CN1265604A - Method for desulfurizing off-gases - Google Patents
Method for desulfurizing off-gases Download PDFInfo
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- CN1265604A CN1265604A CN98807855A CN98807855A CN1265604A CN 1265604 A CN1265604 A CN 1265604A CN 98807855 A CN98807855 A CN 98807855A CN 98807855 A CN98807855 A CN 98807855A CN 1265604 A CN1265604 A CN 1265604A
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- sulphur
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- 239000007789 gas Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 71
- 230000003009 desulfurizing effect Effects 0.000 title description 4
- 238000010521 absorption reaction Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 90
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 76
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 62
- 229910052717 sulfur Inorganic materials 0.000 claims description 50
- 239000011593 sulfur Substances 0.000 claims description 47
- 239000005864 Sulphur Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 47
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 42
- 229910052739 hydrogen Inorganic materials 0.000 description 42
- 241000196324 Embryophyta Species 0.000 description 32
- 238000011084 recovery Methods 0.000 description 24
- 235000010269 sulphur dioxide Nutrition 0.000 description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 14
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 3
- 229940043276 diisopropanolamine Drugs 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- -1 alkyl chain alcohol amine Chemical class 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Images
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
- B01D53/52—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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to a method for removing H2S from off-gases which contain at least 20 % by volume of water vapor, comprising treating the off-gases at a temperature above the water dew point of the off-gases with an aqueous, alkaline solution under absorption of the H2S, followed by subjecting the sulfide-containing solution formed to a biological oxidation of the sulfide.
Description
The present invention relates to a kind of off-gas (off-gas) sulfur method of high water vapor content.More particularly, the present invention includes the method for a kind of reduction from the total sulfur content of the off-gas of sulfur recovery unit.
Utilize oxygen or make hydrogen sulfide (H as the oxygen-containing gas of air
2S) partial oxidation, then, under the condition that has catalyst to exist, the sulfur dioxide (SO that forms by hydrogen sulfide
2) with the reaction of the hydrogen sulfide of residual fraction, thereby the preparation elementary sulfur, this method is referred to as Crouse's method.This method is generally used for refinery and handles the hydrogen sulfide that reclaims from natural gas.Traditional claus plant comprises the combustion furnace with combustion chamber, so-called hot step, next be a plurality of-normally two or three-reactor, wherein filled catalyst.These steps of back have constituted so-called catalytic step.In the combustion chamber, input be rich in H
2The air-flow of S is burning under about 1200 ℃ temperature with air in certain amount.Air capacity should make 1/3rd H
2S becomes SO by following reactive combustion
2:
At H
2After the S partial combustion, unreacted H
2S (be amount about 2/3rds) and formed SO
2Quite a few further reacts by claus reaction:
Therefore, in hot step, about 60% H
2S has changed into elementary sulfur.Gas from the combustion chamber is cooled to about 160 ℃ in sulfur condenser, formed therein sulphur condensation then, flows into the sink (sulfur sink) of sulphur through siphon pipe.The molar ratio of hydrogen sulfide of uncooled gas-wherein and sulfur dioxide still is 2: 1-is heated to about 250 ℃ again, by first hydrogen-catalyst reactor, equilibrium establishment again
Gas from this catalytic reactor cools off in sulfur condenser again, and formed afterwards fluid sulphur is recovered, and residual gas is entering second catalytic reactor after the heating again.
According to the progression of catalytic reaction, the recovery per cent of sulphur is 94-97% in traditional claus plant.Therefore, a certain amount of hydrogen sulfide and sulfur dioxide have been left.
One of critical limitation of Crouse's method is along with hydrogen sulfide changes into sulphur, and the water content of handling in the gas raises.
Because water vapour content raises, and the concentration that has reduced hydrogen sulfide and sulfur dioxide simultaneously, sees on the thermodynamic (al) angle that claus reaction is restricted, and causes the balance of claus reaction (2) to be moved to the left.To be this restriction in order eliminating as far as possible, to wish from handle gas water condensation.Yet because the dew point of water is more much lower than the solidification point of sulphur, in Crouse's method, the condensation of carrying out steam has run into the problem that is difficult to overcome, for example, because the obstruction that the curing of sulphur causes, and owing to form the corrosion that sulfurous acid causes.
In the past, the off-gas of claus process burns in the after-combustion stove.Yet, consider the environment aspect requirement of increasingly stringent, this will not be allowed to.
This has just caused the exploitation of method that the improvement of Crouse's method and Crouse's off-gas are removed.A kind of improvement of Crouse's method is so-called SUPERCLAUS method, is higher than 99% thereby the efficient of Crouse's method is risen to from 94-97%.SUPERCLAUS
Method is disclosed in " SUPERCLAUS
, the answer of the many restrictions of claus plant " and in (being disclosed in the 38th the trade union view of Canadianizing, on October 25th, 1988, Edmonton, Alberta, Canada).
At SUPERCLAUS
In-99 methods, reaction (2) in hot step and claus reaction device is operated under excess hydrogen sulfide, therefore, be about 1 volume % from the hydrogen sulfide content in the reacting gas of afterbody claus reaction device, and the content of sulfur dioxide is about 0.02 volume %.In next reactor step, under the condition that has regioselective oxidation catalyst to exist, hydrogen sulfide by following reaction selectivity be oxidized to elementary sulfur:
These catalyst are described in as in European patent 0242920 and 0409353.
As mentioned above, stricter environmental requirement not only needs to improve Crouse's method, and needs exploitation Claus tail gases (tailgas) processing method, further to make the desulfurizing off-gases from sulfur recovery unit.
Most of claus tail-gas clean-up methods have been used hydrogenation reactor, also are reduction reactor, therein, and sulfur dioxide, carbonyl sulfide (COS), carbon disulfide (CS
2), sulphur steam and any sulphur drop (sulphur mist) and hydrogen (H of carrying secretly
2) or reducibility gas-for example, comprise hydrogen and carbon monoxide-be converted into hydrogen sulfide.
Then, hydrogen sulfide absorbs by solution or gas phase catalysis changes into elementary sulfur and removed.
Only develop a few absorbs sulfur dioxide from funnel gases in Claus tail gases burning back exhaust gas treating method.These methods are not further discussed.Behind claus tail-gas clean-up-hydrogenation with solution absorb resulting hydrogen sulfide-method in, that the most famous is SCOT, BSR-Stretford, BSR-MDEA, Trencor-M and Sulften.These methods are disclosed in " exhaust purifying method summary " (33 by B.G.Goar
RdGas regulation annual meeting, Oklahoma, Norman, 7-9 day March nineteen eighty-three) and hydrocarbon handle in (in February, 1986).
So far the most famous also the most effective tail gas sulfur method is the SCOT method, is disclosed in " gas and liquid desulfurization " (1997) of Maddox.The sulfur recovery rate that the SCOT method reaches is 99.8-99.9%.
Behind vent gas treatment-hydrogenation with resulting hydrogen sulfide gas phase catalyzed conversion-method in, only have seldom several to construct and known, as MODOP, CLINSULF, BSR-Selectox, Sulfreen, SUPERCLAUS-99.5.These methods are disclosed in joumal C﹠amp by B.G.Goar; EN (on May 11st, 1987) is among journal Sulphur (January nineteen ninety-five/February) and the DE-A 2648190.
In all these claus tail-gas clean-up methods, behind hydrogenation, the water that forms in claus reaction (2) and the selective oxidation reaction (3) is condensed, because the existence of water is at follow-up absorption liquid or hydrogen sulfide is catalytically converted into elementary sulfur adverse influence is arranged.The absorption liquid that is used for said method is the second month in a season or uncle's alkyl chain alcohol amine solution, as diisopropanolamine (DIPA) (DIPA) or methyl diethanolamine (MDEA) or combined oxidation reducing solution.Do not anhydrate if do not remove, absorption process will be interfered fully, promptly, perhaps making under too high temperature does not have or only has very little absorption generation, perhaps water condensation in the absorption tower in absorption process, the circulation solution serial dilution is to such an extent as to absorption no longer takes place.
In hydrogen sulfide gas phase catalytic conversion process, do not anhydrate if do not remove, hydrogen sulfide thermodynamic change by claus reaction (2) descends greatly, resulting situation also just with the afterbody reactor of Crouse's method in situation similar, therefore, the overall recovery that is higher than 99.5% sulphur can not reach.
Although use catalyst for selective oxidation as using in the SUPERSLAUS method, obtained higher efficient, SUPERSLAUS 99.5 also is like this, finds, can not realize surpassing 99.5% sulfur recovery rate.
Can say like this that substantially behind the hydrogenation, the shortcoming that the hydrogen sulfide in the gas phase is catalytically converted into the claus tail-gas clean-up method of elementary sulfur is to satisfy needed 99.90% the total sulfur recovery that is higher than.
Crouse's method promptly behind the hydrogenation, with water condensation, is used absorption liquid bulk absorption hydrogen sulfide again, as the SCOT method, can realize that the overall recovery of sulphur surpasses 99.90%, just its major defect is that cost of investment and energy consumption are high.The SCOT method of more recent version realized that as SUPERSCOT and LS-SCOT total sulfur recovery reaches 99.95%, but its cost is higher.
Another shortcoming of these methods is to discharge and to handle the condensate that contains acid cure hydrogen, and as in Sour Water stripper, therefore, the sour gas of dissolving separates with steam, and its cost is high too.
Environment requirement has not only influenced the exploitation of Crouse's method and claus tail-gas clean-up method, has also influenced the processing method of chimney gas, has also related to the flue gas treating process in power plant.The whole bag of tricks of " flue gas desulfurization (FGD) " is known, and wherein sulfur dioxide and milk of lime are converted into gypsum (Ca
2SO
4).Owing to formed superfluous gypsum, be the method for elementary sulfur with Sulphur Dioxide so wish exploitation.The Wellman Lord method that is disclosed among the Gas Purification (purification for gas) (the 4th edition, 1985, A.L.Kohl, F.C.Riesenfeld pp.351-356) is an example of this method, and wherein sulfur dioxide discharges with concentrated gas at last.Sulfur dioxide when 2/3rds changes into hydrogen sulfide in hydrogenation step after, hydrogen sulfide and sulfur dioxide gas are converted into elementary sulfur in claus plant.This method route also is expensive.Another development in this field is the biological desulphurization of flue gas.
The flue gas biological desulphurization is disclosed among the journal Lucht (No. 4, in December, 1994).The BIO-FGD method is used for always the flue gas of spontaneous power plant and removes sulfur dioxide, comprises an absorption tower, and in tower, sulfur dioxide is dissolved in the diluted sodium hydroxide solution by following reaction:
Then, this solution is handled in the two-stage biological reactor.
In first order biological step, formed sodium hydrogensulfite (NaHSO
3) change into vulcanized sodium (NaHS) at anaerobic reactor with electron donor.
Suitable electron donor is as hydrogen, ethanol, hydrogen and glucose.In second step, vulcanized sodium is oxidized to elementary sulfur in aerobic reactor, and elementary sulfur is separated.
Flue gas behind coal or the fuel oil combustion contains steam in a small amount.Water content is usually at 2-15 volume %, and corresponding dew point is 20-55 ℃.
If the BIO-FGD method is used for the desulfurization of Crouse's off-gas of after-combustion, all sulphur components have all changed into sulfur dioxide, and gas must cool off, because the water vapour content height of Crouse's off-gas.Doing like this is to prevent steam condensation in sodium hydroxide solution, consequently must discharge a part of sodium hydroxide solution continuously.
Crouse's off-gas must be cooled, and therefore, has formed acidic condensate, also must discharging.
In the desulfurizing off-gases of coal or oil fired power station, this problem can not take place, because the dew point of water is under the operating temperature on absorption tower.The cooling of this off-gas simply mode is carried out, and the condensation of water can not take place.
First purpose of the present invention provides the sulfur method of a kind of water vapour content up to the off-gas of 20-40 volume %, and therefore the wherein unnecessary condensation of carrying out water, has prevented to form the hydrogen sulfide containing acidic condensate that must discharge.
Second purpose of the present invention provides a kind of method, in the method, is absorbed under the temperature of the formed hydrogen sulfide of hydrogenation dew point of water in being higher than gas in the absorption liquid, in the absorption process of hydrogen sulfide, the condensation of water do not take place.
A further object of the present invention provides a kind of method, and total sulfur recovery surpasses 99.90%, but does not have above-mentioned shortcoming.
The present invention is based on so unexpected discovery, can reach absorbing hydrogen sulphide the gas of 20-40 volume % from water content in the temperature of the dew point that is higher than water with alkaline solution, and afterwards, the solution of formed sulfur compound is through aerobic biooxidation.
Therefore, the present invention relates to a kind of method of from the off-gas of water vapour content 20 volume %, removing hydrogen sulfide at least, be included under the temperature that is higher than water dew point in the off-gas, use the aqueous solution, alkaline solution, processing is in off-gas under the absorption at hydrogen sulfide, then, makes the formed biological oxidation that contains the solution of sulfide through hydrogen sulfide.
Find unexpectedly, be dissolved in alkaline solution-preferred sodium hydroxide solution-in hydrogen sulfide can in the biological aerobic reactor, preferably under the uniform temp that absorbs, change into elementary sulfur with air oxygen.
These water contents are that the dew point of the gas of 20-40 volume % is 60-80 ℃, and this just means that biological oxidation will carry out under at least 65 ℃, particularly carry out under 70-90 ℃ temperature.Especially surprisingly can under so high temperature, effectively and suitably carry out biological oxidation.
In the methods of the invention, at first the temperature of off-gas is brought up to more than 200 ℃, flow through (sulfided) VI family/group VIII metallic catalyst of the sulfuration that loads on the inorganic oxide carrier then with hydrogen and/or the gas that contains carbon monoxide, all sulphur components are all reduced, therefore, transform by following reaction equation as sulfur dioxide, sulphur steam and sulphur mist and hydrogen or the reducibility gas that contains just like hydrogen and carbon monoxide:
If there is oxygen in the off-gas, above-mentioned catalyst also has makes the character of oxygen by following reaction hydrogenation:
Preferably, above-mentioned catalyst also has the COS of making and CS
2Character by following reaction equation hydrogenation:
In the methods of the invention, therefore condensation, can not take place in the temperature from the off-gas of hydrogenation reactor is cooled and is higher than the steam dew point that is present in the gas to be adjusted to.Preferably, be cooled to be higher than dew point 3-5 ℃.
Off-gas, particularly its water vapour content of off-gas from Crouse's reclaimer is 20-40 volume %, its dew point is 60-80 ℃.
In the absorption tower, these off-gas directly with the diluted alkaline solution-preferred sodium hydroxide solution of pH value between 8-9-contact, the hydrogen sulfide in the gas is pressed following reaction and is dissolved:
Unabsorbed part in the above-mentioned off-gas is chosen wantonly after burning, is discharged in the air.
Because the alkaline solution after the regeneration is sulfide hydrogen not, the hydrogen sulfide that is present in the off-gas is absorbed fully, can realize that like this total sulfur recovery surpasses 99.90%.In the methods of the invention, solution preferably under the temperature that absorbs, by the aerobe reactor, therefore, needn't be removed or additional heat under uniform temp.In aerobic reactor, the supply air in certain amount makes the hydrogen sulfide that dissolves by airborne oxygen partial oxidation, presses following reaction forming element sulphur:
Then, at the sulphur separator, also preferably under identical temperature sulphur is separated with sodium hydroxide solution, solution is recycled to the absorption tower afterwards.Before being transported to the aerobe reactor, the sodium hydroxide solution that has absorbed hydrogen sulfide may cool off.Yet after having separated sulphur, before being fed to the absorption tower, solution is heated again.
The present invention will be described below with reference to two accompanying drawings, and wherein the inventive method is with the formal description of square process.
Fig. 1 is a general flow chart.Be adjusted to required hydrogenation temperature from the off-gas of sulfur recovery unit (not shown) and through additional hydrogen or other reducibility gas of pipeline 2 with heater 3 through pipeline 1, be input in the hydrogenation reactor 5 through pipeline 4 again.
In hydrogenation reactor 5, the sulfur dioxide in the gas, sulphur steam and organic sulfur compound and hydrogen change into hydrogen sulfide.If there is oxygen in the gas, then be converted to water.If have COS and CS
2, then become hydrogen sulfide and carbon dioxide with existing steam transforming.
Gas from hydrogenation reactor 5 is adjusted to required absorption temperature through pipeline 6 by cooler 7, then among pipeline 8 is input to the absorption tower 9 of biological plant (bioplant).In the absorption tower, with diluted sodium hydroxide solution hydrogen sulfide wash-out from gas is come out, then, be input to aerobe reactor 11 through pipeline 10, therein, hydrogen sulfide becomes elementary sulfur with oxygen conversion in pipeline 12 air supplied.Sodium hydroxide solution is input to sulphur separator 14 through pipeline 13, formed sulphur through pipeline 15 from wherein discharging.Solution returns the absorption tower through pipeline 16.Very low from the hydrogen sulfide containing amount of the gas on absorption tower, be transported to afterburner 18 through pipeline 17, afterwards, gas is through chimney 19 dischargings.
The flow chart of Fig. 2 has provided equipment of the present invention, wherein from the high H of having of claus plant
2S/SO
2The off-gas of ratio is directly absorbed, and hydrogenation in the middle of not needing.
Off-gas from three grades of claus plant 100 is input in the absorption tower 102 through pipeline 101.Claus plant is at H
2S/SO
2Mol ratio be at least 100 times operations.
In absorption tower 102, with diluted sodium hydroxide solution hydrogen sulfide is washed out from gas, then, sodium hydroxide solution is through pipeline 103 input aerobe reactors 104, and hydrogen sulfide becomes elementary sulfur with oxygen conversion in pipeline 105 air supplied therein.Part sodium hydroxide solution is transported to sulphur separator 109 through pipeline 106, pump 107 and pipeline 108, and formed sulphur is discharged through pipeline 110.This solution is recycled to the absorption tower through pipeline 111 and 112, discharges on a small quantity through pipeline 113.Gas from the absorption tower contains very small amount of hydrogen sulfide, is transported to the afterburner (not shown) through pipeline 114, and gas discharges through the chimney (not shown) then.Embodiment 1
Cling under the pressure of (cutting off), at 45 ℃ and 1.6 from the sour gas 9700Nm of purification for gas equipment
3/ h has following composition:
60.0 volume % H
2S
3.0 volume % NH
3
30.0 volume % CO
2
5.0 volume % H
2O
2.0 volume % CH
4
This sour gas is transported in the claus plant with two claus reaction devices.After hot step and catalytic reactor step, the sulphur that forms in sulfur recovery unit is condensed and discharges.The total amount of sulphur is 7768kg/h.Based on sour gas, the sulfur recovery rate of claus plant is 93.3%.
Under the pressure of 164 ℃ and 1.14 crust (cutting off), be 29749Nm from the amount of the off-gas of claus plant
3/ h, and have following composition:
0.47 volume % H
2S
0.24 volume % SO
2
0.03 volume % COS
0.04 volume % CS
2
0.01 volume % S
6
0.04 volume % S
8
1.38 volume % CO
1.53 volume % H
2
11.37 volume % CO
2
55.96 volume % N
2
0.66 volume % Ar
28.27 volume % H
2O
In this off-gas, supply 103Nm
3The hydrogen of/h is heated to 280 ℃ then as reducing gas, makes all sulfur dioxide (SO
2) and sulphur steam (S
6, S
8) change into hydrogen sulfide and water, and make cos (COS) and nitric sulfid (CS
2) in hydrogenation reactor, be hydrolyzed into hydrogen sulfide, the metallic catalyst of the 6th family and/or the 8th family of sulfuration is housed in this reactor, here be the Co-Mo catalyst.
Under the pressure of 317 ℃ and 1.10 crust (cutting off), be 31574Nm from the amount of the off-gas of hydrogenation reactor
3/ h, and have following composition:
1.24 volume % H
2S
28 ppm COS
2 ppm CS
2
2.02 volume % H
2
12.64 volume % CO
2
56.62 volume % N
2
0.67 volume % Ar
26.80 volume % H
2O
Then, this off-gas is cooled to 72 ℃, and this temperature is higher 3 ℃ than the dew point of steam in the off-gas.
Cooled off-gas is handled in biological plant under 72 ℃, does not have water condensation from off-gas and gets off.In the absorption tower of biological plant, the hydrogen sulfide wash-out is come out from off-gas with diluted sodium hydroxide solution, afterwards, the solution that has absorbed hydrogen sulfide is transported in the aerobe reactor, and there, hydrogen sulfide is converted to elementary sulfur.
In biological plant, need not supply or remove heat, so the absorption of hydrogen sulfide and to change into elementary sulfur be in identical temperature is carried out under 72 ℃.
In the aerobe reactor, supply 945Nm
3The air of/h is to become sulphur with the hydrogen sulfide selective oxidation.Under 72 ℃ and 1.05 crust (cutting off) pressure, be 31189Nm from the gas flow on absorption tower
3/ h, and have following composition:
250 ppm H
2S
28 ppm COS
2 ppm CS
2
2.04 volume % H
2
12.80 volume % CO
2
57.32 volume % N
2
0.68 volume % Ar
27.13 volume % H
2O
After after-combustion, this gas is transported to chimney.The amount of the sulphur that forms in biological plant is 551kg/h.The total amount of the sulphur that generates in sulfur recovery unit and biological plant is 8319kg/h, has improved total desulfuration efficiency, and based on original sour gas, the rate of recovery is 99.87%.Embodiment 2
Sour gas 6481 Nm from purification for gas equipment
3/ h clings under the pressure of (cutting off) at 45 ℃ and 1.6, has following composition:
90.0 volume % H
2S
3.0 volume % NH
3
5.0 volume % H
2O
2.0 volume % CH
4
This sour gas is transported to the SUPERCLAUS of two claus reaction devices and a selective oxidation reaction device
In the equipment.After hot step and catalytic reactor step, the sulphur that forms in sulfur recovery unit is condensed and discharges.The amount of sulphur is 8227kg/h.Based on sour gas, the sulfur recovery rate of claus plant is 98.5%.
Under the pressure of 129 ℃ and 1.14 crust (cutting off), be 21279Nm from the amount of the off-gas of claus plant
3/ h, and have following composition:
0.03 volume % H
2S
0.20 volume % SO
2
20 ppm COS
30 ppm CS
2
10 ppm S
6
0.01 volume % S
8
0.15 volume % CO
1.72 volume % H
2
1.14 volume % CO
2
62.45 volume % N
2
0.74 volume % Ar
33.05 volume % H
2O
0.50 volume % O
2
Supply 133 Nm in this off-gas
3The hydrogen of/h is heated to 280 ℃ then as reducing gas, makes all sulfur dioxide (SO
2) and sulphur steam (S
6, S
8) change into hydrogen sulfide and water, and make cos (COS) and nitric sulfid (CS
2) in hydrogenation reactor, be hydrolyzed into hydrogen sulfide, the metallic catalyst of the 6th family and/or the 8th family of sulfuration is housed in this reactor, here be the Co-Mo catalyst.
Under the pressure of 367 ℃ and 1.10 crust (cutting off), be 22863 Nm from the off-gas amount of hydrogenation reactor
3/ h, and have following composition.
0.37 volume % H
2S
2 ppm COS
0.82 volume % H
2
1.90 volume % CO
2
62.89 volume % N
2
0.75 volume % Ar
33.27 volume % H
2O
Then, this off-gas is cooled to 76 ℃, and this temperature is higher 3 ℃ than steam dew point in the off-gas.
Cooled off-gas is handled in biological plant under 76 ℃, does not have water condensation from off-gas and gets off.In the absorption tower of biological plant, the hydrogen sulfide wash-out is come out from off-gas with diluted sodium hydroxide solution, afterwards, the solution that has absorbed hydrogen sulfide is transported in the aerobe reactor, and there, hydrogen sulfide is converted to elementary sulfur.
Need not supply or remove heat in biological plant, the absorption of hydrogen sulfide and to change into elementary sulfur be in identical temperature is carried out under 76 ℃.In the aerobe reactor, supply 205Nm
3The air of/h is to become elementary sulfur with the hydrogen sulfide selective oxidation.Under 76 ℃ and 1.05 crust (cutting off) pressure, be 22780Nm from the gas flow on absorption tower
3/ h, and have following composition:
75 ppm H
2S
2 ppm COS
0.82 volume % H
2
1.91 volume % CO
2
63.12 volume % N
2
0.75 volume % Ar
33.39 volume % H
2O
After after-combustion, this gas is transported to chimney.The amount of the sulphur that forms in biological plant is 119kg/h.The total amount of the sulphur that reclaims in sulfur recovery unit and biological plant is 8346kg/h, has improved total desulfuration efficiency, and based on original sour gas, the rate of recovery is 99.97%.Embodiment 3
Cling under the pressure of (cutting off), at 40 ℃ and 1.7 from the sour gas 3500Nm of purification for gas equipment
3/ h, and have following composition:
88.0 volume % H
2S
6.1 volume % CO
2
1.5 volume % CH
4
4.4 volume % H
2O
This sour gas is transported in the claus plant of three claus reaction devices.
In claus plant, supply air, make that the reaction (2) in hot step and the claus reaction device is operated under excess hydrogen sulfide, therefore, H behind third level reactor
2S: SO
2Greater than 100: 1, to such an extent as to content of sulfur dioxide is less than 0.009 volume %.
After hot step and catalytic reactor step, the sulphur that forms in sulfur recovery unit is condensed and discharges.The amount of sulphur is 4239kg/h.Based on sour gas, the sulfur recovery rate of claus plant is 96.4%.Under the pressure of 130 ℃ and 1.15 crust (cutting off), be 10001Nm from the amount of the off-gas of claus plant
3/ h, and have following composition:
0.93 volume % H
2S
0.009 volume % SO
2
0.04 volume % COS
0.04 volume % CS
2
0.001 volume S
6
0.01 volume % S
8
0.36 volume % CO
1.83 volume % H
2
2.79 volume % CO
2
59.68 volume % N
2
0.60 volume % Ar
33.71 volume % H
2O
Then, this off-gas is cooled to 78 ℃, and this temperature is higher 3 ℃ than steam dew point in the off-gas.Cooled off-gas is handled in biological plant under 73 ℃, does not get off and do not have water condensation from off-gas.In the absorption tower of biological plant, the hydrogen sulfide wash-out is come out from off-gas with diluted sodium hydroxide solution, afterwards, the solution that has absorbed hydrogen sulfide is transported in the aerobe reactor, and there, hydrogen sulfide is converted to elementary sulfur.Need not supply or remove heat in biological plant, therefore, the absorption of hydrogen sulfide and to change into elementary sulfur be in identical temperature is promptly carried out under 73 ℃.
In the aerobe reactor, supply 320Nm
3The air of/h is to become elementary sulfur with the hydrogen sulfide selective oxidation.Under 73 ℃ and 1.05 crust (cutting off) pressure, be 9901Nm from the gas flow on absorption tower
3/ h, and have following composition:
190 ppm H
2S
7 ppm COS
9 ppm CS
2
1.85 volume % H
2
0.36 volume % CO
2.82 volume % CO
2
60.28 volume % N
2
0.61 volume % Ar
34.06 volume % H
2O
After after-combustion, this gas is transported to chimney.The sulphur that forms in biological plant is 156kg/h.The total amount of the sulphur that generates in sulfur recovery unit and biological plant is 4395kg/h, has improved total desulfuration efficiency, and based on original sour gas, the rate of recovery is 99.93%.
In alkali lye, there is small amounts of sulfur dioxide to change into sulfate.In order not make the sulfate accumulation, discharge a spot of alkali lye-85kg/h, and replace with respective amount.
Claims (9)
1. method of from the off-gas of water vapour content 20 volume %, removing hydrogen sulfide at least, comprise: in being higher than off-gas under the temperature of the dew point of water, be in off-gas under the hydrogen sulfide absorption state with alkaline aqueous solution, then, make the formed biological oxidation that contains the solution of sulfide through sulfide.
2. the process of claim 1 wherein and absorb and oxidation is carried out under essentially identical temperature.
3. claim 1 or 2 method, off-gas wherein to be processed comes bin cure to remove equipment.
4. the method for claim 3, wherein off-gas before absorbing by hydrogenation.
5. the method for claim 1-3, the wherein H of off-gas
2S/SO
2Molar ratio is at least 100, preferably from claus plant.
6. the method for claim 1-5, wherein off-gas contains the steam of 20-40%.
7. the method for claim 1-6, wherein sulfide is converted to elementary sulfur in the aerobic biooxidation reaction.
8. the method for claim 1-7, wherein after biological oxidation, sulphur is separated from fluid.
9. the method for claim 8, wherein after isolating sulphur, liquid is used as and absorbs liquid recirculation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1006339A NL1006339C2 (en) | 1997-06-17 | 1997-06-17 | Process for desulfurizing waste gases. |
| NL1006339 | 1997-06-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1265604A true CN1265604A (en) | 2000-09-06 |
Family
ID=19765181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98807855A Pending CN1265604A (en) | 1997-06-17 | 1998-06-15 | Method for desulfurizing off-gases |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0989902A1 (en) |
| JP (1) | JP2002504858A (en) |
| KR (1) | KR20010013905A (en) |
| CN (1) | CN1265604A (en) |
| AR (1) | AR016072A1 (en) |
| AU (1) | AU737133B2 (en) |
| BR (1) | BR9810187A (en) |
| CA (1) | CA2295443A1 (en) |
| HU (1) | HUP0001892A3 (en) |
| NL (1) | NL1006339C2 (en) |
| NO (1) | NO996257L (en) |
| PL (1) | PL337501A1 (en) |
| SK (1) | SK182099A3 (en) |
| TW (1) | TW386895B (en) |
| WO (1) | WO1998057731A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425324C (en) * | 2006-01-10 | 2008-10-15 | 武汉加华科技有限公司 | Top-push decreasing gas desulfurization at normal-pressure and apparatus thereof |
| CN100553746C (en) * | 2004-03-03 | 2009-10-28 | 国际壳牌研究有限公司 | The method of high efficiente callback sulphur from acid gas stream |
| CN106139812A (en) * | 2015-04-20 | 2016-11-23 | 兰州信元新型材料有限责任公司 | Carbon disulfide Special desulfurizing agent and preparation method thereof |
| CN113209794A (en) * | 2021-05-07 | 2021-08-06 | 南京飞锦环保科技有限公司 | Biological soil deodorization system and deodorization method |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1011490C2 (en) | 1999-03-08 | 2000-09-12 | Paques Bio Syst Bv | Process for desulfurizing gases. |
| EP1720798A2 (en) * | 2004-03-03 | 2006-11-15 | Shell Internationale Research Maatschappij B.V. | A process for the high recovery efficiency of sulfur from an acid gas stream |
| CA2562845C (en) * | 2004-04-22 | 2009-09-29 | Fluor Technologies Corporation | Cos-claus configurations and methods |
| KR20120008523A (en) * | 2009-04-08 | 2012-01-30 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | Method of treating an off-gas stream and an apparatus therefor |
| EP3034157A1 (en) | 2015-02-19 | 2016-06-22 | Paqell B.V. | Process for treating a hydrogen sulphide and mercaptans comprising gas |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE7612503L (en) * | 1975-11-11 | 1977-05-12 | Courtaulds Ltd | TREATMENT OF GASES |
| DE3204907A1 (en) * | 1982-02-12 | 1983-08-25 | Dr. C. Otto & Co. Gmbh, 4630 Bochum | METHOD FOR REMOVING SULFUR HYDROGEN FROM GASES, IN PARTICULAR CARBON DISTILLATION GASES |
| DE3542345A1 (en) * | 1985-11-29 | 1987-06-04 | Imhausen Chemie Gmbh | METHOD FOR REMOVING SULDURATE FROM EXHAUST GAS |
| NL8801009A (en) * | 1988-04-19 | 1989-11-16 | Rijkslandbouwuniversiteit | Oxidative biological removal of sulphide from waste water - using short-fall in oxygen, giving conversion largely to sulphur |
| NL9001369A (en) * | 1990-06-15 | 1992-01-02 | Pacques Bv | PROCESS FOR THE REMOVAL OF H2S FROM BIOGAS. |
| NL9002661A (en) * | 1990-12-04 | 1992-07-01 | Pacques Bv | PROCESS FOR THE REMOVAL OF H2S FROM GAS. |
| US5236677A (en) * | 1992-03-13 | 1993-08-17 | Grupo Cydsa S.A. De C.V. | Biological process for the elimination of sulphur compounds present in gas mixtures |
| NL9301000A (en) * | 1993-06-10 | 1995-01-02 | Pacques Bv | Method for the purification of waste water containing sulphide. |
-
1997
- 1997-06-17 NL NL1006339A patent/NL1006339C2/en not_active IP Right Cessation
-
1998
- 1998-06-15 CA CA002295443A patent/CA2295443A1/en not_active Abandoned
- 1998-06-15 TW TW087109447A patent/TW386895B/en not_active IP Right Cessation
- 1998-06-15 CN CN98807855A patent/CN1265604A/en active Pending
- 1998-06-15 SK SK1820-99A patent/SK182099A3/en unknown
- 1998-06-15 HU HU0001892A patent/HUP0001892A3/en unknown
- 1998-06-15 PL PL98337501A patent/PL337501A1/en unknown
- 1998-06-15 AU AU81321/98A patent/AU737133B2/en not_active Ceased
- 1998-06-15 BR BR9810187-0A patent/BR9810187A/en not_active IP Right Cessation
- 1998-06-15 EP EP98931121A patent/EP0989902A1/en not_active Ceased
- 1998-06-15 JP JP50420299A patent/JP2002504858A/en active Pending
- 1998-06-15 WO PCT/NL1998/000342 patent/WO1998057731A1/en not_active Application Discontinuation
- 1998-06-15 KR KR1019997011927A patent/KR20010013905A/en not_active Application Discontinuation
- 1998-06-16 AR ARP980102855A patent/AR016072A1/en not_active Application Discontinuation
-
1999
- 1999-12-16 NO NO996257A patent/NO996257L/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100553746C (en) * | 2004-03-03 | 2009-10-28 | 国际壳牌研究有限公司 | The method of high efficiente callback sulphur from acid gas stream |
| CN100425324C (en) * | 2006-01-10 | 2008-10-15 | 武汉加华科技有限公司 | Top-push decreasing gas desulfurization at normal-pressure and apparatus thereof |
| CN106139812A (en) * | 2015-04-20 | 2016-11-23 | 兰州信元新型材料有限责任公司 | Carbon disulfide Special desulfurizing agent and preparation method thereof |
| CN113209794A (en) * | 2021-05-07 | 2021-08-06 | 南京飞锦环保科技有限公司 | Biological soil deodorization system and deodorization method |
| CN113209794B (en) * | 2021-05-07 | 2022-05-17 | 南京飞锦环保科技有限公司 | Biological soil deodorization system and deodorization method |
Also Published As
| Publication number | Publication date |
|---|---|
| HUP0001892A2 (en) | 2000-11-28 |
| NO996257D0 (en) | 1999-12-16 |
| NL1006339C2 (en) | 1998-12-21 |
| NO996257L (en) | 2000-02-16 |
| JP2002504858A (en) | 2002-02-12 |
| SK182099A3 (en) | 2000-07-11 |
| AU8132198A (en) | 1999-01-04 |
| KR20010013905A (en) | 2001-02-26 |
| AU737133B2 (en) | 2001-08-09 |
| AR016072A1 (en) | 2001-06-20 |
| CA2295443A1 (en) | 1998-12-23 |
| PL337501A1 (en) | 2000-08-28 |
| WO1998057731A1 (en) | 1998-12-23 |
| TW386895B (en) | 2000-04-11 |
| BR9810187A (en) | 2000-08-08 |
| HUP0001892A3 (en) | 2002-02-28 |
| EP0989902A1 (en) | 2000-04-05 |
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