CA2041157A1 - Process of purifying an h2s- and co2-containing gas - Google Patents
Process of purifying an h2s- and co2-containing gasInfo
- Publication number
- CA2041157A1 CA2041157A1 CA002041157A CA2041157A CA2041157A1 CA 2041157 A1 CA2041157 A1 CA 2041157A1 CA 002041157 A CA002041157 A CA 002041157A CA 2041157 A CA2041157 A CA 2041157A CA 2041157 A1 CA2041157 A1 CA 2041157A1
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- Prior art keywords
- gas
- supplied
- zone
- scrubbing
- process according
- 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.)
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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
- B01D53/14—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 absorption
- B01D53/1418—Recovery of products
-
- 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
- B01D53/14—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 absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
- Carbon And Carbon Compounds (AREA)
- Industrial Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
A process of purifying a gas which con-tains combustible components as well as carbon dioxide and sulfur compounds, particularly H2S, in that the gas is scrubbed in a scrubbing zone with a scrubbing solution, which is regenerated and re-used. The scrub-bing solution to be regenerated is pressure-relieved, stripped, and heated in a hot regenerating zone. An exhaust gas which is rich in H2S and comes from the hot regenerating zone is partly combusted in a combustion chamber with oxygen, oxygen-containing gas or air. A gas mixture which is at a temperature in the range from 1000 to 2000 °C and in which at least 30 mole percent of the sulfur supplied to the combustion chamber are contained as elementary sulfur and which also contains the compo-nents H2S and SO2 in a molar ratio of 4:1 to 1:1 is produced in the combustion chamber. The gas mixture is cooled below the dew point temperature of sulfur; con-densed elementary sulfur is removed; the gas mixture is subsequently heated to temperatures of 180 to 280 °C and is then directly subjected to a catalytic hydrogenation and/or hydrolysis, whereby the residual content of SO2 is substantially converted to H2S. At least part of the gas which has thus been treated is contacted as an H2S-containing residual gas with scrubbing solution.
A process of purifying a gas which con-tains combustible components as well as carbon dioxide and sulfur compounds, particularly H2S, in that the gas is scrubbed in a scrubbing zone with a scrubbing solution, which is regenerated and re-used. The scrub-bing solution to be regenerated is pressure-relieved, stripped, and heated in a hot regenerating zone. An exhaust gas which is rich in H2S and comes from the hot regenerating zone is partly combusted in a combustion chamber with oxygen, oxygen-containing gas or air. A gas mixture which is at a temperature in the range from 1000 to 2000 °C and in which at least 30 mole percent of the sulfur supplied to the combustion chamber are contained as elementary sulfur and which also contains the compo-nents H2S and SO2 in a molar ratio of 4:1 to 1:1 is produced in the combustion chamber. The gas mixture is cooled below the dew point temperature of sulfur; con-densed elementary sulfur is removed; the gas mixture is subsequently heated to temperatures of 180 to 280 °C and is then directly subjected to a catalytic hydrogenation and/or hydrolysis, whereby the residual content of SO2 is substantially converted to H2S. At least part of the gas which has thus been treated is contacted as an H2S-containing residual gas with scrubbing solution.
Description
? ~
This invention relates to a process of purifylng a gas which con~ains combusti~le components as well as carbon dioxids and sulfur compounds, parti~
cularly H2S, in that ~he ~as i~ scrubbed in a scrubbing z.one with a scrubbing solution, which is regenerated and re-used, whereill the sc~llbbing solution to ~e regene-rated is pressure-relieved, stripped, and heated in a hot regenerating zone, an exhaust ~'G3 rich in H2S pro-duc~d in the l!ot regenerati~g zone is processed to form ele~enbary sulfur and a residual gas which contains H2S, an~ the residual gas i3 contacted with scrubbing solution~
`~uropean ~atent 0 054 772 describes a process which s of that ~ind and in which the exhaust gas that is supr.lied to the Claus proces~ plan~ contains considerable amounts o~ ~,C, i n addition to ~S. That exhaust ~as i5 proces~:ed rurther in a relatively ex-pe.nsive Claus process Dlant~ which inlcudes two or three . .,.. . .
.. ..
,' `
S ~
catalytic stages, in which after a partial com~ustion of H2S to S02 the exhaust ias is catal,~tically con-verted as completely as possible to elementary sulfur and water by the Claus re~ction H2S + ~2 -' 3 S + 2 H20 ae~ore and behind each of ~ d catalytic stages, elemen~
tary sulfur is condensed ~rom the mi~ed gases and is removed. In the l{nown proces,~ the catalytic conversion stages are succeeded c~ a hydro~enation and the exhaust gas is therea~ter recycled to the scrubber.
Those catalytic processing stages give rise tc conserable costs and have the disadvantage that they render the star~-up of the plant from stand-still expensive and time-consuming. There is also a risk that in case of frequent start-ups and shutdowns and of extreme load changes the catalysts will soon lose their activity.
It is an object of the invention so to process the exhaust gas rich in H2S that is formed in the hot regenerating zone that a fast start-up from a standstill can be effected in a simple manner and even a frequent load change will not be problematic.
In the process which has been described first herein-before this is accomplished in accordance with the in-vention in that the exhaust gas which is rich in H2S
and has been produced in the hot regenerating zone is .. - ~ ~, ~ ~,'. ' , ,:
s ~
~3--partly combusted in a combustion chamber with oxygen, oxygen-containing ga~ or air; a ~,as mixture which is at a temperature in the range from lO00 to 2000C and in which ~ e percent of the sulfur supplied to the combustion chamber are contained a~ elementary sulfur and which also contains the components H2S and S02 in a molar ratio of 4:l to 1:1 is produced in the combustion the chamber; ~as mixture is cooled below the dew point tem-perature of sulfur; condensed elementary sulfur is re-moved; the gas ~ixture is subsequently heated to tem-peratures of 180 to 280C and is th~n directl~ subjected to a catalytic hydrogenation and/or hydrolysis, wherebg the residual content o~ S02 is substantiall~ converted to H2S ;
and at least part of the gas which has thus been treated is contacted as an H2S-containing residual gas with scrubbing solution. The process in accordance with the invention is particularly desir-able for the desulfurization of fuel gases to be used as fuel in a gas turbine-steam turbine power pla~.
In the process in accordance with the invention, ca~ is taken to ensure that the ga~ which is rich in H2S and supplied to the combustion chamber is highly enriched with H2S so that a large share of the hydrogen sulfide is reacted to elementary sulfur by the reaction , .~ "
.
H2S + 2 ~ S ~ H20 in and immediately after the combustion chamber and there is no longer a need for a further processing of the gas mixture by a catalytic reaction of -H~S and S2 according to the Claus reaction 2 H2$ ~ S02 = 3 S + 2 H20 reaction of H2~ to a lower degree i5 in~entionally tolerated and this will also increase the demand for hydrogen for the hydrogenation. But in the process in accordance with the invention the h~per rate of hydro-genation requires that the h~drogenation catalyst is cooled and in the process in accordance with the in-vention that cooling can be effected by the ~eeding of a cooling gas, which ma~ also be used to supply the de-ficient hydrogenatin~ hydro~en.
'~he residual ~as which is ~igh in ~I2S and has been produced iD the hydro~enating and/or hydrolyzing stage may be recycled, e.~., to the scrubbing zone or to the regeneratin~ stage. Alternatively, part of that residual .sas may directl~ be supplied to the combustion chamber and this will be recommendable particularl~ if oxygen and an exhaust ~as which is highly enriched with H2S are supplied to the com~ustion chamberO
;''he hot regenerat~on proauces an exhaust ~as which has a low C02 content not in excess of l~o by volume or will have a much lower C02 content if the laden scrubbing solution ;`rom -;he ;crubbirg zone is pressure-relieved iD at least ~10 re~en~atin~ columns . : :
', ' , ., '.~ ' , , . ' ~:
~ 4 , ~i!
before the hot re~eneration. In ~,hat c~se it wiil be recommendable to feed at least ~art of ~he flashed-off gas as a stripr,ing gas to u~e E!recedinLr s~a~e. Lr addition, inert gas ~ay be used as a stripping gas in the hot regenerating ~oneO
The process is particularl~ desir-able for effecting a desulfurization oi` gases which have a high heatin~ value and are intended for use in a gas turbine-steam turbine po~ver plant~ Such gases having a high heatin~ value ma~- be ~roduced in a manner known per se, e.~ y a gasification oi` solid fuels.
'rhe gas may be purified by means of various ~crubbing solutions, which ~re selec~ite for ~l2S and which are known per se and may consist, e~g., of physicallù~ acting scrubbing solutions, such ~IS ;netne;nol, N-methyl pyrrolidone, methyl diethanol~mine or also dimethyl ether of polyethylene glyc~ he ~as is scrub-bed in most cases under pressures in the ran~e from 5 to 100 hars and at the ~no~rn te~peratures which are ~ypical of the scrub~ing solution employed and lie in the range from -80C to ~100C. ~ha e].emen',Gry sulfur is produced under pressures of about 1 to ,~0 bars or even ligrher pressures. Pressure~ o~ 1 to 10 bars are presently pre-ferred.
Further features of the process will be explained with reference to the ~Irawing. Figures 1, 3, ~nd 4 are flow schemes illustratinLr various variants " .:.: . .- .
,.
` . ~ ` ' . - ' ~ 3,i of the process. ~igure 2 is a simplified represen~
tation of an example of the Claus ~rocess plant which may be used in accordance with +~he inven~ion, Pu~ps and compressors have been omitted in t;he drawing for the sake of simplicity and of a clearer arrangement~
In the process illustrated in Figure 1 ~e gas which is to be desulfurized is fed in l~ne 1 to a scrubbing zone 2, which is supplie~1 with regenerated scrubbing solution through line 3. Purified ~as is withdrawn in line 4. Laden scrubbing solution~
which contains H2S and C02, is supplied in line 5 with a partial pressure relief to a re-absorber 6. ~he re-absorber consists OL` a regenerating column, ~vhich contains mass transfer-promo~in~ elements known per se 9 such as liquid- and gas-permeable plates. I~he re-absorber 6, C02 is substantially stripped off whereas as much H2S as possible is ~ept in the scrubbing solution.
~or thls purpose the re-absorber is supplied at its top through line ~ with regenerated scrubbing solution, which prefercntially takes up the sulf'ur compounds from the rising gases. Y2S-containing ~ases from lines 10 and 11 are SUPP1ierI to the lower portiun of the re-ab-sorber and in the re-absorber 6 act as stri-~ing gases to strip off particularly C02. ~n exhaust ~as which is rich in C02 is withdrawn from the re-absorber through line 12 and becnuse it has substantiallv been ~lesul-furized may be combined for most appllcation with the Oas frQm line 4.
. .: ~ : :,: .:
: , . . . :.:. :
l`he scrubbing solution from the re~
absorber 6 is supplied in line 13 to a heat exchanger 14 and is heated therein and then flo~ls in line 15 to the hot regenerating apparatus 16, in which a reboiler 17 effects the temperature rise which is required for a release of impurities, particularly H2S, which are bound to the scrubbing solution. In case of need, a strip~in~ gas may additionall~- be supplied through the line 18, which is indicated by a dotted linè. ~hat stripping gas may consist7 e.g., ot` hydrogen rr nitrogen or of a desulfurized exhaust gas.
~ egenerated scrubbing solution le~ves the hot regenerating zone 16 in line 20 and is cooled in the heat exchanger 1~ and in line 21 is recycled to the scrubbing zone 2 and to the re-absor`oer 6. ~xhaust gas which is rich in H2S is withdrawn in line 23 from the top of the hot regenerating apparatus 16 and a partial stream thereor is supplied in line 24 to a Claus process plant, vhich consists of a burner section ~ and a suc-ceeding hydrogenati~g ~ection Ho Details of the Claus process plant consisting of sections ~ and H will be explained hereinafter with reference to Figure 2. and it ill also be explained that the hydrogenating section H
comprises a hydrogenating and/or hydrolyzing 5 ~age. Re-maining exhaust gas i5 withdrawn in line 23 from the hot regenerating apparatus 16 and is supplied through a cooler 26 and through line 11 to the re-absorber 6.
It is indicated in ~igure 1 that in addition ..
h.~ . .. ..
to the exhaust ~as which is rich in H2S and conducted in line 24 the Claus ~rocess plant is supplied through line 28 with oxygen or a.ir or oxygen-enriched air, that elementary sulfur is ~thdrawn in line 30, that exhaust gas which contains H25 and S02 is supplied in line 45 to the hydrogenating sectiorl H, and that a part of the H2S-containing residual as frcm the hydrogenating section is recycled in line lOa for a control of the temperature in the hydrogenating re~ctor. ~he scrubbing zo~e 2, the re-absorber ~j an~ t~e hot regenerating appa-ratus 16 may contain elements known per se, such as plates, for im?roving the mass transfer.
'rhe ~aus process plant which i~
shown in ~etail in ~igure 2 essentially consists of the burner section ~ (between items 24 and 40) and the hydro-genating section H (bet~ieen items 45 and 50) and is o~erat-ed as follows: ~xhaust gas from line 24 and oxygen-con-tainin~ gas from line 28 are initially sup~lied to a Claus process burner 31 ~ or a plurality of burners - provided with an integrated combustion chamber. Details of such a combuster are described in Published German Application 37 35 002 and in U.S. r~tent 4,632,~19. By the combustion, a gas mixture at temperetures of~b`out lO00 to 2000C is produced and the oxygen in line 28 is metered to ensure that the mole ratio of ~2~ to ~2 in the gas mixture lies between 4:1 and 1:1 and preferably at about 2:1.
" . ~ , . ~ . ~ .
. .
,. . ~: ,,,, ,;, _9_ The succe~ding indirect cooler 32 is provided with a feed ~fJater sup?ly line 34 and ~,vith a ~Jater v~por-withdr~wing line 33 and is used -to cool the gas mixture below the dew point temperature of sulfur so that ele-mentary sulfur ls condensed. ~hat elementary sulfur is delivered in line ~Oa to ~ collectir.g bin Z5.
~ he cooled gas mi:~ture ~lows in ;ine ~7 ~o a further indirect cooler ~8, which i9 used to improve the yield of elementary sulfur. That elementar~
sulfur flows in line ~Ob also to the bin 35. The gas in line 40 is still at temperatures of about 125 to 135C
and is heated in an indirect heat exchan~er 430 ~he thus preheated gas is supplied at tem~eratures of 180 to 280C in line 45 to a catalytic h~Jdrogenator 46, which .vill be supplied through line 46a with hydrogen-co~taining gases if the hydro~en produced in ~he com-bustion chamber 31 is not sufficient. The h~drogenator may be used entirely or in part as a hJdrolyzer and is used in known manner mainly ~o convert S02 co H2S.
Co~t-molybdenum catalysts ma~ be used, for instance, fo~ that purpose. The gas mixture from the h~drogenator 46 is initially precooled in the cooler 47 and is ther fed to a direct cooler 48 for a remo~Jal of water~
The cooler 48 is 5upplied with cooli~g ~ater, which is circulated throu~h an indirect cooler 49. Surplus wa~er is withdrawn in line 50. H2S-containing residual gas at temperatures of a~out 20 to 40~ leaves ~he cooler 48 in line 10 and a partial stream of tha~ residual gas is ` . '` ' ~ ' ~ " ' , ' r;) recycled in line lOa -to the hydrogenator 46 to control the temperature in the nydrogenator. Lines lOa and 46a may alternatively open in~o line 45. The residual gas flOw~ng in line 10 will be ~rocessed further in the manner that is ex~ained with reference to Figures 1, 3, and 4.
The p~ocess variants illustrated in ~'igures 3 and 4 agree with the rrocess of Figure 1 in part so that like reference characters are employed and reference is made to the explan~tions furnished with reference to ~igure 1. In accordance with Figure 3, gas which is to be desulfurized is supplied in line la and after it has been mixed with the gas flowing in line 10 is supplied in line 1 tothe scrubbing zone 2. In the processes illustrated in ~'igures 3 and 4 the regenerating appara-tus also compriSQs two regenerating columns 7 and 51, in which the scrubbing solution i9 partly pressure-relieved and is treated with a strip~ing gas. The stripping gas for the column 7 comes from line 52 and consists of an exhaust gas which comes fxom the regenerating column 51 and has flown through the cooler 53. In accordance with Figure 3 a part of the exhaust gas from column 7 is supplied in line 60 to the scrubbing zone 2 and the remainder flows through line 61 to the hydroge~atiDg section H of the Claus process plant~ Hydrogen-contain-ing gas is added through line 46a and may be tapped, e.g., from the pure gas flowing in line 4 if that pure gas is .... . .....
.;: .:.
,~ : ~ ~ ................. . .
: :.
; . ~ . .
- , . , - . :, . , .: , .. ..
'' : ! ; ; : .
~ . .. . `
suitable for the purposeO
StripDin, gas is supplied i~ line 18 also t~ the hot regenerating apparatus 16, and a part of the exhaust gas from the hot regenerating appa-ratus flows through the control valve 66 and line 67 as a stripping gas to the second regenerating column 51. ~he scrubbing solu~ion from line 15 flo~s throush the pressure relief valve 15a and subsequently enters the column 51. H2S-containing residual gas from-the hy-drogenating section H is admixed from line 10 to the gas to be purified, which flows in line lo The proce~s illustrated in Figure 4 is similar to that shown in Figure 3. In that case the H2S-containing residual gas from line 10 is used as an additional stripPing g~s in the first regenerating column 7 and the entire exhaust gas from that column is supplied through line 60 to the scrubbing zone 2. ~he sntire ex-haust gas which is rich in H2S and comes from the hot regenerating apparaGus 16 is supplied in line 24 to ~he Claus process plant. ~itrogen, e.g., is used as a stripping ~as in the second regenerating column 51 and is supplied in line 62. Hydrogen usually coming ~rom an extraneous source is sup~lied as a hydrogenating gas through line 46a ~o ~he hydrogenati~g section H. Alter-natively, a partial stream of the scrubbed gas in line 4 may be used as a hydrogenating gas.
- , . ..
..
,. - , ' .
, .
;
~xample 1 In R processing system as shown in Figure 3, comprisiDg a Claus process plant as shown in Figure 2, a dedusted product gas from the gasifi-cation of coal is treated with NMP as a scrubbing solution. Data indicating the rates, pressures and ~as components in various lines are apparent from the following tables. All rates, also those of the compo-nents,are stated in all examples in kilomoles per hour.
Line 1a 4 5 10 60 61 ;~ateloooo 10039.4 395-7 192.5 247 119.9 (bars) 37 36 37 1.1 1.4 1.4 Components:
2 1650 1656.4 294 104.3 196.8 95.7 s 33 - 75 22.7 19.3 9.4 ~2 4317 431404 11 2.8 7.5 3.5 co 4000 3993.6 15.5 0.4 10.5 5.0 N2 - 75 002 62.3 1209 603 Line 13 24 46a 52 54 67 .
~ate 124.4 lC3.8 4.4 95.6 65.9 37.1 Pressure (bars) 105 1.8 36 1.6 108 1.8 Components:
C2 49.2 105 C.7 47.7 2 o.5 H2S 74-9 4603 - 28.6 63 1607 2 - 1.9 _ _ co - - 1.8 ~2 0. 3 56 _ 19.3 o O 9 19.9 ..
.
,-, , . ..
~ f~ J~
.~itrogen at a rate of 75 kilomoles per hour is conducted as a strippin~ g~s through line 18. Pure oxygen at a rate of 21 kilomoles per hour is supplied through line 28 ~o the combustion chamber 31.
The laden scrubbing solution in line 5 is at a tempe-rature of 37C. ~lementar~J sulfur is collected in the bin 35 at a rate of 33 kilomoles per hour. In the hydrogenator 46, a cobalt-mol~Jbdenum catalyst is used, which comprises a carrier consistin~ of activated alu-mina, A partial stream of the pure gas in liue 4 is supplied in line 46a as an additional hydrogenating gas. 35.6 kilomoles of water at 70C are withdrawn per hour in line 50.
Example 2 A processing s~stem as shown in Figure 4 combined with the Claus process plant of Figure 2 is used to process a gas that has been produced by a gasification of coal and is supplied in li~e la.
NMP is used as a scrubbing solution. Nitroge~ at a rate of 45 kilomoles per hour is supplied as a stripping gas in line 62. ~he combustion in the combustion chamber 31 is effected with pura 2 supplied at a rate of 12.1 kilomoles per hour, and elementary sulfur at a rate of 19 kilomoles per hour is collected in the bin 35. '~ater at a rate of 24.1 kilomoles per hour is withdrawn in line 50. Further data are stated in the following tables, , , .
in which all rates, also those of the components, are stated in kilomoles per hourO
Line 1 4 5 10 13 24 .
Rate 10000 10026.8 372.6 9 128.127.2 (bars) 37 36 37 1.4 1051.8 ~emperature (C) 3 38 36 3 31 Components:
~2 1650 1650 3 ~ 27 H2~ 19 _ 4603 6.3 100~52503 H2 + C0 8331 8331.8 26.3 008 - _ N - 45 - 1.9 0.61.9 Line 46a 52 54 60 Rate 6 14509 2702 399.4 Pressure (bars) 2.5 104 1.8 1~3 ~emperature (C) 30 30 31 Components:
C2 ~ 27 - 300 H2~ ~ 7502 2503 2703 H2 ~ C0 6 - _ 2701 _ 43.7 1.9 45.0 . . ...
.
This invention relates to a process of purifylng a gas which con~ains combusti~le components as well as carbon dioxids and sulfur compounds, parti~
cularly H2S, in that ~he ~as i~ scrubbed in a scrubbing z.one with a scrubbing solution, which is regenerated and re-used, whereill the sc~llbbing solution to ~e regene-rated is pressure-relieved, stripped, and heated in a hot regenerating zone, an exhaust ~'G3 rich in H2S pro-duc~d in the l!ot regenerati~g zone is processed to form ele~enbary sulfur and a residual gas which contains H2S, an~ the residual gas i3 contacted with scrubbing solution~
`~uropean ~atent 0 054 772 describes a process which s of that ~ind and in which the exhaust gas that is supr.lied to the Claus proces~ plan~ contains considerable amounts o~ ~,C, i n addition to ~S. That exhaust ~as i5 proces~:ed rurther in a relatively ex-pe.nsive Claus process Dlant~ which inlcudes two or three . .,.. . .
.. ..
,' `
S ~
catalytic stages, in which after a partial com~ustion of H2S to S02 the exhaust ias is catal,~tically con-verted as completely as possible to elementary sulfur and water by the Claus re~ction H2S + ~2 -' 3 S + 2 H20 ae~ore and behind each of ~ d catalytic stages, elemen~
tary sulfur is condensed ~rom the mi~ed gases and is removed. In the l{nown proces,~ the catalytic conversion stages are succeeded c~ a hydro~enation and the exhaust gas is therea~ter recycled to the scrubber.
Those catalytic processing stages give rise tc conserable costs and have the disadvantage that they render the star~-up of the plant from stand-still expensive and time-consuming. There is also a risk that in case of frequent start-ups and shutdowns and of extreme load changes the catalysts will soon lose their activity.
It is an object of the invention so to process the exhaust gas rich in H2S that is formed in the hot regenerating zone that a fast start-up from a standstill can be effected in a simple manner and even a frequent load change will not be problematic.
In the process which has been described first herein-before this is accomplished in accordance with the in-vention in that the exhaust gas which is rich in H2S
and has been produced in the hot regenerating zone is .. - ~ ~, ~ ~,'. ' , ,:
s ~
~3--partly combusted in a combustion chamber with oxygen, oxygen-containing ga~ or air; a ~,as mixture which is at a temperature in the range from lO00 to 2000C and in which ~ e percent of the sulfur supplied to the combustion chamber are contained a~ elementary sulfur and which also contains the components H2S and S02 in a molar ratio of 4:l to 1:1 is produced in the combustion the chamber; ~as mixture is cooled below the dew point tem-perature of sulfur; condensed elementary sulfur is re-moved; the gas ~ixture is subsequently heated to tem-peratures of 180 to 280C and is th~n directl~ subjected to a catalytic hydrogenation and/or hydrolysis, wherebg the residual content o~ S02 is substantiall~ converted to H2S ;
and at least part of the gas which has thus been treated is contacted as an H2S-containing residual gas with scrubbing solution. The process in accordance with the invention is particularly desir-able for the desulfurization of fuel gases to be used as fuel in a gas turbine-steam turbine power pla~.
In the process in accordance with the invention, ca~ is taken to ensure that the ga~ which is rich in H2S and supplied to the combustion chamber is highly enriched with H2S so that a large share of the hydrogen sulfide is reacted to elementary sulfur by the reaction , .~ "
.
H2S + 2 ~ S ~ H20 in and immediately after the combustion chamber and there is no longer a need for a further processing of the gas mixture by a catalytic reaction of -H~S and S2 according to the Claus reaction 2 H2$ ~ S02 = 3 S + 2 H20 reaction of H2~ to a lower degree i5 in~entionally tolerated and this will also increase the demand for hydrogen for the hydrogenation. But in the process in accordance with the invention the h~per rate of hydro-genation requires that the h~drogenation catalyst is cooled and in the process in accordance with the in-vention that cooling can be effected by the ~eeding of a cooling gas, which ma~ also be used to supply the de-ficient hydrogenatin~ hydro~en.
'~he residual ~as which is ~igh in ~I2S and has been produced iD the hydro~enating and/or hydrolyzing stage may be recycled, e.~., to the scrubbing zone or to the regeneratin~ stage. Alternatively, part of that residual .sas may directl~ be supplied to the combustion chamber and this will be recommendable particularl~ if oxygen and an exhaust ~as which is highly enriched with H2S are supplied to the com~ustion chamberO
;''he hot regenerat~on proauces an exhaust ~as which has a low C02 content not in excess of l~o by volume or will have a much lower C02 content if the laden scrubbing solution ;`rom -;he ;crubbirg zone is pressure-relieved iD at least ~10 re~en~atin~ columns . : :
', ' , ., '.~ ' , , . ' ~:
~ 4 , ~i!
before the hot re~eneration. In ~,hat c~se it wiil be recommendable to feed at least ~art of ~he flashed-off gas as a stripr,ing gas to u~e E!recedinLr s~a~e. Lr addition, inert gas ~ay be used as a stripping gas in the hot regenerating ~oneO
The process is particularl~ desir-able for effecting a desulfurization oi` gases which have a high heatin~ value and are intended for use in a gas turbine-steam turbine po~ver plant~ Such gases having a high heatin~ value ma~- be ~roduced in a manner known per se, e.~ y a gasification oi` solid fuels.
'rhe gas may be purified by means of various ~crubbing solutions, which ~re selec~ite for ~l2S and which are known per se and may consist, e~g., of physicallù~ acting scrubbing solutions, such ~IS ;netne;nol, N-methyl pyrrolidone, methyl diethanol~mine or also dimethyl ether of polyethylene glyc~ he ~as is scrub-bed in most cases under pressures in the ran~e from 5 to 100 hars and at the ~no~rn te~peratures which are ~ypical of the scrub~ing solution employed and lie in the range from -80C to ~100C. ~ha e].emen',Gry sulfur is produced under pressures of about 1 to ,~0 bars or even ligrher pressures. Pressure~ o~ 1 to 10 bars are presently pre-ferred.
Further features of the process will be explained with reference to the ~Irawing. Figures 1, 3, ~nd 4 are flow schemes illustratinLr various variants " .:.: . .- .
,.
` . ~ ` ' . - ' ~ 3,i of the process. ~igure 2 is a simplified represen~
tation of an example of the Claus ~rocess plant which may be used in accordance with +~he inven~ion, Pu~ps and compressors have been omitted in t;he drawing for the sake of simplicity and of a clearer arrangement~
In the process illustrated in Figure 1 ~e gas which is to be desulfurized is fed in l~ne 1 to a scrubbing zone 2, which is supplie~1 with regenerated scrubbing solution through line 3. Purified ~as is withdrawn in line 4. Laden scrubbing solution~
which contains H2S and C02, is supplied in line 5 with a partial pressure relief to a re-absorber 6. ~he re-absorber consists OL` a regenerating column, ~vhich contains mass transfer-promo~in~ elements known per se 9 such as liquid- and gas-permeable plates. I~he re-absorber 6, C02 is substantially stripped off whereas as much H2S as possible is ~ept in the scrubbing solution.
~or thls purpose the re-absorber is supplied at its top through line ~ with regenerated scrubbing solution, which prefercntially takes up the sulf'ur compounds from the rising gases. Y2S-containing ~ases from lines 10 and 11 are SUPP1ierI to the lower portiun of the re-ab-sorber and in the re-absorber 6 act as stri-~ing gases to strip off particularly C02. ~n exhaust ~as which is rich in C02 is withdrawn from the re-absorber through line 12 and becnuse it has substantiallv been ~lesul-furized may be combined for most appllcation with the Oas frQm line 4.
. .: ~ : :,: .:
: , . . . :.:. :
l`he scrubbing solution from the re~
absorber 6 is supplied in line 13 to a heat exchanger 14 and is heated therein and then flo~ls in line 15 to the hot regenerating apparatus 16, in which a reboiler 17 effects the temperature rise which is required for a release of impurities, particularly H2S, which are bound to the scrubbing solution. In case of need, a strip~in~ gas may additionall~- be supplied through the line 18, which is indicated by a dotted linè. ~hat stripping gas may consist7 e.g., ot` hydrogen rr nitrogen or of a desulfurized exhaust gas.
~ egenerated scrubbing solution le~ves the hot regenerating zone 16 in line 20 and is cooled in the heat exchanger 1~ and in line 21 is recycled to the scrubbing zone 2 and to the re-absor`oer 6. ~xhaust gas which is rich in H2S is withdrawn in line 23 from the top of the hot regenerating apparatus 16 and a partial stream thereor is supplied in line 24 to a Claus process plant, vhich consists of a burner section ~ and a suc-ceeding hydrogenati~g ~ection Ho Details of the Claus process plant consisting of sections ~ and H will be explained hereinafter with reference to Figure 2. and it ill also be explained that the hydrogenating section H
comprises a hydrogenating and/or hydrolyzing 5 ~age. Re-maining exhaust gas i5 withdrawn in line 23 from the hot regenerating apparatus 16 and is supplied through a cooler 26 and through line 11 to the re-absorber 6.
It is indicated in ~igure 1 that in addition ..
h.~ . .. ..
to the exhaust ~as which is rich in H2S and conducted in line 24 the Claus ~rocess plant is supplied through line 28 with oxygen or a.ir or oxygen-enriched air, that elementary sulfur is ~thdrawn in line 30, that exhaust gas which contains H25 and S02 is supplied in line 45 to the hydrogenating sectiorl H, and that a part of the H2S-containing residual as frcm the hydrogenating section is recycled in line lOa for a control of the temperature in the hydrogenating re~ctor. ~he scrubbing zo~e 2, the re-absorber ~j an~ t~e hot regenerating appa-ratus 16 may contain elements known per se, such as plates, for im?roving the mass transfer.
'rhe ~aus process plant which i~
shown in ~etail in ~igure 2 essentially consists of the burner section ~ (between items 24 and 40) and the hydro-genating section H (bet~ieen items 45 and 50) and is o~erat-ed as follows: ~xhaust gas from line 24 and oxygen-con-tainin~ gas from line 28 are initially sup~lied to a Claus process burner 31 ~ or a plurality of burners - provided with an integrated combustion chamber. Details of such a combuster are described in Published German Application 37 35 002 and in U.S. r~tent 4,632,~19. By the combustion, a gas mixture at temperetures of~b`out lO00 to 2000C is produced and the oxygen in line 28 is metered to ensure that the mole ratio of ~2~ to ~2 in the gas mixture lies between 4:1 and 1:1 and preferably at about 2:1.
" . ~ , . ~ . ~ .
. .
,. . ~: ,,,, ,;, _9_ The succe~ding indirect cooler 32 is provided with a feed ~fJater sup?ly line 34 and ~,vith a ~Jater v~por-withdr~wing line 33 and is used -to cool the gas mixture below the dew point temperature of sulfur so that ele-mentary sulfur ls condensed. ~hat elementary sulfur is delivered in line ~Oa to ~ collectir.g bin Z5.
~ he cooled gas mi:~ture ~lows in ;ine ~7 ~o a further indirect cooler ~8, which i9 used to improve the yield of elementary sulfur. That elementar~
sulfur flows in line ~Ob also to the bin 35. The gas in line 40 is still at temperatures of about 125 to 135C
and is heated in an indirect heat exchan~er 430 ~he thus preheated gas is supplied at tem~eratures of 180 to 280C in line 45 to a catalytic h~Jdrogenator 46, which .vill be supplied through line 46a with hydrogen-co~taining gases if the hydro~en produced in ~he com-bustion chamber 31 is not sufficient. The h~drogenator may be used entirely or in part as a hJdrolyzer and is used in known manner mainly ~o convert S02 co H2S.
Co~t-molybdenum catalysts ma~ be used, for instance, fo~ that purpose. The gas mixture from the h~drogenator 46 is initially precooled in the cooler 47 and is ther fed to a direct cooler 48 for a remo~Jal of water~
The cooler 48 is 5upplied with cooli~g ~ater, which is circulated throu~h an indirect cooler 49. Surplus wa~er is withdrawn in line 50. H2S-containing residual gas at temperatures of a~out 20 to 40~ leaves ~he cooler 48 in line 10 and a partial stream of tha~ residual gas is ` . '` ' ~ ' ~ " ' , ' r;) recycled in line lOa -to the hydrogenator 46 to control the temperature in the nydrogenator. Lines lOa and 46a may alternatively open in~o line 45. The residual gas flOw~ng in line 10 will be ~rocessed further in the manner that is ex~ained with reference to Figures 1, 3, and 4.
The p~ocess variants illustrated in ~'igures 3 and 4 agree with the rrocess of Figure 1 in part so that like reference characters are employed and reference is made to the explan~tions furnished with reference to ~igure 1. In accordance with Figure 3, gas which is to be desulfurized is supplied in line la and after it has been mixed with the gas flowing in line 10 is supplied in line 1 tothe scrubbing zone 2. In the processes illustrated in ~'igures 3 and 4 the regenerating appara-tus also compriSQs two regenerating columns 7 and 51, in which the scrubbing solution i9 partly pressure-relieved and is treated with a strip~ing gas. The stripping gas for the column 7 comes from line 52 and consists of an exhaust gas which comes fxom the regenerating column 51 and has flown through the cooler 53. In accordance with Figure 3 a part of the exhaust gas from column 7 is supplied in line 60 to the scrubbing zone 2 and the remainder flows through line 61 to the hydroge~atiDg section H of the Claus process plant~ Hydrogen-contain-ing gas is added through line 46a and may be tapped, e.g., from the pure gas flowing in line 4 if that pure gas is .... . .....
.;: .:.
,~ : ~ ~ ................. . .
: :.
; . ~ . .
- , . , - . :, . , .: , .. ..
'' : ! ; ; : .
~ . .. . `
suitable for the purposeO
StripDin, gas is supplied i~ line 18 also t~ the hot regenerating apparatus 16, and a part of the exhaust gas from the hot regenerating appa-ratus flows through the control valve 66 and line 67 as a stripping gas to the second regenerating column 51. ~he scrubbing solu~ion from line 15 flo~s throush the pressure relief valve 15a and subsequently enters the column 51. H2S-containing residual gas from-the hy-drogenating section H is admixed from line 10 to the gas to be purified, which flows in line lo The proce~s illustrated in Figure 4 is similar to that shown in Figure 3. In that case the H2S-containing residual gas from line 10 is used as an additional stripPing g~s in the first regenerating column 7 and the entire exhaust gas from that column is supplied through line 60 to the scrubbing zone 2. ~he sntire ex-haust gas which is rich in H2S and comes from the hot regenerating apparaGus 16 is supplied in line 24 to ~he Claus process plant. ~itrogen, e.g., is used as a stripping ~as in the second regenerating column 51 and is supplied in line 62. Hydrogen usually coming ~rom an extraneous source is sup~lied as a hydrogenating gas through line 46a ~o ~he hydrogenati~g section H. Alter-natively, a partial stream of the scrubbed gas in line 4 may be used as a hydrogenating gas.
- , . ..
..
,. - , ' .
, .
;
~xample 1 In R processing system as shown in Figure 3, comprisiDg a Claus process plant as shown in Figure 2, a dedusted product gas from the gasifi-cation of coal is treated with NMP as a scrubbing solution. Data indicating the rates, pressures and ~as components in various lines are apparent from the following tables. All rates, also those of the compo-nents,are stated in all examples in kilomoles per hour.
Line 1a 4 5 10 60 61 ;~ateloooo 10039.4 395-7 192.5 247 119.9 (bars) 37 36 37 1.1 1.4 1.4 Components:
2 1650 1656.4 294 104.3 196.8 95.7 s 33 - 75 22.7 19.3 9.4 ~2 4317 431404 11 2.8 7.5 3.5 co 4000 3993.6 15.5 0.4 10.5 5.0 N2 - 75 002 62.3 1209 603 Line 13 24 46a 52 54 67 .
~ate 124.4 lC3.8 4.4 95.6 65.9 37.1 Pressure (bars) 105 1.8 36 1.6 108 1.8 Components:
C2 49.2 105 C.7 47.7 2 o.5 H2S 74-9 4603 - 28.6 63 1607 2 - 1.9 _ _ co - - 1.8 ~2 0. 3 56 _ 19.3 o O 9 19.9 ..
.
,-, , . ..
~ f~ J~
.~itrogen at a rate of 75 kilomoles per hour is conducted as a strippin~ g~s through line 18. Pure oxygen at a rate of 21 kilomoles per hour is supplied through line 28 ~o the combustion chamber 31.
The laden scrubbing solution in line 5 is at a tempe-rature of 37C. ~lementar~J sulfur is collected in the bin 35 at a rate of 33 kilomoles per hour. In the hydrogenator 46, a cobalt-mol~Jbdenum catalyst is used, which comprises a carrier consistin~ of activated alu-mina, A partial stream of the pure gas in liue 4 is supplied in line 46a as an additional hydrogenating gas. 35.6 kilomoles of water at 70C are withdrawn per hour in line 50.
Example 2 A processing s~stem as shown in Figure 4 combined with the Claus process plant of Figure 2 is used to process a gas that has been produced by a gasification of coal and is supplied in li~e la.
NMP is used as a scrubbing solution. Nitroge~ at a rate of 45 kilomoles per hour is supplied as a stripping gas in line 62. ~he combustion in the combustion chamber 31 is effected with pura 2 supplied at a rate of 12.1 kilomoles per hour, and elementary sulfur at a rate of 19 kilomoles per hour is collected in the bin 35. '~ater at a rate of 24.1 kilomoles per hour is withdrawn in line 50. Further data are stated in the following tables, , , .
in which all rates, also those of the components, are stated in kilomoles per hourO
Line 1 4 5 10 13 24 .
Rate 10000 10026.8 372.6 9 128.127.2 (bars) 37 36 37 1.4 1051.8 ~emperature (C) 3 38 36 3 31 Components:
~2 1650 1650 3 ~ 27 H2~ 19 _ 4603 6.3 100~52503 H2 + C0 8331 8331.8 26.3 008 - _ N - 45 - 1.9 0.61.9 Line 46a 52 54 60 Rate 6 14509 2702 399.4 Pressure (bars) 2.5 104 1.8 1~3 ~emperature (C) 30 30 31 Components:
C2 ~ 27 - 300 H2~ ~ 7502 2503 2703 H2 ~ C0 6 - _ 2701 _ 43.7 1.9 45.0 . . ...
.
Claims (12)
1. A process of purifying a gas which contains combustible components as well as carbon dioxide and sulfur compounds, particularly H2S, wherein the gas is scrubbed in a scrubbing zone with a scrubbing solution, which is regenerated and re-used, wherein the scrubbing solution to be regenerated is pressure-relieved, strip-ped, and heated in a hot regenerating zone, an exhaust gas rich in H2S produced in the hot regenerating zone is pro-cessed to form elementary sulfur and a residual gas which contains H2S, and the residual gas is contacted with scrubbing solution, characterized in that the ex-haust gas which is rich in H2S and has been produced in the hot regenerating zone is partly combusted in a combustion chamber with oxygen, oxygen-containing gas or air; a gas mixture which is at a temperature in the range from 1000 to 2000 °C and in which at least 30 mole percent of the sul-fur supplied to the combustion chamber are contained as elementary sulfur and which also contains the components H2S and SO2 in a molar ratio of 4:1 to 1:1 is produced in the combustion chamber; the gas mixture is cooled below the dew point temperature of sulfur; condensed elementary sul-fur is removed; the gas mixture is subsequently heated to temperatures of 180 to 280°C and is directly sub-jected to a catalytic hydrogenation and/or hydrolysis, whereby the residual content of SO2 is substantially con-verted to H2S; and at least part of the gas which has thus been treated is contacted as an H2S-containing residual gas with scrubbing solution.
2. A process according to claim 1, characterized in that H2S containing residual gas which comes from the hydrogenating and/or hydrolyzing stage is supplied to the scrubbing zone.
3. A process according to claim 1 or 2, characterized in that an exhaust gas which is rich in H2S and contains CO2 not in excess of 10 % by volume is supplied to the combustion chamber.
4. A process according to claim 1 or any of the following claims, characterized in that a partial stream of the residual gas coming from the hydrogenating and/or hydrolyzing stage is recycled to a point which precedes the hydrogenating or hydrolyzing stage.
5. A process according to claim 1 or any of the following claims, characterized in that scrubbing solution which comes from the scrubbing zone and contains impuri-ties is partly pressure-relieved in a first regenerating column, which contains mass transfer-promoting elements, a first exhaust gas, which contains CO2, is withdrawn from the first regenerating column and is supplied at least in part to the scrubbing zone, the scrubbing so-lution from the first regenerating column is heated and is partly pressure-relieved in a second regenerating column, which contains mass transfer-promoting elements, partly regenerated scrubbing solution from the second re-generating column is supplied to the hot regenera-ting zone, a stripping gas is supplied to the second regenerating column, and a second exhaust gas is withdrawn from the second regenerating column and is supplied as a stripping gas to the first re-generating column.
6. A process according to claim 5, characterized in that H2S-containing residual gas which comes from the hydrogenating and/or hydrolyzing stage is supplied as a stripping gas to the second regeneration column.
7. A process according to claim 5, characterized in that nitrogen containing gas is supplied as a stripping gas into the hot regeneration zone and a partial stream of the exhaust gas from the hot regeneration zone is supplied as a stripping gas to the second regeneration column.
8. A process according to claim 5, characterized in that H2S-containing residual gas which comes from the hydrogenating and/or hydrolyzing stage is supplied as a stripping gas to the first regeneration column.
9. A process according to claim 1 or any of the following claims, characterized in that a portion of the H2S-containing residual gas coming from the hydrogenating and/or hydrolyzing zone is supplied into the combustion chamber.
10. A process according to claim 5 or any of the following claims, characterized in that a partial stream of the first exhaust gas coming from the first regeneration column is supplied to the catalytic hydrogenation and/or hydrolysis zone.
11. A process according to claim 1 or any of the following claims, characterized in that 30 to 80 % of the sulfur which is contained in the exhaust gas which is supplied to the combustion chamber, is gained as elementary sulfur.
12. A process according to claim 1 or any of the following claims, characterized in that the purified gas withdrawn from the scrubbing zone is supplied to a gas turbine-steam turbine power plant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4014018.0 | 1990-05-01 | ||
| DE4014018A DE4014018A1 (en) | 1990-05-01 | 1990-05-01 | Gas purificn. using recyclable scrubber soln. - esp. for desulphurisation of fuel gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2041157A1 true CA2041157A1 (en) | 1991-11-02 |
Family
ID=6405536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002041157A Abandoned CA2041157A1 (en) | 1990-05-01 | 1991-04-24 | Process of purifying an h2s- and co2-containing gas |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0455285B1 (en) |
| JP (1) | JPH0584422A (en) |
| CN (1) | CN1031817C (en) |
| AT (1) | ATE96339T1 (en) |
| AU (1) | AU634881B2 (en) |
| BR (1) | BR9101744A (en) |
| CA (1) | CA2041157A1 (en) |
| CZ (1) | CZ283005B6 (en) |
| DE (2) | DE4014018A1 (en) |
| DK (1) | DK0455285T3 (en) |
| ES (1) | ES2046004T3 (en) |
| PL (1) | PL164978B1 (en) |
| SK (1) | SK279282B6 (en) |
| ZA (1) | ZA913277B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008052325A1 (en) * | 2006-10-31 | 2008-05-08 | John Keum-Ho Hwang | A method and system for recovering sulphur from gas streams |
| CN101985082A (en) * | 2009-07-28 | 2011-03-16 | 林德股份公司 | Method and apparatus for separating mixture of gases in washing device |
| US8007569B2 (en) | 2003-07-16 | 2011-08-30 | Uhde Gmbh | Method for removing hydrogen sulphide and other acidic gas components from pressurized technical gases |
| CN114317037A (en) * | 2021-12-31 | 2022-04-12 | 唐山中溶科技有限公司 | Method for preparing hydrogen from coke oven gas by utilizing decarbonization liquid regeneration through decomposition gas |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5391278A (en) * | 1993-02-25 | 1995-02-21 | Idemitsu Kosan Co., Ltd. | Process for removal of hydrogen sulfide |
| GB9606685D0 (en) * | 1996-03-29 | 1996-06-05 | Boc Group Plc | Gas separation |
| DE10245164B4 (en) * | 2002-09-26 | 2014-11-13 | Evonik Degussa Gmbh | Process for the conversion of polysulfanes |
| US7455828B2 (en) * | 2004-03-01 | 2008-11-25 | H2S Technologies, Ltd. | Process and apparatus for converting hydrogen sulfide into hydrogen and sulfur |
| ES2369511T3 (en) * | 2007-07-31 | 2011-12-01 | Shell Internationale Research Maatschappij B.V. | PROCESS TO PRODUCE PURIFIED GAS FROM GAS THAT INCLUDES H2S, CO2, AND HCN AND / OR COS. |
| DE102007055296A1 (en) * | 2007-11-20 | 2009-05-28 | Linde Aktiengesellschaft | Regeneration of washing agent from a gas scrubber applies an initial heat and pressure to hold metal carbonyls in a solution for further heating and pressure for them to be separated by precipitation |
| CA2707106A1 (en) * | 2007-11-27 | 2009-06-04 | Linde Aktiengesellschaft | Process and apparatus for the regeneration of the laden scrubbing medium in a physical gas scrubbing |
| DE102009015368A1 (en) * | 2009-03-27 | 2010-09-30 | Linde Ag | Method for cleaning synthesis raw gas containing hydrogen, carbon monoxide, and carbon dioxide, involves utilizing generated gas as stripping gas for removing co-absorbed materials from loaded washing agents |
| DE102010013279B3 (en) * | 2010-03-29 | 2011-07-28 | Uhde GmbH, 44141 | Process and apparatus for processing a carbon dioxide rich sour gas in a Claus process |
| US8425655B2 (en) * | 2010-07-09 | 2013-04-23 | Carbon Capture Scientific, Llc | Gas pressurized separation column and process to generate a high pressure product gas |
| DE102012006748A1 (en) * | 2012-04-03 | 2013-10-10 | Linde Aktiengesellschaft | Process and apparatus for sulfur recovery |
| CN102631827A (en) * | 2012-04-11 | 2012-08-15 | 山东三维石化工程股份有限公司 | Zero-emission sulfur recovery technology combined with low-temperature methanol washing acid gas treatment |
| DE102013008852A1 (en) * | 2013-05-23 | 2014-11-27 | Linde Aktiengesellschaft | Process and apparatus for treating a sulfur-containing exhaust gas from a sulfur recovery |
| NO2821120T3 (en) * | 2013-07-03 | 2018-02-03 | ||
| CN103822217B (en) * | 2014-02-14 | 2016-06-01 | 江苏新世纪江南环保股份有限公司 | A kind of sour gas pretreatment technology |
| CN103897760B (en) * | 2014-04-10 | 2016-01-20 | 开封黄河空分集团有限公司 | Methane purification system |
| JP6906766B2 (en) | 2017-11-30 | 2021-07-21 | 株式会社神戸製鋼所 | Gas treatment method and gas treatment equipment |
| CN111888859B (en) * | 2020-09-02 | 2021-11-23 | 杭州广丰实业有限公司 | Energy-concerving and environment-protective type industrial waste gas recovery processing device |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3047830A1 (en) * | 1980-12-18 | 1982-07-15 | Linde Ag, 6200 Wiesbaden | METHOD FOR CLEANING A GAS FLOW |
| DE3415722A1 (en) * | 1984-04-27 | 1985-10-31 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR REMOVING SULFUR HYDROGEN FROM EXHAUST GAS AND FOR GENERATING IN SULFUR AFTER THE CLAUS PROCESS |
| GB2192347B (en) * | 1986-07-07 | 1989-12-13 | Shell Int Research | Removing hydrogen sulphide and carbon dioxide from a gas mixture containing hydrogen sulphide and carbon dioxide. |
| NZ223528A (en) * | 1987-02-19 | 1991-08-27 | Dow Chemical Co | Process and scrubbing solution for removal of h 2 s and/or co 2 from gas streams |
| DE3735002A1 (en) * | 1987-10-16 | 1989-04-27 | Metallgesellschaft Ag | PROCESS FOR REMOVING SULFUR HYDROGEN FROM EXHAUST GAS |
| GB8804728D0 (en) * | 1988-02-29 | 1988-03-30 | Shell Int Research | Process for removing h2s from gas stream |
-
1990
- 1990-05-01 DE DE4014018A patent/DE4014018A1/en active Granted
-
1991
- 1991-04-09 EP EP91200822A patent/EP0455285B1/en not_active Expired - Lifetime
- 1991-04-09 DK DK91200822.4T patent/DK0455285T3/en active
- 1991-04-09 AT AT91200822T patent/ATE96339T1/en not_active IP Right Cessation
- 1991-04-09 DE DE91200822T patent/DE59100520D1/en not_active Expired - Fee Related
- 1991-04-09 ES ES91200822T patent/ES2046004T3/en not_active Expired - Lifetime
- 1991-04-24 CA CA002041157A patent/CA2041157A1/en not_active Abandoned
- 1991-04-29 CN CN91102671A patent/CN1031817C/en not_active Expired - Fee Related
- 1991-04-29 AU AU76179/91A patent/AU634881B2/en not_active Ceased
- 1991-04-30 CZ CS911241A patent/CZ283005B6/en not_active IP Right Cessation
- 1991-04-30 PL PL91290092A patent/PL164978B1/en unknown
- 1991-04-30 ZA ZA913277A patent/ZA913277B/en unknown
- 1991-04-30 BR BR919101744A patent/BR9101744A/en not_active Application Discontinuation
- 1991-04-30 SK SK1241-91A patent/SK279282B6/en unknown
- 1991-05-01 JP JP3128710A patent/JPH0584422A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8007569B2 (en) | 2003-07-16 | 2011-08-30 | Uhde Gmbh | Method for removing hydrogen sulphide and other acidic gas components from pressurized technical gases |
| WO2008052325A1 (en) * | 2006-10-31 | 2008-05-08 | John Keum-Ho Hwang | A method and system for recovering sulphur from gas streams |
| CN101985082A (en) * | 2009-07-28 | 2011-03-16 | 林德股份公司 | Method and apparatus for separating mixture of gases in washing device |
| CN114317037A (en) * | 2021-12-31 | 2022-04-12 | 唐山中溶科技有限公司 | Method for preparing hydrogen from coke oven gas by utilizing decarbonization liquid regeneration through decomposition gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CS9101241A2 (en) | 1991-11-12 |
| EP0455285A1 (en) | 1991-11-06 |
| ES2046004T3 (en) | 1994-01-16 |
| DK0455285T3 (en) | 1993-11-22 |
| DE4014018C2 (en) | 1992-04-30 |
| PL290092A1 (en) | 1992-03-09 |
| CZ283005B6 (en) | 1997-12-17 |
| AU634881B2 (en) | 1993-03-04 |
| PL164978B1 (en) | 1994-10-31 |
| CN1031817C (en) | 1996-05-22 |
| DE59100520D1 (en) | 1993-12-02 |
| SK279282B6 (en) | 1998-09-09 |
| JPH0584422A (en) | 1993-04-06 |
| ATE96339T1 (en) | 1993-11-15 |
| EP0455285B1 (en) | 1993-10-27 |
| CN1056064A (en) | 1991-11-13 |
| AU7617991A (en) | 1991-11-07 |
| ZA913277B (en) | 1992-02-26 |
| DE4014018A1 (en) | 1991-11-07 |
| BR9101744A (en) | 1991-12-10 |
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