DK170394B1 - Process for removing H2S and CO2 from a gas mixture containing H2S and CO2 - Google Patents
Process for removing H2S and CO2 from a gas mixture containing H2S and CO2 Download PDFInfo
- Publication number
- DK170394B1 DK170394B1 DK337487A DK337487A DK170394B1 DK 170394 B1 DK170394 B1 DK 170394B1 DK 337487 A DK337487 A DK 337487A DK 337487 A DK337487 A DK 337487A DK 170394 B1 DK170394 B1 DK 170394B1
- Authority
- DK
- Denmark
- Prior art keywords
- absorbent
- gas mixture
- pressure
- contact zone
- purified gas
- Prior art date
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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
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
- B01D53/526—Mixtures of hydrogen sulfide and carbon dioxide
-
- 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
Description
DK 170394 B1DK 170394 B1
Den foreliggende opfindelse angår en fremgangsmåde til fjernelse af H^S og C02 fra en gasblanding, som indeholder H2S og C02, navnlig til fjernelse af disse sure komponenter fra en gasblanding, som indeholder kulbrinter, mellem 10 og 5 50 rumfangs% CC>2 og en kun ringe mængde H2S, hvor f.eks.The present invention relates to a process for removing H 2 S and CO 2 from a gas mixture containing H 2 S and CO 2, in particular for removing these acidic components from a gas mixture containing hydrocarbons, between 10 and 50% by volume of CC> 2 and a small amount of H2S, where e.g.
rumfangsforholdet H2S/C02 er mellem 10 og 0,1. Et eksempel på en sådan gasblaning er naturgas.the volume ratio H2S / CO2 is between 10 and 0.1. An example of such gas blending is natural gas.
Det er opfindelsens formål at tilvejebringe en fleksibel proces til i det væsentlige fuldstændig fjernelse 10 af de små mængder H2S og store mængder af C02.It is the object of the invention to provide a flexible process for substantially complete removal of the small amounts of H2S and large amounts of CO 2.
Til dette formål er fremgangsmåden til fjernelse af H2S og C02 fra en gasblanding indeholdende H2S og C02 fra en gasblanding indeholdende H2S og C02 ejendommelig ved, at man 15 a) i en første kontaktzone bringer gasblandingen i kontakt med en vandig reagensopløsning indeholdende en effektiv mængde af et oxiderende reagens til dannelse af en delvis renset gasblanding og en vandig opløsning indeholdende svovl og reduceret reagens, hvorpå man fører den 20 delvis rensede gasblanding til en anden kontaktzone, og b) i den anden kontaktzone bringer den delvis rensede gasblanding i kontakt med en vandig opløsning af en regenererbar absorbent til frembringelse af en renset gasblanding og en belastet absorbent.For this purpose, the process for removing H2S and CO2 from a gas mixture containing H2S and CO2 from a gas mixture containing H2S and CO2 is characterized by contacting the gas mixture with an aqueous reagent solution containing an effective amount of an oxidizing reagent to form a partially purified gas mixture and an aqueous solution containing sulfur and reduced reagent, then passing the partially purified gas mixture to another contact zone, and b) in the second contact zone bringing the partially purified gas mixture into contact with an aqueous solution of a regenerable absorbent to produce a purified gas mixture and a loaded absorbent.
25 Svovl, som vindes i trin a) , kan fjernes fra den i trin a) dannede vandige opløsning før eller efter rege-nering af i det mindste en del af det reducerede reagens ved oxidation af reagenset.Sulfur obtained in step a) may be removed from the aqueous solution formed in step a) before or after regeneration of at least a portion of the reduced reagent by oxidation of the reagent.
Den delvis rensede gasblanding føres uden yderligere 30 behandling eller omdannelse til den anden kontaktzone, omend man efter behov kan opvarme eller afkøle den delvis rensede gasblaning.The partially purified gas mixture is conducted without further treatment or conversion to the second contact zone, although it is possible to heat or cool the partially purified gas mixture as required.
Hvert af trinnene a) og b) er i og for sig kendte, men valget af rækkefølgen af de to trin medfører, at udgangs-35 strømmen fra trin b) er renset gas og efter regenerering H2S-fri C02.Each of steps a) and b) are known per se, but the choice of the order of the two steps results in the output stream from step b) being purified gas and after regeneration H2S-free CO 2.
Ved en hensigtsmæssig udførelsesform indeholder den DK 170394 B1 2 ! vandige reagensopløsning et koordinationskompleks af Fe(III) med en organisk syre, f.eks. nitrilotrieddikesyre (NTA) eller ætylendiamintetraeddikesyre (EDTA) .In a suitable embodiment, it contains DK 170394 B1 2! aqueous reagent solution a coordination complex of Fe (III) with an organic acid, e.g. nitrilotriacetic acid (NTA) or ethylenediaminetetraacetic acid (EDTA).
Ved en foretrukken udførelsesform indeholder den 5 vandige reagensopløsning en ammoniumform af et koordinationskompleks af Fe(III) med NTA og en ammoniumform af et koordinationskompleks af Fe(II) med NTA. Den vandige reagensopløsning kan endvidere indeholde ammoniakvand. Opløsningens pH er hensigtsmæssigt mellem 5 og 8,5, og 10 molforholdet mellem på den ene side koordinationskomplekset af Fe (III) med NTA og på den anden ammoniumformen af kooordinationskomplekset af Fe (II) med NTA i opløsningen er hensigtsmæssigt mellem 0,2 og 6. Den vandige reagensopløsning indeholder omkring 2-15 mol af en ammoniumform af et 15 koordinationskompleks af Fe(III) med NTA pr. mol H2S, der skal fjernes.In a preferred embodiment, the aqueous reagent solution contains an ammonium form of a coordination complex of Fe (III) with NTA and an ammonium form of a coordination complex of Fe (II) with NTA. The aqueous reagent solution may further contain ammonia water. The pH of the solution is conveniently between 5 and 8.5, and the 10 molar ratio between on the one hand the coordination complex of Fe (III) with NTA and on the other the ammonium form of the coordination complex of Fe (II) with NTA in the solution is preferably between 0.2 and 6. The aqueous reagent solution contains about 2-15 moles of an ammonium form of a Fe (III) coordination complex with NTA per ml. moles of H2S to be removed.
Den delvis rensede gasblanding indeholder C02, der fjernes i trin b) ved hjælp af væsken og den regenererbare absorbent. For at fjerne CC>2 fra den i trin b) vundne 20 belastede absorbent momentanfordampes den belastede absorbent mindst én gang ved aflastning af trykket til et niveau under partialtrykket af C02 ved den herskende temperatur.The partially purified gas mixture contains CO 2, which is removed in step b) by the liquid and the regenerable absorbent. To remove CC> 2 from the absorbent 20 obtained in step b), the charged absorbent is momentarily evaporated at least once by relieving the pressure to a level below the partial pressure of CO 2 at the prevailing temperature.
Hvis der er behov for at fjerne coabsorberede kul-25 brinter, kan der forud for dette trin foretages en hurtig fordampning af den belastede absorbent mindst én gang ved aflastning af trykket til et niveau mellem det tryk,der hersker ved kontakten i trin b) , og partialtrykket af CC>2 ved den herskende temperatur.If there is a need to remove coabsorbed hydrocarbons, prior to this step, a rapid evaporation of the loaded absorbent can be performed at least once by relieving the pressure to a level between the pressure prevailing at the contact in step b). and the partial pressure of CC> 2 at the prevailing temperature.
30 Ved yderligere en hensigtsmæssig udførelsesform er den regenererbare absorbent en amin, f.eks. en tertiær amin såsom metyldiætanolamin (MDEA).In yet another convenient embodiment, the regenerable absorbent is an amine, e.g. a tertiary amine such as methyl diethanolamine (MDEA).
Væsken og den regenererbare absorbent kan tillige omfatte et fysisk opløsningsmiddel som f.eks. sulfolan. » 35 Væsken og den regenererbare absorbent omfatter hensigtsmæssigt en vandig opløsning af 10-60 vægt% MDEA, * 15-55 vægt% sulfolan og 5-35 vægt% vand.The liquid and the regenerable absorbent may also comprise a physical solvent, e.g. sulfolane. Conveniently, the liquid and the regenerable absorbent comprise an aqueous solution of 10-60 wt% MDEA, * 15-55 wt% sulfolane and 5-35 wt% water.
3 DK 170394 B13 DK 170394 B1
Fremgangsmåden ifølge opfindelsen skal i det følgende belyses nærmere under henvisning til tegningen, der skematisk viser et apparat til udøvelse af fremgangsmåden ifølge opfindelsen.The method according to the invention will now be described in more detail with reference to the drawing, which schematically shows an apparatus for carrying out the method according to the invention.
5 Apparatet har en første kontaktzone 1, en svovludvin dingszone 3, en første regenerations zone 5, en anden kontaktzone 6, en første momentanfordampningsbeholder 8 og en anden momentanfordampningsbeholder 9.5 The apparatus has a first contact zone 1, a sulfur recovery zone 3, a first regeneration zone 5, a second contact zone 6, a first instantaneous evaporation vessel 8 and a second instantaneous evaporation vessel 9.
Til den første kontaktzone 1 er der forbundet en 10 tilførselsledning 10 for sur gas. Den første kontaktzone 1 er forbundet med svovludvindings zonen 3 ved hjælp af en ledning 12 og med den anden kontaktzone 6 ved hjælp af en ledning 14. Svovludvindings zonen 3 er forsynet med en svovludgang 15, og zonen 3 er forbundet med den første 15 regenerations zone 5 ved hjælp af en ledning 16. Den første regenerationszone 5 er forbundet med en oxidanttilførsels-ledning 17 og en udgang 19 for brugt gas, og den første regenerationszone 5 er endvidere forbundet med den første kontaktzone 1 ved hjælp af en ledning 20.To the first contact zone 1 is connected a 10 supply gas 10 for acid gas. The first contact zone 1 is connected to the sulfur recovery zone 3 by means of a conduit 12 and to the second contact zone 6 by means of a conduit 14. The sulfur recovery zone 3 is provided with a sulfur outlet 15 and the zone 3 is connected to the first zone of regeneration 15 5 by means of a conduit 16. The first regeneration zone 5 is connected to an oxidant supply conduit 17 and a spent gas outlet 19, and the first regeneration zone 5 is also connected to the first contact zone 1 by means of a conduit 20.
20 Den anden kontaktzone 6 har en udgang 21 for renset gas, og denne zone 6 er forbundet med den første momentanfordampningsbeholder 8 ved hjælp af en ledning 22, der er forsynet med en trykaflastningsventil 23. Den første momentanfordampningsbeholder 8 har en gasudgang 25 og er 25 ved hjælp af en ledning 26, forsynet med en trykaflastningsventil 27, forbundet med den anden momentanfordampningsbeholder 9. Den anden momentanfordampningsbeholder 9 har en gasudgang 30 og er forbundet med den anden kontaktzone 6 ved hjælp af en ledning 31.The second contact zone 6 has an outlet 21 for purified gas, and this zone 6 is connected to the first instantaneous evaporation vessel 8 by means of a conduit 22 provided with a pressure relief valve 23. The first instant evaporation vessel 8 has a gas outlet 25 and is 25 by means of a conduit 26, provided with a pressure relief valve 27, connected to the second instantaneous evaporation vessel 9. The second instantaneous evaporation vessel 9 has a gas outlet 30 and is connected to the second contact zone 6 by means of a conduit 31.
3030
EksempelExample
En kulbrinteholdig sur gasblanding indeholdende 15 - rumfangs% C02 og 250 rumfangs-dpm (rumfangsdele pr.A hydrocarbonaceous acidic gas mixture containing 15% by volume CO 2 and 250 volume ppm (parts by volume).
35 million) H2S føres til den første kontaktzone 1 gennem tilførselsledningen 10 for sur gas. I den første kontaktzone 1 bringes den sure gasblanding i kontakt med en vandig 4 DK 170394 B1 reagensopløsning indeholdende 0,65 mol/1 af en ammoniumform af et koordinationskompleks af Fe (III) med NTA til dannelse af en delvis renset gasblanding, som indeholder 12 rum-fangs% C02 og 2 rumfangs-dpm H^S, og en vandig opløsning 5 indeholdende svovl og reduceret reagens indeholdende en yderligere mængde af en ammoniumform af et koordinations-kompleks af Fe(II) med NTA. Den vandige opløsning indeholdende svovl og reduceret reagens føres gennem ledningen 12 til svovlfjernelseszonen 3, og fra den fjernes svovl 10 gennem udgangen 15, mens den i det væsentlige svovlfri vandige opløsning føres gennem ledningen 16 til den første regenerations zone 5, hvor i det mindste en del af det reducerede reagens oxideres ved, at den vandige opløsning bringes i kontakt med luft, der tilføres gennem oxidanttil-15 førselsledningen 17. Den regenererede vandige reagensopløsning føres til den første kontaktzone 1 gennem ledningen 20, og brugt luft fjernes fra den første regenerationszone 5 gennem udgangen 19 for brugt gas.35 million H2S is passed to the first contact zone 1 through the acid gas supply line 10. In the first contact zone 1, the acidic gas mixture is contacted with an aqueous 4 reagent solution containing 0.65 mol / l of an ammonium form of a coordination complex of Fe (III) with NTA to form a partially purified gas mixture containing 12 2% and 2 volumes ppm H 2 S, and an aqueous solution 5 containing sulfur and reduced reagent containing an additional amount of an ammonium form of a coordination complex of Fe (II) with NTA. The aqueous solution containing sulfur and reduced reagent is passed through conduit 12 to the sulfur removal zone 3, and from it, sulfur 10 is removed through outlet 15, while the substantially sulfur-free aqueous solution is passed through conduit 16 to the first regeneration zone 5, where at least one part of the reduced reagent is oxidized by contacting the aqueous solution with air supplied through the oxidant supply conduit 17. The regenerated aqueous reagent solution is fed to the first contact zone 1 through conduit 20 and used air is removed from the first regeneration zone 5 through the outlet 19 for used gas.
Den delvis rensede gasblanding føres uden at blive 20 behandlet gennem ledningen 14 til den anden kontaktzone 6, hvor den bringes i kontakt med en væske og en regenererbar absorbent i form af en vandig opløsning indeholdende 30 vægt% MDEA under sådanne betingelser, at C02 fjernes fra den delvis rensede gasblanding til frembringelse af en 25 renset gasblanding og en belastet absorbent. Den rensede gasblanding, der indeholder 1 rumfangs% CC>2 og 1,5 rum-fangs-dpm H2S, fjernes fra den anden kontaktzone 7 gennem udgangen 21 for renset gas, og den belastede absorbent føres gennem ledningen 22 til den første momentanfor-30 dampningsbeholder 8. I denne første momentanfordampningsbeholder 8 fjernes kulbrinter, der ligeledes er absorberet af absorbenten, ved at den belastede absorbent underkastes momentanfordampning, ved at trykket aflastes til et niveau mellem det tryk, der hersker i den anden kontaktzone 6, og t, 35 partialtrykket af C02 ved den herskende temperatur. Den desorberede kulbrinteholdige gasblanding, der i det * væsentlige er fri for CC>2, fjernes fra den første momentan- 5 DK 170394 B1 fordampningsbeholder 8 gennem gasudgangen 25. Den delvis belastede absorbent, som vindes i den første momentanfordampningsbeholder 8, føres gennem ledningen 26 til den anden momentanfordampningsbeholder 9. I den anden momentan-5 fordampningsbeholder 9 fjernes C02 fra den delvis belastede absorbent, ved at trykket aflastes til et niveau under partialtrykket af C02 ved den herskende temperatur, hvorved der vindes en regenereret absorbent, som føres tilbage til den anden kontaktzone 6 gennem ledningen 31. Det desorbere-10 de C02, der er i det væsentlige frit for H2S, fjernes fra den anden momentanfordampningsbeholder 9 gennem gasudgangen 30.The partially purified gas mixture is passed without being treated through conduit 14 to the second contact zone 6, where it is contacted with a liquid and a regenerable absorbent in the form of an aqueous solution containing 30% by weight MDEA under conditions such that CO the partially purified gas mixture to produce a purified gas mixture and a loaded absorbent. The purified gas mixture containing 1 volume% CC> 2 and 1.5 volume-captive ppm H2S is removed from the second contact zone 7 through the purified gas outlet 21 and the charged absorbent is passed through line 22 to the first instantaneous feed 30 evaporating vessel 8. In this first instantaneous evaporation vessel 8, hydrocarbons also absorbed by the absorbent are subjected to instantaneous evaporation by relieving the pressure to a level between the pressure prevailing in the second contact zone 6 and t, the partial pressure. of CO 2 at the prevailing temperature. The desorbed hydrocarbon-containing gas mixture substantially free of CC> 2 is removed from the first instantaneous evaporation vessel 8 through the gas outlet 25. The partially loaded absorbent obtained in the first instantaneous evaporation vessel 8 is passed through the conduit 26 to the second instantaneous evaporation vessel 9. In the second instantaneous evaporation vessel 9, the CO2 is removed from the partially loaded absorbent by relieving the pressure to a level below the partial pressure of the CO2 at the prevailing temperature, thereby obtaining a regenerated absorbent which is returned to the second contact zone 6 through conduit 31. The desorbed CO 2 which is substantially free of H2 S is removed from the second instantaneous evaporator vessel 9 through the gas outlet 30.
Den første kontaktzone 1 og den første regenerations-zone 5 kan være kolonner, som egner sig til modstrømskon-15 takt mellem gas og væske, eller kolonner, der egner sig til medstrømskontakt mellem gas og væske.The first contact zone 1 and the first regeneration zone 5 may be columns suitable for gas-liquid countercurrent contact, or columns suitable for gas-liquid co-current contact.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8616508A GB2192347B (en) | 1986-07-07 | 1986-07-07 | Removing hydrogen sulphide and carbon dioxide from a gas mixture containing hydrogen sulphide and carbon dioxide. |
| GB8616508 | 1986-07-07 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK337487D0 DK337487D0 (en) | 1987-07-01 |
| DK337487A DK337487A (en) | 1988-01-08 |
| DK170394B1 true DK170394B1 (en) | 1995-08-21 |
Family
ID=10600677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK337487A DK170394B1 (en) | 1986-07-07 | 1987-07-01 | Process for removing H2S and CO2 from a gas mixture containing H2S and CO2 |
Country Status (9)
| Country | Link |
|---|---|
| CN (1) | CN1016166B (en) |
| AU (1) | AU590866B2 (en) |
| CA (1) | CA1296160C (en) |
| DE (1) | DE3721789A1 (en) |
| DK (1) | DK170394B1 (en) |
| GB (1) | GB2192347B (en) |
| IN (1) | IN169707B (en) |
| NL (1) | NL194362C (en) |
| NO (1) | NO166920C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| DE4014018A1 (en) * | 1990-05-01 | 1991-11-07 | Metallgesellschaft Ag | Gas purificn. using recyclable scrubber soln. - esp. for desulphurisation of fuel gas |
| GB9606685D0 (en) * | 1996-03-29 | 1996-06-05 | Boc Group Plc | Gas separation |
| DE102008052612A1 (en) * | 2008-10-21 | 2010-04-22 | Uhde Gmbh | Wash solution for gas scrubbing with amines in aqueous ammonia solution and use |
| CN102350174A (en) * | 2011-07-11 | 2012-02-15 | 中国石油化工集团公司 | Method for selective removal of H2S by dynamic wave scrubber |
| CN104667714A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院过程工程研究所 | Device and method for deep removal of acid gas in industrial mixed gas |
| CN110218596B (en) * | 2019-05-30 | 2020-09-29 | 中石化石油机械股份有限公司研究院 | Deacidifying technological process of natural gas |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4091073A (en) * | 1975-08-29 | 1978-05-23 | Shell Oil Company | Process for the removal of H2 S and CO2 from gaseous streams |
| US4359450A (en) * | 1981-05-26 | 1982-11-16 | Shell Oil Company | Process for the removal of acid gases from gaseous streams |
| US4409199A (en) * | 1981-12-14 | 1983-10-11 | Shell Oil Company | Removal of H2 S and COS |
-
1986
- 1986-07-07 GB GB8616508A patent/GB2192347B/en not_active Expired
-
1987
- 1987-05-22 NL NL8701225A patent/NL194362C/en not_active IP Right Cessation
- 1987-05-27 CA CA000538120A patent/CA1296160C/en not_active Expired - Fee Related
- 1987-06-30 CN CN87104539A patent/CN1016166B/en not_active Expired
- 1987-07-01 DK DK337487A patent/DK170394B1/en not_active IP Right Cessation
- 1987-07-01 AU AU75007/87A patent/AU590866B2/en not_active Ceased
- 1987-07-01 DE DE19873721789 patent/DE3721789A1/en not_active Withdrawn
- 1987-07-01 NO NO872756A patent/NO166920C/en not_active IP Right Cessation
- 1987-07-01 IN IN473/MAS/87A patent/IN169707B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO166920B (en) | 1991-06-10 |
| IN169707B (en) | 1991-12-14 |
| NL194362B (en) | 2001-10-01 |
| GB2192347A (en) | 1988-01-13 |
| DE3721789A1 (en) | 1988-01-21 |
| GB2192347B (en) | 1989-12-13 |
| AU7500787A (en) | 1988-01-14 |
| CN1016166B (en) | 1992-04-08 |
| DK337487A (en) | 1988-01-08 |
| NL8701225A (en) | 1988-02-01 |
| NO166920C (en) | 1991-09-18 |
| CA1296160C (en) | 1992-02-25 |
| AU590866B2 (en) | 1989-11-16 |
| GB8616508D0 (en) | 1986-08-13 |
| NO872756D0 (en) | 1987-07-01 |
| CN87104539A (en) | 1988-02-17 |
| DK337487D0 (en) | 1987-07-01 |
| NL194362C (en) | 2002-02-04 |
| NO872756L (en) | 1988-01-08 |
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