the hydrogen sulphide from the mixture gas.
- H2S hydrogen sulphide
- H2S ammonium thiosulfate
- S element sulphur
- the present invention relates to a method for removing hydrogen sulphide from the mixture gas, in which, before a waste gas mixture (generally containing: 60-70 vol % of steam, 5-20 vol % of ammonia, 2-5 vol% of hydrogen sulphide, and other inert gases) of a steel manufacturing plant is incinerated in an incineration furnace, the waste mixture gas is reacted on a catalyst by means of air or oxygen so as to convert the hydrogen sulphide (H2S) into ammonium thiosulfate ((NH4)2S2 ⁇ 3) or into element sulphur (S), thereby completely removing the hydrogen sulphide from the mixture gas.
- a waste gas mixture generally containing: 60-70 vol % of steam, 5-20 vol % of ammonia, 2-5 vol% of hydrogen sulphide, and other inert gases
- the method for directly removing hydrogen sulphide through oxidation includes a Claus process, a Super Claus process and a MODOP process.
- a Claus process an acidic gas containing a high level of hydrogen sulphide (over 20 vol %) is subjected to a thermal decomposition reaction within a Claus furnace at a temperature of 1100 - 1200°C based on Formulas 1 and 2 below.
- the sulphur gas which is produced based on Formula 1 is made to pass through a cooling device in which the sulphur gas is converted to a liquid so as to be recovered.
- the unreacted hydrogen sulphide and the sulphur dioxide which is produced based on Formula 2 are subjected to a catalytic reaction within a 2-stage or 3-stage catalyst reaction vessel at a temperature of 200 - 350'C based on Formula 3 below.
- the recovering rate for the sulphur (S) in the Claus process is about 90 - 96% in the case of the 2-stage catalyst reaction process, and 95 - 98% in the case of 3- stage catalyst reaction process.
- the MODOP process (Oil And Gas Journal, January 11, 63 (1988)) uses a catalyst of Ti ⁇ 2 series to directly oxidize hydrogen sulphide of about 1 vol % (contained in the Claus tail gas) by means of air so as to recover sulphur.
- the sulphur recovering rate in this method is about 70 - 95%.
- the conversion, X, for hydrogen sulphide of the mixture gas was 98%
- the selectivity Si for the ammonium thiosulfate was 45%
- the selectivity S2 for sulphur was 55%
- the selectivity S3 for the sulphur dioxide was 0%.
- Example 2 The conditions were the same as those of Example 1, and only the reaction temperatures were different.
- the conversion rates for the different reaction temperatures are shown in Table 2 below. As shown in Table 2, at temperatures over 170°C, the removal of hydrogen sulphide was possible by 95%, and the production ratio of sulphur to ammonium thiosulfate could be adjusted to some degree.
- Example 12 In order to elicit the influence of hydrocarbons and CO and CO2 on the removal of hydrogen sulphide besides ammonia and water in the mixture gas, a mixture gas composed of ammonia (100 ml/min), hydrogen sulphide (30 ml/min), steam (700 ml/min), CO (50 ml/min), CO2 (100 ml/min), methane (100 ml/min), ethylene (100 ml/min) and nitrogen (700 ml/min) was made to react in the same manner as that of Example.1.
- the concentration of hydrogen sulphide in the mixture gas was varied within the range of 1 - 10% by varying the flow rate of nitrogen, but the conversion X and the selectivities were not significantly affected.
- Example 2 The process was carried out in the same manner as that of Example 1, except that there was used a catalyst formed by supporting 5 wt % of cobalt and 5 wt % of molybdenum on Ti ⁇ 2• In this case, the conversion rate was 93%, and the selectivity for sulphur was 81%, while the rest of the materials formed was a mixture of ammonium sulfite-hydrate ( ( NH 4)2 S0 3" H 2°) and ammonium sulfate ((NH4)2S ⁇ 4).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Catalysts (AREA)
- Industrial Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69403055T DE69403055T2 (en) | 1993-08-09 | 1994-08-06 | METHOD FOR REMOVING HYDROGEN SULFIDE FROM A HYDROGEN SULFIDE AND EXCESSING QUANTITIES OF VAPOR AND A GAS MIXTURE CONTAINING AMMONIA |
EP94922391A EP0663850B1 (en) | 1993-08-09 | 1994-08-06 | Method for removing hydrogen sulphide from mixture gas containing hydrogen sulphide and excessive amounts of steam and ammonia |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1993/15403 | 1993-08-09 | ||
KR1019930015403A KR970001270B1 (en) | 1993-08-09 | 1993-08-09 | Process for removing h2s |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995004588A1 true WO1995004588A1 (en) | 1995-02-16 |
Family
ID=19360984
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR1994/000107 WO1995004588A1 (en) | 1993-08-09 | 1994-08-06 | Method for removing hydrogen sulphide from mixture gas containing hydrogen sulphide and excessive amounts of steam and ammonia |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0663850B1 (en) |
JP (1) | JP2601256B2 (en) |
KR (1) | KR970001270B1 (en) |
DE (1) | DE69403055T2 (en) |
DK (1) | DK0663850T3 (en) |
WO (1) | WO1995004588A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7115227B2 (en) * | 2018-11-05 | 2022-08-09 | 住友金属鉱山株式会社 | Hydrogen sulfide gas production plant, hydrogen sulfide gas production method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3230553A1 (en) * | 1981-08-19 | 1983-03-31 | Société Nationale Elf Aquitaine (Production), 92400 Courbevoie | CATALYTIC METHOD FOR THE PRODUCTION OF SULFUR FROM A GAS CONTAINING SULFUR HYDROGEN |
DE3333679A1 (en) * | 1983-09-17 | 1985-04-04 | Basf Ag, 6700 Ludwigshafen | Process for oxidising hydrogen sulphide contained in exhaust gases |
DE4141173A1 (en) * | 1991-12-13 | 1993-06-17 | Linde Ag | METHOD FOR PURIFYING A H (ARROW DOWN) 2 (ARROW DOWN) RAW GAS AND NITROGEN-CONTAINING GAS |
-
1993
- 1993-08-09 KR KR1019930015403A patent/KR970001270B1/en not_active IP Right Cessation
-
1994
- 1994-08-06 WO PCT/KR1994/000107 patent/WO1995004588A1/en active IP Right Grant
- 1994-08-06 EP EP94922391A patent/EP0663850B1/en not_active Expired - Lifetime
- 1994-08-06 DE DE69403055T patent/DE69403055T2/en not_active Expired - Fee Related
- 1994-08-06 DK DK94922391.1T patent/DK0663850T3/en active
- 1994-08-06 JP JP7506348A patent/JP2601256B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3230553A1 (en) * | 1981-08-19 | 1983-03-31 | Société Nationale Elf Aquitaine (Production), 92400 Courbevoie | CATALYTIC METHOD FOR THE PRODUCTION OF SULFUR FROM A GAS CONTAINING SULFUR HYDROGEN |
DE3333679A1 (en) * | 1983-09-17 | 1985-04-04 | Basf Ag, 6700 Ludwigshafen | Process for oxidising hydrogen sulphide contained in exhaust gases |
DE4141173A1 (en) * | 1991-12-13 | 1993-06-17 | Linde Ag | METHOD FOR PURIFYING A H (ARROW DOWN) 2 (ARROW DOWN) RAW GAS AND NITROGEN-CONTAINING GAS |
Non-Patent Citations (2)
Title |
---|
Hydrocarbon Processing, Vol. 68, No. 4, April 1989 (Houston, Texas, USA), J.A. LAGAS et al., "Claus Process Gets Extra Boost"; pages 40-42; totality. * |
The Oil and Gas Journal, Vol. 86, No. 2, 11 January 1988 (Tulsa, Okla., USA), R. KETTNER et al., "New Claus Tail-Gas Process Proved in German Operation"; pages 63-66; totality. * |
Also Published As
Publication number | Publication date |
---|---|
KR970001270B1 (en) | 1997-02-05 |
EP0663850A1 (en) | 1995-07-26 |
DE69403055D1 (en) | 1997-06-12 |
DK0663850T3 (en) | 1997-12-08 |
KR950005357A (en) | 1995-03-20 |
JPH07507724A (en) | 1995-08-31 |
DE69403055T2 (en) | 1997-08-14 |
EP0663850B1 (en) | 1997-05-07 |
JP2601256B2 (en) | 1997-04-16 |
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