CA1059765A - Process for purifying gases produced by gasification of solid or liquid fossile fuels, by treatment with water vapor and oxygen under superatmospheric pressure - Google Patents
Process for purifying gases produced by gasification of solid or liquid fossile fuels, by treatment with water vapor and oxygen under superatmospheric pressureInfo
- Publication number
- CA1059765A CA1059765A CA231,109A CA231109A CA1059765A CA 1059765 A CA1059765 A CA 1059765A CA 231109 A CA231109 A CA 231109A CA 1059765 A CA1059765 A CA 1059765A
- Authority
- CA
- Canada
- Prior art keywords
- scrubbing
- solvent
- gas
- water
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
-
- 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
- B01D53/1406—Multiple stage absorption
-
- 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
- B01D53/1456—Removing acid components
-
- 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
- B01D53/1487—Removing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
- C10K1/06—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials combined with spraying with water
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Gas Separation By Absorption (AREA)
- Industrial Gases (AREA)
- Treating Waste Gases (AREA)
- Electromechanical Clocks (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
A process for purifying-raw gases produced by gasifica-tion of solid or liquid fossile fuels, by treatment with water vapor and oxygen under superatmospheric pressure, in order to remove therefrom catalyst-deteriorating impurities, such as mono- or polyunsaturated hydrocarbons, mercaptans, HCN, HCl, H2S, CS2, COS, and NH3, and to desulfurize the gases, while producing an exhaust gas which is rich in H2S, which process comprises indirectly cooling to ambient temperature the raw gas, which is available at a temperature of 150-170°C, separating and removing therefrom the condensible hydrocarbons, subsequently scrubbing the gas with water to remove ammonia in a first scrubbing stage, in which the water rate is controlled to be just sufficient to remove the ammonia, then scrubbing the gas with a high-boiling organic solvent, which is miscible with water, adding sulfur to that solvent and using it in a second scrubbing stage, in which the solvent rate is controlled in dependence on the solubility of the methylmercaptan, which is to be removed, in the solvent, subsequently adding to the same solvent a soluble activator having a boiling point which is approximatively as high as or higher than that of the boiling organic solvent, adjusting the activator content and using the so adjusted solvent in a third scrubbing stage, in which the water content of the solvent is kept at 5-30 mole percent H2O and in which H2S and COS are entirely and selectively removed from the gas, the scrubbing solvents from the second and third scrubbing stages being separately regenerated and recycled to the second and third scrubbing stages for re-use. The resulting pure gas may be directly used for various chemical syntheses, such as ammonia, methane, methanol, oxosyntheses or Fisher Tropsch syntheses.
A process for purifying-raw gases produced by gasifica-tion of solid or liquid fossile fuels, by treatment with water vapor and oxygen under superatmospheric pressure, in order to remove therefrom catalyst-deteriorating impurities, such as mono- or polyunsaturated hydrocarbons, mercaptans, HCN, HCl, H2S, CS2, COS, and NH3, and to desulfurize the gases, while producing an exhaust gas which is rich in H2S, which process comprises indirectly cooling to ambient temperature the raw gas, which is available at a temperature of 150-170°C, separating and removing therefrom the condensible hydrocarbons, subsequently scrubbing the gas with water to remove ammonia in a first scrubbing stage, in which the water rate is controlled to be just sufficient to remove the ammonia, then scrubbing the gas with a high-boiling organic solvent, which is miscible with water, adding sulfur to that solvent and using it in a second scrubbing stage, in which the solvent rate is controlled in dependence on the solubility of the methylmercaptan, which is to be removed, in the solvent, subsequently adding to the same solvent a soluble activator having a boiling point which is approximatively as high as or higher than that of the boiling organic solvent, adjusting the activator content and using the so adjusted solvent in a third scrubbing stage, in which the water content of the solvent is kept at 5-30 mole percent H2O and in which H2S and COS are entirely and selectively removed from the gas, the scrubbing solvents from the second and third scrubbing stages being separately regenerated and recycled to the second and third scrubbing stages for re-use. The resulting pure gas may be directly used for various chemical syntheses, such as ammonia, methane, methanol, oxosyntheses or Fisher Tropsch syntheses.
Description
~Os9765 Thi~ invention relates to a process for purifying ga~e~
produced by ga~ification of ~olid or liquid fossile ~uel~, by treatment with water ~apor and oxygen under superatmospheric pres-sure, which proces~ serves to remove catalyst-deteriorating im-purities, ~uch as mono- or polyunsaturated hydrocarbons, mercaptans, HCN, ~Cl, H2S, CS2, COS~ and N~39 and to de~ul~urize the gase~,while producing an exhau~t gas ~hich is rich in ~2s. ~his proces~
es~entially comprises cooling ~nd ~crubbing the gas under ~uper-atmospheric pressure at normal temperature.
It i~ known that hydrogen u~ed for the ~ynthe3is of am-monia or for catalytic hydrogenation, and hydrogen-carbon oxide ml~ture~ used for catalytic syntheses of hydrocarbons (methane synthe~is, Fischer-~ropsch ~ynthesis, methanol synthesis or oxo-synthesis) can be produced by gasification of variou~ fo~sile fuels by treatment wi-th water vapor accompanied by a direct supply of heat (by a partial combustion with oxygen or air) or by an indirect . ~upply of heat from the out~ide In all case , the resulting raw gase~ must b~ puri~ied to remo~e catalyst-deteriorating constituents, particul~rly sulfur compounds. In mo~t cases, this is accomplish~d by scrubblng processe~, by which the gases, which are u~ually pro-duced and kep~ under superatmo~pheric pres~ure, are scrubbed under ~uperatmospheric pre~ure with aqueous or organic scrubbing agents to remove the impurities.
In gases produced ~rom natural gas or petroleum or ~rac-tions thereof, the cataly~t-deteriorating impurities to be removed cons~t mainly of H2S9 certain proportion~ of COS, and ~mall amounts Of HC~.
The puri~ication of these gases is simpler than that of coal gase~, which in addition to the above-mentioned constituents contain other impurities~ such as NH3, CS2, mercaptans, and mono-and polyunsaturated hydrocarbons having 2 to 8 10 carbon atoms, ~5976S
i.e., acetylenes, olefin~ and diolefi-ns9 which tend to polymerize therm~lly or catalytically to form resin~ ~hich depo~it at various point~ and re~ult in clogging.
~or the rea~ons stated abo~e, the puri~ication of coal ga~es ha~ always been very expensi~e, Thi~ has been the ca~e even with coke oven gase~, even if they were used only a9 fuel gase~.
The purifi~ation has alw~y~ included several stages ~or the separate remo~al of naphthalenes, benzene hydrocarbons~ hydrogen sulfide, ammonia, and nitric oxideO Since the advent of the u~e of coal gase~, e.g., tho~e produced by a pre~sure gasification of coal, for catalyti~ ~ynthesi~, further ~tages have be~n added to the abcve-mentioned puri~ying proce3~e3. High concentrations of C02 had to be removed9 and the gase~ havs been ~orubbed with water under super-atmospheri¢ pressure ~or this purpo~e, and purification processes are required to remove all organic Elulfur compounds. Alkalinized iron 02ide compo~itions have been u~led for the latter purpose at temperatures of about 180-240C.
A new scrubbing proces~ h2s been introduced (German Patent Specification 843,5459 Germa~ Pate~t Speci~ication 935,144;
German Patent Specification 936,714), which is based on phy~ical ab~orption and in which only methanol is u~ed a~ a scrubbing agent to remove all impurities from coal gasea and to provide a gas which is sufficiently pure for catalytic ~ynthe~e~. ~hi~ proce~s re-present~ a great technological progres~ specifically in the puri-fication o~ c081 gases. ~ethanol used as a ~crubbing agent for thi~ purpo~e can easily be thermally regenerated ~thout any chem-ical change so that it can be continually re-used. The only di~-advantage of methanol i9 its relatively high vapor pre~sure. ~o re-duce the latter and al90 to increase the 30lubility o~ the gase~ to be ~crubbed, the proce~ carried out at lo~ temperature, although this requires a refrigerating pIant and a corresponding consumption of refrigerating energg.
~2--~)S97~;5 Whereas, it succeeds in removing all catalys-t-dete-riorating components and the acid gases H2S and CO2, the process in spite of the high expenditure lnvolved, enables a selective desulfurization only to such an extent that the scrubbed gases are only slightly enriched with hydrogen sulfide and for this reason the latter cannot be processed in some cases by the Claus process to produce elementary sulfur unless an additional treatment to increase the concentration of H2S is adopted.
So far, no process has succeeded in satisfactory purifying coal distillation gases by means of a single scrubbing agent so as to remove catalyst-deteriorating substances and to effect a selective desulfurization at the same time.
The subject invèntion æroposes to eliminate these and other disadvantages of the prior art and to provide a process for purifying gases that have been produced by gasification of solid and/or liquid fuels, by treatment with water vapor and oxygen un-der pressure, which purification results in a removal of catalyst-deteriorating impurities together with a desulfurization, whe-reas the need for an expensive refrigerating process required in the previously disclosed processes is eliminated. The pure gas resulting from this process should be directly usable as a synthesis gas for various chemical syntheses, such as the production of ammonia, methane, methanol, or for the Fischer-Tropsch synthesis.
This is accomplished, according to the invention, by indirectly cooling to ambient temperature the raw gas, which is available at a temperature of 150-170 C, separating and remov-ing -therefrom the condensible hydrocarbons; subsequently - scrubbing the gas with water to remove ammonia in a first scrubbing stage, in which the water rate is controlled to be just sufficient to remove the ammonia, then scrubbing the gas with a high-boiling organic solvent, which is miscible with water; adding sulfur to that solvent, in the amount of 0.1 to ,, j ~q:35~765 10 g per liter of scrubbing liquid and using the so sulEerized solvent in a second scrubbing stage, in which the solvent rate is controlled in dependence on the solubility of the methyl-mercaptan, which is to be removed, in the solvent; subsequently adding to the same solvent a soluble activator having a boiling point that is approximatively as high as or higher than that of the boiling organic solvent, adjusting the solvent -to an activator content of 1-20% by weight and using the so adjusted solvent in a third scrubbing stage, in which the water content of the solvent is kept at 5-30 molé percent H20 and H2S
and COS are entirely and selectively removed from the gas, the scrubbing solvents from the second and third scrubbing stages being separatively regenerated and recycled to the second and third scrubbing stages for re-use.
The cooling of the raw gas to ambient temperature has the rPsult that the condensible hydrocarbons as well as the water vapor are separated until the saturation pressure has been reached. The obtained mixture is removed and can be separately separated if desired.
The gas is subsequently scrubbed in a first scrubbing stage with water at such a rate that any NH3 is entirely removed.
This can-be accomplished with water at a low rate because the high C02 content of the gas causes all NH3 to be combined to (NH4 ) 2C03 or (NH4) HC03 whereby the solubility in water is increased.
That has the result that in the second scrubbing treat-ment, which succeeds the first scrubbing treatment and in which the gas is scrubbed with a high-boiling organic solvent, the dissolved components of the gas, such as HCN, H2S, CO2, can no longer participate in a formation of salts and for this reason can be removed Erom the scrubbing agent by strictly physical treatments, such as hea-ting, stripping or flashing.
According to the invention, the second scrubbing ~ - 4 -~0~;97Çi5 treatment o the gas, from which NH3 has been removed, with a high-boiling organic solvent is accomplished in two separate scrubbing stages in which the gas is conducted in a counter-current with a scrubbing - 4a -~ 0S97165 agent under the operating pres~ure o~ the gas_producing mean~, the scrubbing agent being recycled through ~bsorption and regeneration atages~ The ~crubbing agent i9 circulated through the ~econd ~crubbing stage at such a rate that methylmercaptan i~ remo~ed, ~hich ha~ the lowest boiling point o~ all organic ~ul~ur compound~
contained in the gas. The solvent u~ed in the second ~crubbing ~tage may contain a c~rtain amount o~ water. A minimum content of water i9 e~sential in the organic solvent used i~ the third scrub-bing ~tage. According to the invention, the water content of the 10 organic solvent i~ kept at 5-30 mole percent ~o that the COS which i8 contained in the gas after the second ~crubbing ~age in addi-tion to H2S i~ hydrolytioally dissociated to ~orm C02 a~d H2S and the resulting hydrogen ~ulfide i~ entirely removed together with the maln amount of hydrogen ~ul~ide~
/~ According to an additional feature of the inve~tiont ~ul-~ur i8 added to the scrubbing agent in the second ~crubbing ~tage in an amou~t o~ 0.1 to 10 g, pre~erably 3 to 8 g, per liter o~
s~rubbing liquid, The ~ul~ur used i~ the ~econd ~tage may be f~rmed by re~
acting hydrogen ~ul~ide contained i~ the ga~.leaving the first scrubbing stage in a known manner accordi~g to the equation
produced by ga~ification of ~olid or liquid fossile ~uel~, by treatment with water ~apor and oxygen under superatmospheric pres-sure, which proces~ serves to remove catalyst-deteriorating im-purities, ~uch as mono- or polyunsaturated hydrocarbons, mercaptans, HCN, ~Cl, H2S, CS2, COS~ and N~39 and to de~ul~urize the gase~,while producing an exhau~t gas ~hich is rich in ~2s. ~his proces~
es~entially comprises cooling ~nd ~crubbing the gas under ~uper-atmospheric pressure at normal temperature.
It i~ known that hydrogen u~ed for the ~ynthe3is of am-monia or for catalytic hydrogenation, and hydrogen-carbon oxide ml~ture~ used for catalytic syntheses of hydrocarbons (methane synthe~is, Fischer-~ropsch ~ynthesis, methanol synthesis or oxo-synthesis) can be produced by gasification of variou~ fo~sile fuels by treatment wi-th water vapor accompanied by a direct supply of heat (by a partial combustion with oxygen or air) or by an indirect . ~upply of heat from the out~ide In all case , the resulting raw gase~ must b~ puri~ied to remo~e catalyst-deteriorating constituents, particul~rly sulfur compounds. In mo~t cases, this is accomplish~d by scrubblng processe~, by which the gases, which are u~ually pro-duced and kep~ under superatmo~pheric pres~ure, are scrubbed under ~uperatmospheric pre~ure with aqueous or organic scrubbing agents to remove the impurities.
In gases produced ~rom natural gas or petroleum or ~rac-tions thereof, the cataly~t-deteriorating impurities to be removed cons~t mainly of H2S9 certain proportion~ of COS, and ~mall amounts Of HC~.
The puri~ication of these gases is simpler than that of coal gase~, which in addition to the above-mentioned constituents contain other impurities~ such as NH3, CS2, mercaptans, and mono-and polyunsaturated hydrocarbons having 2 to 8 10 carbon atoms, ~5976S
i.e., acetylenes, olefin~ and diolefi-ns9 which tend to polymerize therm~lly or catalytically to form resin~ ~hich depo~it at various point~ and re~ult in clogging.
~or the rea~ons stated abo~e, the puri~ication of coal ga~es ha~ always been very expensi~e, Thi~ has been the ca~e even with coke oven gase~, even if they were used only a9 fuel gase~.
The purifi~ation has alw~y~ included several stages ~or the separate remo~al of naphthalenes, benzene hydrocarbons~ hydrogen sulfide, ammonia, and nitric oxideO Since the advent of the u~e of coal gase~, e.g., tho~e produced by a pre~sure gasification of coal, for catalyti~ ~ynthesi~, further ~tages have be~n added to the abcve-mentioned puri~ying proce3~e3. High concentrations of C02 had to be removed9 and the gase~ havs been ~orubbed with water under super-atmospheri¢ pressure ~or this purpo~e, and purification processes are required to remove all organic Elulfur compounds. Alkalinized iron 02ide compo~itions have been u~led for the latter purpose at temperatures of about 180-240C.
A new scrubbing proces~ h2s been introduced (German Patent Specification 843,5459 Germa~ Pate~t Speci~ication 935,144;
German Patent Specification 936,714), which is based on phy~ical ab~orption and in which only methanol is u~ed a~ a scrubbing agent to remove all impurities from coal gasea and to provide a gas which is sufficiently pure for catalytic ~ynthe~e~. ~hi~ proce~s re-present~ a great technological progres~ specifically in the puri-fication o~ c081 gases. ~ethanol used as a ~crubbing agent for thi~ purpo~e can easily be thermally regenerated ~thout any chem-ical change so that it can be continually re-used. The only di~-advantage of methanol i9 its relatively high vapor pre~sure. ~o re-duce the latter and al90 to increase the 30lubility o~ the gase~ to be ~crubbed, the proce~ carried out at lo~ temperature, although this requires a refrigerating pIant and a corresponding consumption of refrigerating energg.
~2--~)S97~;5 Whereas, it succeeds in removing all catalys-t-dete-riorating components and the acid gases H2S and CO2, the process in spite of the high expenditure lnvolved, enables a selective desulfurization only to such an extent that the scrubbed gases are only slightly enriched with hydrogen sulfide and for this reason the latter cannot be processed in some cases by the Claus process to produce elementary sulfur unless an additional treatment to increase the concentration of H2S is adopted.
So far, no process has succeeded in satisfactory purifying coal distillation gases by means of a single scrubbing agent so as to remove catalyst-deteriorating substances and to effect a selective desulfurization at the same time.
The subject invèntion æroposes to eliminate these and other disadvantages of the prior art and to provide a process for purifying gases that have been produced by gasification of solid and/or liquid fuels, by treatment with water vapor and oxygen un-der pressure, which purification results in a removal of catalyst-deteriorating impurities together with a desulfurization, whe-reas the need for an expensive refrigerating process required in the previously disclosed processes is eliminated. The pure gas resulting from this process should be directly usable as a synthesis gas for various chemical syntheses, such as the production of ammonia, methane, methanol, or for the Fischer-Tropsch synthesis.
This is accomplished, according to the invention, by indirectly cooling to ambient temperature the raw gas, which is available at a temperature of 150-170 C, separating and remov-ing -therefrom the condensible hydrocarbons; subsequently - scrubbing the gas with water to remove ammonia in a first scrubbing stage, in which the water rate is controlled to be just sufficient to remove the ammonia, then scrubbing the gas with a high-boiling organic solvent, which is miscible with water; adding sulfur to that solvent, in the amount of 0.1 to ,, j ~q:35~765 10 g per liter of scrubbing liquid and using the so sulEerized solvent in a second scrubbing stage, in which the solvent rate is controlled in dependence on the solubility of the methyl-mercaptan, which is to be removed, in the solvent; subsequently adding to the same solvent a soluble activator having a boiling point that is approximatively as high as or higher than that of the boiling organic solvent, adjusting the solvent -to an activator content of 1-20% by weight and using the so adjusted solvent in a third scrubbing stage, in which the water content of the solvent is kept at 5-30 molé percent H20 and H2S
and COS are entirely and selectively removed from the gas, the scrubbing solvents from the second and third scrubbing stages being separatively regenerated and recycled to the second and third scrubbing stages for re-use.
The cooling of the raw gas to ambient temperature has the rPsult that the condensible hydrocarbons as well as the water vapor are separated until the saturation pressure has been reached. The obtained mixture is removed and can be separately separated if desired.
The gas is subsequently scrubbed in a first scrubbing stage with water at such a rate that any NH3 is entirely removed.
This can-be accomplished with water at a low rate because the high C02 content of the gas causes all NH3 to be combined to (NH4 ) 2C03 or (NH4) HC03 whereby the solubility in water is increased.
That has the result that in the second scrubbing treat-ment, which succeeds the first scrubbing treatment and in which the gas is scrubbed with a high-boiling organic solvent, the dissolved components of the gas, such as HCN, H2S, CO2, can no longer participate in a formation of salts and for this reason can be removed Erom the scrubbing agent by strictly physical treatments, such as hea-ting, stripping or flashing.
According to the invention, the second scrubbing ~ - 4 -~0~;97Çi5 treatment o the gas, from which NH3 has been removed, with a high-boiling organic solvent is accomplished in two separate scrubbing stages in which the gas is conducted in a counter-current with a scrubbing - 4a -~ 0S97165 agent under the operating pres~ure o~ the gas_producing mean~, the scrubbing agent being recycled through ~bsorption and regeneration atages~ The ~crubbing agent i9 circulated through the ~econd ~crubbing stage at such a rate that methylmercaptan i~ remo~ed, ~hich ha~ the lowest boiling point o~ all organic ~ul~ur compound~
contained in the gas. The solvent u~ed in the second ~crubbing ~tage may contain a c~rtain amount o~ water. A minimum content of water i9 e~sential in the organic solvent used i~ the third scrub-bing ~tage. According to the invention, the water content of the 10 organic solvent i~ kept at 5-30 mole percent ~o that the COS which i8 contained in the gas after the second ~crubbing ~age in addi-tion to H2S i~ hydrolytioally dissociated to ~orm C02 a~d H2S and the resulting hydrogen ~ulfide i~ entirely removed together with the maln amount of hydrogen ~ul~ide~
/~ According to an additional feature of the inve~tiont ~ul-~ur i8 added to the scrubbing agent in the second ~crubbing ~tage in an amou~t o~ 0.1 to 10 g, pre~erably 3 to 8 g, per liter o~
s~rubbing liquid, The ~ul~ur used i~ the ~econd ~tage may be f~rmed by re~
acting hydrogen ~ul~ide contained i~ the ga~.leaving the first scrubbing stage in a known manner accordi~g to the equation
2 H2S ~ 2-~ 2S + 2 X20 ~Claus process) with the oxyge~ contained in said gas, ~his ha~
the adYantage that the oxygsn i8 removed from the gas at the same~
time. ~his addition of sulfur to the organic sol~t used in the .. ~econd ~crubbing ~tage promote~ the removal of the ~eth~lmercaptan becau~e the la~ter i~ converted into dimethyl di~ul~ide according to 4 CH3SH ~ S2 - 2Ca3 SS CH3 ~ 2H~S~
According to ~ ~urther ~eature of the invention, a ~ol-s9765 uble activator is added to the scrubbing agent used in -the third scrubbingstage. This activator consists preferably of a compound which has a boiling point that is approximately as high as or higher than the boiling point of the high-boiling organic solvent.
Such compounds are, e.g., nitrogen-containing organic compounds, such as imidazole and its derivatives. Within the scope of the invention the activator consis-ts preferably of 1,2-dimethylimidazole.
The solvent is suitable adjusted to an activator content of 1-20% by weight, preEerably 5-15~ by weight.
When the scrubbing solvent used in the second scrubbing stage has been laden with the saturated and unsaturated hydro-carbons, with mercaptans and with hydrocyanic acid, it is rege-nerated in a regenerator to remove the subs-tances which have been taken up and is then recycled to the absorber for re-use. The regeneration may be accomplished in a known manner by flashing the scrubbing agent to atmospheric pressure and stripping off the substances taken up with water vapor or inert gas or ther-mally by indirect heating. The scrubbing solvent laden with H2S and COS which has le-Et the third scrubbing stage is regene-rated for re-use and for this purpose is fractionally flashed to atmospheric pressure and is then regenerated in a regenerator in which it is stripped with inert gas and/or subjected to a vacuum or a thermal treatment and is then cooled and fed back to the absorber so that the scrubbing agent is circulated through the absorber and regenerator.
Pyrrolidone or a derivative of pyrrolidone, prefera-bly N-methylpyrrolidone, can be used as a high-boiling organic solvent within the scope of the invention.
Polyglycolether can also be used with good success.
Sulfolan, butyrolactone, morpholine and/or N-methyl-~-caprolactam can further be used as organic solvents.
- 1~597~5 ~ he advantages afforded by the invention reside mainly in that a simple and economical process hac bee~ provided for the purification of the gases ~hich have been produced by a gasifica-~on of solid fos~ile fuels, such as coal, by a treatment with ~ater vapor and oxygen under superatmospher~c pressure. According to the invention, this purification to remove particularly catslyst-deteriorating compounds i~ accompanied b~ a simultaneous selective de~ulfurization. ~he scrubbing in three stages once wlth water and twice with a high-boiling, water-soluble organic solvent results in a removal of the impurities in three parts..~
The gas i~ ~irst scrubbed with water ~o remove ammonia.
In the second scrubbing stage, an organic ~ol~ent is used to re-move 811 cataly~t poi90n~ except for H2S and COS ~he~e two con-stituents are finally removed in a third stage. ~he use o~ a ~ater-containing org~nic sol~ent in the third stage results in a hydrolysi~ of COS
~ ecau~e the H2S i~ removecl and the COS i5 hydrolyæed at the ~ame time, le~s scrubbing agent is needed than ~ould be required ~or a complete phy3ical 3crubbing of the COS, Which ha~ a low 30-lubility in the solvent3 in question~ particularly in N-methylpyr~
rolidone and polygl~colether bu-t al~o in sulfolan and others.
The re~ulting pure g~s may be directly used ~or variou~
chemical ~ynthe~es. The pure gas may be u~ed, e.g.~ to produce ammonia, methane, methanol, oxosynthe~es or Fischer-Tropsch synthese~
As a result of the reduced solvent requirement, the ~trip-ping step used to regenerate the scrubbin~ sgent laden in the third stage re~ult~ in an e~haust ga~ which i~ highly enriched wlth hydro-gen ~ulfide.
~ or this rea~on, this gas c~n be proce~ed by the alaus proce3s to con~ert the hydrogen ~ulfide to element~ry ~ulfur.
The invention will be now better under~tood with reference to the following e~ample a~d the accompanying drawing ~herein fig,1 ~ -7-.~
lOS9765 ~chematically represents a flo~ diagram of the proces~ accord~ng to the i~vention.
Example In accordance with Fig. l, a gas produced by a presqure ga~ification of hard coal with water vapor and oxygen i8 fir~t dixectly cooled to 170C by being sprinkled with ~ater a~d i~ then i~dlrectly cooled further to ambient temperature and separated ~ro~
the condensate. ~he re~ulting gas had the following compo~ition 28.2% by volume C02 0~65 " Cn~m 0.1 " 0~
20 . 8 n C0 39 . 2 1~ ~2 9 . 7 1l ~H4 ~ ~, O 1~ ~2 O. 35 1l ~r2s organic sulfkr compound3 (COS, CS2, RSH, ~ _ SH
a~d others: 256 mg/standard m3 10 mg/standard m3 HCN
~7 mg/standard m3 ~H3 ~he unsatura~d hydrocarbons C~m amounting to 0.65% by ~olume included 8,9 ~/standard m3 h~drocarbons boiling in the range of 40-1 25C, q!he ga~ i8 under a pressure of 25 kg/cm2. 100.000 s~an-dard m3 /h of the gas are fed through conduit 0 lnto the qcrubbing tower 1 and for a removal of ammonia are scrubbed in the tower 1 w.ith 5 m3 /h water, ~hich are conducted in a countercurrent and fed bg mean~ of pump 2 through conduit 3.
~ he ~urther purification 19 accompli~hed i~ two additio-n_ -1~59765 al ~crubbing stages 4 and 6 with N-methylpyrrolidone as ~crubbing agent. The circulating scrubbing age-nt (34 m3 /h) from scrubbing stage 4 contain~ 6 g/l elementary ~ulfur. The ga~ leaving this . ~scrubbing stage is en~irely free of HCN, all organic sulfur com-pounds, mainly mercapta~s, CS2, and mono- and polyun~aturated : hydrocarbon~ having a higher bolling point than methylmercaptan.
0~ all catalyst poisons~ it contains only H2S and residual COS.
: Of the organic ~ulfur compounds originally contained in the gas in a total amount of 256 mg/standard m3, only 48 mg/~tan-dard m3 are left~ ~he mercaptans, inclu~ive of methylmercaptan, which has the lowe~t boillng point, have largel~ been scxubbed of~
as ~uch and ha~e partl~ been reacted to form higher-boiling di-sulfides, which hav~ been scrubbed off. The organic sul~ur com-pound residue consists only of COS, ~he thus pretreated ga~ fe~ through conduit 5 into ~c~ubbing stage 6~ in which it i3 scrub~ with 270 m3 /h N-methyl~
pgrrolidone which flows in a countercurr~t and which contains 10 mole percent H20 and 8% by weight 1,2-di~thylimidazole a~ an acti-~ator. COS i~ hydrolyzed to form H2S an~ C02 b~ the coaction of water and acti~ator. ~he pure g~s which lea~es the ~crubber in con-duit 7 containa le~ than 0.2 pp-~ S and ~ free of a~y other oatalyst poison.
The ~crubbing agent laden in ao~ubbing ~tage 4 is pre-flashed in that it is fed through pre~u~ relie~ val~e 8 and con-duit 9 into the fla~hing ve~el 109 from ~hich the scrubbing age:nl;
~lows through conduit 11 into the regenewti-ng tower 12. ~he flashed -o~ ga~ is ~uc~ed ~rom vessel 10 through conduit 13 by a compre~or 14, which compresse~ the gas to the operar~ g pre~sure. ~he gas i8 then fed through conduit 15 a:nd admixe~ to the raw gas, The ~crubbi~g agent i9 regenera~ed in the regenerator 12 and for thi~ purpose i3 heated to its bo~ing point under sub-16~S976S
atmospheric pressure to remove the hydrocarbons, mercaptans and the like which have been taken up. By the circulating pump 18, the regenerated scrubbing agent is ~ed through conduit 16 and coo-ler 17 to the top of the scrubbing tower 4 for re-use. The impuri-ties and water which have been removed are fed through conduit 31 to the condenser 30. Part of the condensate is fed through conduit 32 as reflux to the regenerator. At the rate at which condensibles are supplied in the raw gas, the condensate is fed through conduit 33 to a separating system.
The scrubbing agent from scrubbing stage 6 is preflashed by being fed through the pressure relief valve l9 and conduit 20 into the flashing vessel 21, and is then fed through conduit 22 in-to the regenerating tower 23, in which it is degasified by a su~ply of heat (heater 24), under the action of a vacuum, or by means of a stripping gas (fed through conduit 25). The exhaust gas which is rich in H2S is fed through conduit 26 to a Claus process plant for further processing and may previously be re-scrubbed with water to remoVe solvent vapor. The stripped gas has the following composi-tion;
12,0% by volume H2S
87.4 " C2 0~2 " H2 0.2 " CO
0.2 " CH4 The degasified scrubbing agent is fed by the circulating pump 28 through the aftercooler 27 and conduit 29 back to the top of the scrubbing tower 6 and is re-used.
The gas which has been flashed off in the preflashing vessel 21 is sucked through conduit 35 by the compressor 34, which compresses the gas to operating pressure. The compresses gas is admixed to the gas flowing in conduit 5.
B
~ 59765 The pure ga~ lea~ing the third ~crubbing stage has the ~ollowing composition:
0.2 ppm H~S
27.4% by volume C02 40, 3 ~ ~
21.3 " C0 10 ~ 0 CH4 1 ~0 N2 ~he gas ha~ing this ~ompo~ition may be used a~ such, or 10 after a modiiEication oî the CO/H2 ratio in a succeedi:ng ~hift con-~rersion ~tage, for various catalytic syntheses~ e.g., for the syn-tl~1~ of` ammonia or for the ~thesi~ o:t`~methane.
.
; .
the adYantage that the oxygsn i8 removed from the gas at the same~
time. ~his addition of sulfur to the organic sol~t used in the .. ~econd ~crubbing ~tage promote~ the removal of the ~eth~lmercaptan becau~e the la~ter i~ converted into dimethyl di~ul~ide according to 4 CH3SH ~ S2 - 2Ca3 SS CH3 ~ 2H~S~
According to ~ ~urther ~eature of the invention, a ~ol-s9765 uble activator is added to the scrubbing agent used in -the third scrubbingstage. This activator consists preferably of a compound which has a boiling point that is approximately as high as or higher than the boiling point of the high-boiling organic solvent.
Such compounds are, e.g., nitrogen-containing organic compounds, such as imidazole and its derivatives. Within the scope of the invention the activator consis-ts preferably of 1,2-dimethylimidazole.
The solvent is suitable adjusted to an activator content of 1-20% by weight, preEerably 5-15~ by weight.
When the scrubbing solvent used in the second scrubbing stage has been laden with the saturated and unsaturated hydro-carbons, with mercaptans and with hydrocyanic acid, it is rege-nerated in a regenerator to remove the subs-tances which have been taken up and is then recycled to the absorber for re-use. The regeneration may be accomplished in a known manner by flashing the scrubbing agent to atmospheric pressure and stripping off the substances taken up with water vapor or inert gas or ther-mally by indirect heating. The scrubbing solvent laden with H2S and COS which has le-Et the third scrubbing stage is regene-rated for re-use and for this purpose is fractionally flashed to atmospheric pressure and is then regenerated in a regenerator in which it is stripped with inert gas and/or subjected to a vacuum or a thermal treatment and is then cooled and fed back to the absorber so that the scrubbing agent is circulated through the absorber and regenerator.
Pyrrolidone or a derivative of pyrrolidone, prefera-bly N-methylpyrrolidone, can be used as a high-boiling organic solvent within the scope of the invention.
Polyglycolether can also be used with good success.
Sulfolan, butyrolactone, morpholine and/or N-methyl-~-caprolactam can further be used as organic solvents.
- 1~597~5 ~ he advantages afforded by the invention reside mainly in that a simple and economical process hac bee~ provided for the purification of the gases ~hich have been produced by a gasifica-~on of solid fos~ile fuels, such as coal, by a treatment with ~ater vapor and oxygen under superatmospher~c pressure. According to the invention, this purification to remove particularly catslyst-deteriorating compounds i~ accompanied b~ a simultaneous selective de~ulfurization. ~he scrubbing in three stages once wlth water and twice with a high-boiling, water-soluble organic solvent results in a removal of the impurities in three parts..~
The gas i~ ~irst scrubbed with water ~o remove ammonia.
In the second scrubbing stage, an organic ~ol~ent is used to re-move 811 cataly~t poi90n~ except for H2S and COS ~he~e two con-stituents are finally removed in a third stage. ~he use o~ a ~ater-containing org~nic sol~ent in the third stage results in a hydrolysi~ of COS
~ ecau~e the H2S i~ removecl and the COS i5 hydrolyæed at the ~ame time, le~s scrubbing agent is needed than ~ould be required ~or a complete phy3ical 3crubbing of the COS, Which ha~ a low 30-lubility in the solvent3 in question~ particularly in N-methylpyr~
rolidone and polygl~colether bu-t al~o in sulfolan and others.
The re~ulting pure g~s may be directly used ~or variou~
chemical ~ynthe~es. The pure gas may be u~ed, e.g.~ to produce ammonia, methane, methanol, oxosynthe~es or Fischer-Tropsch synthese~
As a result of the reduced solvent requirement, the ~trip-ping step used to regenerate the scrubbin~ sgent laden in the third stage re~ult~ in an e~haust ga~ which i~ highly enriched wlth hydro-gen ~ulfide.
~ or this rea~on, this gas c~n be proce~ed by the alaus proce3s to con~ert the hydrogen ~ulfide to element~ry ~ulfur.
The invention will be now better under~tood with reference to the following e~ample a~d the accompanying drawing ~herein fig,1 ~ -7-.~
lOS9765 ~chematically represents a flo~ diagram of the proces~ accord~ng to the i~vention.
Example In accordance with Fig. l, a gas produced by a presqure ga~ification of hard coal with water vapor and oxygen i8 fir~t dixectly cooled to 170C by being sprinkled with ~ater a~d i~ then i~dlrectly cooled further to ambient temperature and separated ~ro~
the condensate. ~he re~ulting gas had the following compo~ition 28.2% by volume C02 0~65 " Cn~m 0.1 " 0~
20 . 8 n C0 39 . 2 1~ ~2 9 . 7 1l ~H4 ~ ~, O 1~ ~2 O. 35 1l ~r2s organic sulfkr compound3 (COS, CS2, RSH, ~ _ SH
a~d others: 256 mg/standard m3 10 mg/standard m3 HCN
~7 mg/standard m3 ~H3 ~he unsatura~d hydrocarbons C~m amounting to 0.65% by ~olume included 8,9 ~/standard m3 h~drocarbons boiling in the range of 40-1 25C, q!he ga~ i8 under a pressure of 25 kg/cm2. 100.000 s~an-dard m3 /h of the gas are fed through conduit 0 lnto the qcrubbing tower 1 and for a removal of ammonia are scrubbed in the tower 1 w.ith 5 m3 /h water, ~hich are conducted in a countercurrent and fed bg mean~ of pump 2 through conduit 3.
~ he ~urther purification 19 accompli~hed i~ two additio-n_ -1~59765 al ~crubbing stages 4 and 6 with N-methylpyrrolidone as ~crubbing agent. The circulating scrubbing age-nt (34 m3 /h) from scrubbing stage 4 contain~ 6 g/l elementary ~ulfur. The ga~ leaving this . ~scrubbing stage is en~irely free of HCN, all organic sulfur com-pounds, mainly mercapta~s, CS2, and mono- and polyun~aturated : hydrocarbon~ having a higher bolling point than methylmercaptan.
0~ all catalyst poisons~ it contains only H2S and residual COS.
: Of the organic ~ulfur compounds originally contained in the gas in a total amount of 256 mg/standard m3, only 48 mg/~tan-dard m3 are left~ ~he mercaptans, inclu~ive of methylmercaptan, which has the lowe~t boillng point, have largel~ been scxubbed of~
as ~uch and ha~e partl~ been reacted to form higher-boiling di-sulfides, which hav~ been scrubbed off. The organic sul~ur com-pound residue consists only of COS, ~he thus pretreated ga~ fe~ through conduit 5 into ~c~ubbing stage 6~ in which it i3 scrub~ with 270 m3 /h N-methyl~
pgrrolidone which flows in a countercurr~t and which contains 10 mole percent H20 and 8% by weight 1,2-di~thylimidazole a~ an acti-~ator. COS i~ hydrolyzed to form H2S an~ C02 b~ the coaction of water and acti~ator. ~he pure g~s which lea~es the ~crubber in con-duit 7 containa le~ than 0.2 pp-~ S and ~ free of a~y other oatalyst poison.
The ~crubbing agent laden in ao~ubbing ~tage 4 is pre-flashed in that it is fed through pre~u~ relie~ val~e 8 and con-duit 9 into the fla~hing ve~el 109 from ~hich the scrubbing age:nl;
~lows through conduit 11 into the regenewti-ng tower 12. ~he flashed -o~ ga~ is ~uc~ed ~rom vessel 10 through conduit 13 by a compre~or 14, which compresse~ the gas to the operar~ g pre~sure. ~he gas i8 then fed through conduit 15 a:nd admixe~ to the raw gas, The ~crubbi~g agent i9 regenera~ed in the regenerator 12 and for thi~ purpose i3 heated to its bo~ing point under sub-16~S976S
atmospheric pressure to remove the hydrocarbons, mercaptans and the like which have been taken up. By the circulating pump 18, the regenerated scrubbing agent is ~ed through conduit 16 and coo-ler 17 to the top of the scrubbing tower 4 for re-use. The impuri-ties and water which have been removed are fed through conduit 31 to the condenser 30. Part of the condensate is fed through conduit 32 as reflux to the regenerator. At the rate at which condensibles are supplied in the raw gas, the condensate is fed through conduit 33 to a separating system.
The scrubbing agent from scrubbing stage 6 is preflashed by being fed through the pressure relief valve l9 and conduit 20 into the flashing vessel 21, and is then fed through conduit 22 in-to the regenerating tower 23, in which it is degasified by a su~ply of heat (heater 24), under the action of a vacuum, or by means of a stripping gas (fed through conduit 25). The exhaust gas which is rich in H2S is fed through conduit 26 to a Claus process plant for further processing and may previously be re-scrubbed with water to remoVe solvent vapor. The stripped gas has the following composi-tion;
12,0% by volume H2S
87.4 " C2 0~2 " H2 0.2 " CO
0.2 " CH4 The degasified scrubbing agent is fed by the circulating pump 28 through the aftercooler 27 and conduit 29 back to the top of the scrubbing tower 6 and is re-used.
The gas which has been flashed off in the preflashing vessel 21 is sucked through conduit 35 by the compressor 34, which compresses the gas to operating pressure. The compresses gas is admixed to the gas flowing in conduit 5.
B
~ 59765 The pure ga~ lea~ing the third ~crubbing stage has the ~ollowing composition:
0.2 ppm H~S
27.4% by volume C02 40, 3 ~ ~
21.3 " C0 10 ~ 0 CH4 1 ~0 N2 ~he gas ha~ing this ~ompo~ition may be used a~ such, or 10 after a modiiEication oî the CO/H2 ratio in a succeedi:ng ~hift con-~rersion ~tage, for various catalytic syntheses~ e.g., for the syn-tl~1~ of` ammonia or for the ~thesi~ o:t`~methane.
.
; .
Claims (10)
1. A process for purifying raw gases produced by gasi-fication of solid or liquid fossile fuels, by treatment with wa-ter vapor and oxygen under superatmospheric pressure, in order to remove therefrom catalyst-deteriorating impurities, such as mono- or polyunsaturated hydrocarbons, mercaptans, HCN, HCl, H2S, CS2, COS, and NH3, and to desulfurize the gases, while pro-ducing an exhaust gas which is rich in H2S, which process com-prises the steps of:
indirectly cooling to ambient temperature the raw gas, which is available at a temperature of 150-170°C, separating and removing therefrom the condensible hydrocarbons, subsequently scrubbing the gas with water to remove ammonia in a first scrubbing stage, in which the water rate is controlled to be just sufficient to remove the ammonia, then scrubbing the gas with a high-boiling organic solvent miscible with water and selected from the group consist-ing of pyrrolidone or a derivative of pyrrolidone, polyglycol-ether, sulfolane, butyrolactone, morpholine and N-methyl-?-ca-prolactam;
adding sulfur to that solvent in the amount of 0.1 to 10 g per liter of scrubbing liquid and using this sulfurized solvent in a second scrubbing stage in which the solvent rate is controlled in dependence on the solubility of the methyl-mercaptan which is to be removed in the solvent, subsequently adding to the same solvent a soluble activator having a boiling-point that is approximatively as high as or higher than that of the boiling organic solvent adjusting the solvent to an activator content of 1-20% by weight and using this adjusted solvent in a third scrubbing stage, in which the water content of the solvent is kept at 5-30 mole percent H2O and H2S and COS are entirely and selecti-vely removed from the gas, the scrubbing solvents from the second and third scrubbing stages being separatively regenerated and recycled to the second and third scrubbing stages for re-use.
indirectly cooling to ambient temperature the raw gas, which is available at a temperature of 150-170°C, separating and removing therefrom the condensible hydrocarbons, subsequently scrubbing the gas with water to remove ammonia in a first scrubbing stage, in which the water rate is controlled to be just sufficient to remove the ammonia, then scrubbing the gas with a high-boiling organic solvent miscible with water and selected from the group consist-ing of pyrrolidone or a derivative of pyrrolidone, polyglycol-ether, sulfolane, butyrolactone, morpholine and N-methyl-?-ca-prolactam;
adding sulfur to that solvent in the amount of 0.1 to 10 g per liter of scrubbing liquid and using this sulfurized solvent in a second scrubbing stage in which the solvent rate is controlled in dependence on the solubility of the methyl-mercaptan which is to be removed in the solvent, subsequently adding to the same solvent a soluble activator having a boiling-point that is approximatively as high as or higher than that of the boiling organic solvent adjusting the solvent to an activator content of 1-20% by weight and using this adjusted solvent in a third scrubbing stage, in which the water content of the solvent is kept at 5-30 mole percent H2O and H2S and COS are entirely and selecti-vely removed from the gas, the scrubbing solvents from the second and third scrubbing stages being separatively regenerated and recycled to the second and third scrubbing stages for re-use.
2. A process according to claim 1, characterized in that sulfur is added to the scrubbing solvent in the second scrubbing stage in an amount of 3-8 g per liter of scrubbing liquid.
3. A process according to claim 1 or 2, characterized in that the sulfur is produced in the second scrubbing stage by reaction of the hydrogen sulfide contained in the gas leaving the first scrubbing stage with the oxygen which is present in the gas, the oxygen thus being simultaneously removed from the gas.
4. A process according to claim 1, characterized in that the activator is a basic, nitrogen-containing organic compound.
5. A process according to claim 4, characterized in that the activator is an imidazole derivative.
6. A process according to claim 5, characterized in that the activator is 1,2-dimethylimidazole.
7. A process according to claim 1, characterized in that the solvent is adjusted to an activator content of 5-15% by weight.
8. A process according to claim 1, characterized in that the scrubbing solvent from the second scrubbing stage when laden, is regenerated by heating and flashing and stripping off of the substances taken up with water vapor or inert gas.
9. A process according to claim 1 or 8, characterized in that the scrubbing solvent from the third scrubbing stage when laden, is regenerated by flashing and subsequently stripping with inert gas or by treatment under vacuum or both.
10. A process according to claim 1, characterized in that the high-boiling organic solvent is N-methylpyrrolidone.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2433078A DE2433078C3 (en) | 1974-07-10 | 1974-07-10 | Process for the purification of gases produced by gasifying solid fossil fuels using water vapor and oxygen under pressure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1059765A true CA1059765A (en) | 1979-08-07 |
Family
ID=5920146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA231,109A Expired CA1059765A (en) | 1974-07-10 | 1975-07-09 | Process for purifying gases produced by gasification of solid or liquid fossile fuels, by treatment with water vapor and oxygen under superatmospheric pressure |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS598316B2 (en) |
| BR (1) | BR7504390A (en) |
| CA (1) | CA1059765A (en) |
| DE (1) | DE2433078C3 (en) |
| GB (1) | GB1483038A (en) |
| ZA (1) | ZA754439B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6991769B2 (en) | 2000-02-29 | 2006-01-31 | Mitsubishi Heavy Industries, Ltd. | Biomass gasifycation furnace and system for methanol synthesis using gas produced by gasifying biomass |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2654579A1 (en) * | 1976-12-02 | 1978-06-08 | Metallgesellschaft Ag | METHOD FOR REGENERATING LOADED WASHING LIQUIDS |
| DE2854684C2 (en) * | 1978-12-18 | 1980-10-30 | Original Hanau Heraeus Gmbh, 6450 Hanau | Light guides, in particular for operating or examination lights |
| JPS58199702A (en) * | 1982-05-18 | 1983-11-21 | Ube Ind Ltd | Method for purifying synthesis gas |
| US8361421B2 (en) | 2008-11-28 | 2013-01-29 | Shell Oil Company | Method of treating a syngas stream and an apparatus therefor |
| EP2484427B1 (en) | 2011-02-08 | 2017-07-19 | Neste Oyj | A two-stage gas washing method |
| JP6076961B2 (en) * | 2011-03-28 | 2017-02-08 | ザ ボード オブ トラスティーズ オブ ザ ユニヴァーシティ オブ アラバマ | N-functionalized imidazole-containing system and method of use |
| EP2564918B1 (en) | 2011-08-31 | 2018-03-07 | Neste Oyj | A two-stage gas washing method applying sulfide precipitation and alkaline absorption |
| WO2016126957A1 (en) | 2015-02-04 | 2016-08-11 | The Board Of Trustees Of The University Of Alabama | Gas treating solutions containing imidazole-amine compounds |
| EP3583997B1 (en) * | 2018-06-18 | 2022-09-28 | L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude | Method and system for the production of synthesis gas |
| CN109012100B (en) * | 2018-08-23 | 2021-02-26 | 武汉坤久环保科技有限公司 | Coking waste gas treatment system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4828371A (en) * | 1971-08-19 | 1973-04-14 | ||
| DE2227071C2 (en) * | 1972-06-03 | 1985-10-17 | Metallgesellschaft Ag, 6000 Frankfurt | Process for cleaning technical fuel and synthesis gases |
-
1974
- 1974-07-10 DE DE2433078A patent/DE2433078C3/en not_active Expired
-
1975
- 1975-07-08 GB GB28783/75A patent/GB1483038A/en not_active Expired
- 1975-07-09 CA CA231,109A patent/CA1059765A/en not_active Expired
- 1975-07-10 BR BR7504390*A patent/BR7504390A/en unknown
- 1975-07-10 ZA ZA00754439A patent/ZA754439B/en unknown
- 1975-07-10 JP JP50084881A patent/JPS598316B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6991769B2 (en) | 2000-02-29 | 2006-01-31 | Mitsubishi Heavy Industries, Ltd. | Biomass gasifycation furnace and system for methanol synthesis using gas produced by gasifying biomass |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1483038A (en) | 1977-08-17 |
| AU8286775A (en) | 1977-01-13 |
| ZA754439B (en) | 1976-07-28 |
| DE2433078C3 (en) | 1979-12-06 |
| JPS5131678A (en) | 1976-03-17 |
| DE2433078A1 (en) | 1976-01-29 |
| BR7504390A (en) | 1976-07-20 |
| DE2433078B2 (en) | 1979-04-12 |
| JPS598316B2 (en) | 1984-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4088735A (en) | Process for purifying gases from the gasification of fossil fuels | |
| US4011066A (en) | Process of purifying gases produced by the gasification of solid or liquid fossil fuels | |
| US4153674A (en) | Sulfur recovery from gases rich in H2 S and CO2 as well as COS or organic sulfur | |
| CA1157841A (en) | Process of removing h.sub.2s.sub.1co.sub.2 cos and mercaptans from gases by absorption | |
| CN100406106C (en) | Method for the selective removal of hydrogen sulphide and co2 from crude gas | |
| Hochgesand | Rectisol and purisol | |
| CA1298457C (en) | Process for the removal of acid gases from gas mixtures | |
| CA1166824A (en) | Scrubbing system yielding high concentration of hydrogen sulfide | |
| US3965244A (en) | Selective removal of sulfur compounds from acid gas mixtures containing significant quantities of carbonyl sulfide | |
| RU2095124C1 (en) | Method of selectively cleaning carbon dioxide-containing gas from sulfur compounds | |
| RU2533146C2 (en) | Method of sulphur removal | |
| CA1059765A (en) | Process for purifying gases produced by gasification of solid or liquid fossile fuels, by treatment with water vapor and oxygen under superatmospheric pressure | |
| CA1176823A (en) | Recycle of hydrogenated sulfur plant tail gas to sour gas scrubbing system | |
| CA1131883A (en) | Process for the further processing of hydrogen sulphide-containing gases | |
| CN101918104B (en) | Method for treating a process gas flow containing CO2 | |
| JPH0253365B2 (en) | ||
| US3910777A (en) | Absorption system for separate recovery of carbon dioxide and hydrogen sulfide impurities | |
| CN103320176A (en) | Low temperature methanol washing method and device with high CO2 yield | |
| US4891187A (en) | Plural absorption stages for hydrogen purification | |
| US3653810A (en) | Process for a fine purification of hydrogen-containing gases | |
| CA1205277A (en) | Process of regenerating absorbent solutions for sulfur-containing gases | |
| US4263270A (en) | Process for working-up hydrogen sulphide-containing gases | |
| JPS6139093B2 (en) | ||
| AU2014211773B2 (en) | Method and device for generating fuel for a gas turbine | |
| AU2008249822B2 (en) | Process for the removal of carbon dioxide from gas streams |