IE55266B1 - Procedure for thermal cracking of hydrocarbon oils - Google Patents
Procedure for thermal cracking of hydrocarbon oilsInfo
- Publication number
- IE55266B1 IE55266B1 IE1379/83A IE137983A IE55266B1 IE 55266 B1 IE55266 B1 IE 55266B1 IE 1379/83 A IE1379/83 A IE 1379/83A IE 137983 A IE137983 A IE 137983A IE 55266 B1 IE55266 B1 IE 55266B1
- Authority
- IE
- Ireland
- Prior art keywords
- pressure vessel
- process according
- fluid
- gas mixture
- rotation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 20
- 238000004227 thermal cracking Methods 0.000 title claims abstract description 12
- 239000003921 oil Substances 0.000 title claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000012530 fluid Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 241000252095 Congridae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- -1 petrol Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00823—Mixing elements
- B01J2208/00831—Stationary elements
- B01J2208/0084—Stationary elements inside the bed, e.g. baffles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00761—Details of the reactor
- B01J2219/00763—Baffles
- B01J2219/00765—Baffles attached to the reactor wall
- B01J2219/0077—Baffles attached to the reactor wall inclined
- B01J2219/00772—Baffles attached to the reactor wall inclined in a helix
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A procedure for thermal cracking of hydrocarbons. In the procedure, the hydrocarbons are heated to reaction temperature and conducted into the reaction zone, where the flow is upward from below. The fluid/gas mixture is by the aid of a helix system (16, 17) or by nozzles set in tangential rotation in the pressure vessel (14), which constitutes the reaction zone (18), whereby a uniform delay time is obtained without any intermediate bottoms impeding cleaning operations.
[GB2133034A]
Description
55266 5 The present invention concerns a procedure for thermal cracking of hydrocarbon oils, in which procedure the hydrocarbons are heated to reaction temperature and conducted into a reaction zone, where the 10 flow is upward from below.
In thermal cracking of hydrocarbon oils, heavy oil fractions are cracked :to lighter fractions, thereby increasing the yield of the latter. In cracking, the feed oil is heated in the heating 15 tubes of the cracking furnace to cracking temperature. As a rule, two alternative procedures are available. In one of them, crooking takes place in the heating tubes of the.cracking furnace and partly in the. pipelines which lead to the process steps followng after the cracking. In this cracking procedure the delay times are not 20 exactly known, but they are relatively short, that is in the order of one minute. The pressure varies greatly, going down from the furnace entrance to the furnace exit. In the other cracking procedure, the hydrocarbon feed is first heated in the cracking furnace to a suitable reaction temperature, and the actual cracking reac-25 tion takes place in a separate reaction zone, where the delay time is considerably longer than in the preceding procedure, that is, of the order of 10 to 30 minutes. No heat is introduced to the reaction zone.
In the procedure last mentioned, the reaction zone as a rule con sists of an upright, cylindrical pressure vessel, at one end of which the oil feed heated in the cracking furnace is introduced, at the other end being extracted a mixture of liquid and gas to go to further refining steps, for instance to distilling. The flow 35 direction in the reaction zone has been either downward from above or upward from below.
In thermal cracking of hydrocarbon oils, reactions of substantially two kinds take place. One of them is the cracking reaction proper, -2- the long-chain molecules being split into smaller molecules, causing reduction of viscosity. The other reaction type is called polycondensation, whereby the molecules combine and produce pitch and coke as hydrogen is set free. The last-mentioned reaction is an undesired reaction because it results in greater quantities of asphaltenes. Since the condensing reactions grow to be significant at higher temperatures, endeavours are made to use lower reaction temperatures and correspondingly longer delay times.
The delay time is very important for thermal cracking. The cracking has not time to take place if the delay time is too short. In a case when the delay time is too long, the cracking products begin to react and to form undesired reaction products. As a result, an unstable product is formed which causes difficulties in the further use of the fuel. The aim is therefore a cracking as uniform a3 possible. If the flows in-the pressure vessel serving as reaction zone are non-uniform, the result will be varying delay times.
In the cracking reaction, light components are formed which evaporate at the temperature and pressure in the reaction zone. Therefore, the density of the liquid/gas mixture decreases as the mixture flows upward in the pressure vessel. Owing to the hydrostatic pressure differential in the pressure vessel, the density of the gas part also decreases as the mixture flows upward. The liquid fractions formed in the cracking reactor have lower density than the feed, which also lowers the density of the liquid/gas mixture. Therefore, the flow velocity is not constant in the usually employed cylindrical reactor with uniform thickness, but accelerates as the mixture flows upward.
The thermal cracking procedure disclosed in U.S. Patent No. 4,247,387 has a cylindrical vertical pressure vessel serving as reaction zone, and in which with a view to preventing refluxes within the reactor have been disposed perforated intermediate bottoms constituting a plurality of mixing sites in the reactor. This aims towards achieving a delay time as uniform as possible for the fraction fed into the zone. The use of intermediate plates -3- hao its drawbacks. Faulty operation of the reactor may cause the whole reactor to be coked to occlusion. The intermediate bottoms make the coke removal and reactor cleaning inconvenient and expensive.
The object of the invention is to achieve an improvement in procedures known in the art. The more detailed object of the invention is to provide a procedure in which a uniform delay time can be attained without intermediate bottoms hampering the cleaning process.
The present invention provides a process for thermal cracking of hydrocarbon oils, in which the hydrocarbons are heated to reaction temperature and conducted as a gas/fluid mixture into a reaction zone in the form of a pressure vessel, where the flow is upward from below, the fluid/gas mixture being set in substantially tangential rotation in the pressure vessel about a vertical axis of said vessel and flowing uniformly upward without any return flow causing non-uniform delay times.
According to the invention , in the reaction zone is generated a tangentially rotating, but vertically uniformly upward progressing fluid/gas flow with no return flows causing non-uniform delay times.
The tangentially rotating flow of the fluid/gas mixture can be obtained in a number of ways. According to an advantageous embodiment, the rotary motion is produced by means of helical members which form a helically ascending corridor in the pressure vessel serving as reactor. In tj^3 pa33agei the flow is always in upward direction and no downflows occur. The helix system may extend over the entire length of the reaction zone, or only over part of it. In some instances, it may suffice to restrict the helix system to the entrance section of the reaction zone.
It is also possible to provide in the reactor two or more helix-like members, which reverse the direction of rotation of the fluid/gas mixture. Hereby are produced one or several mixing steps -4- for the fluid/gas mixture flowing in the reaction zone.
Another embodiment serving to set the fluid/gas mixture in tangential rotary motion is that in which tangentially mounted nozzles are used. Through the nozzles part of the feed or another fluid, e.g. steam, may be introduced to set the feed proper in rotary motion. The number of the nozzles is selected according to the need, for instance from 2 to 20 nozzles. It is also possible to dispose the feed pipes for the hydrocarbon being cracked entering the reaction zone tangentially in the entrance section of the zone.
According to still another advantageous embodiment, the reaction zone has the shape of an outwardly expanding cone over its entire length or in part, for instance only on the part of the supply section. Such conical shape already in itself has the effect that the distribution of delay.time is uniform.
From the point of view of the cracking reaction, it has been established that the appropriate temperature is between 4-10 to 470 degrees and the pressure between 2 and 20 bar. The ratio of the average diameter and the length of the reaction zone is favourbaly in the range from 1:1 to 1:20.
The invention is described in detail, referring to some advantageous embodiments of the invention presented in the figures of the attached drawing, but to which the invention 13 not meant to be exclusively confined.
Fig. 1 presents an advantageous embodiment of the procedure in a schematic process diagram.
Fig. 2 presents an advantageous embodiment of the reactor used in the invention in schematic elevational view.
Fig. 3A presents another advantageous embodiment of the reactor employed in the procedure of the invention viewed from above.
Fig. 3B presents the reactor of Fig. 3A in elevational view.
Fig. 4A presents a further advantageous embodiment of the reactor used in the invention viewed from above.
Fig. 4B presents the reactor of Fig. 4A in elevational view.
In Fig. 1, the feed oil is conducted through the pipe 11 into the furnace 12, where its temperature is raised to between 410 and 470 degrees. From the furnace 12, the oil is conducted through the pipe 13 into the reactor 14, where it flows upward and departs at the top of the reactor through the pipe 15 to a separate unit (not depicted), wherein for instance gas, petrol, light and heavy fuel oil may be separated from each other. The average delay time in the reaction zone i3 between 5 and 100 minutes.
In the embodiment of Fig. 2, a helical member 16 has been formed within the reactor 14. The hydrocarbons to be cracked are conducted into the reactor 14 where the flow is upward from below, whereby they enter a helical corridor formed by the spiral member 16, and where the actual cracking takes place.
In the embodiment of Fig. 2, the reaction zone 18 may equally have two helical members 16 and 17, with opposite directions of the helix, Hereby, the fluid/gas mixture flowing in the reaction zone 18 will reverse its rotation.
Figs 3A and 3B show the lower part of the pressure vessel 14 acting a3 reaction zone 18 and in which the hydrocarbon flow to be cracked is introduced upward from below. With the lower part of the pressure vessel 14 communicate tangentially the nozzles 19, through which either part of the feed or another fluid, such as steam for instance, may be introduced in order to set in rotation the hydrocarbon flow that is being cracked.
In the embodiment of Figs 4A and 4B, on the end of the feed pipe 20 for the hydrocarbons to be cracked have been formed nozzles 21 -6- which force the feed into rotary motion.
Example I: On pilot plant scale, thermal cracking of crude oil was carried out, using a reactor as in Fig. 1, and a similar reactor having no helix system. In other respects, the conditions were equal. The feed oil was the vacuum distilling base of Soviet crude oil. The results are shown in the table attached:- Characteristic Feed Properties of the base product (Distillation fraction 180 C+) Without With helix system helix system Density (g/cra 20 C) 1.0011 1.001 1.002 Asphaltene content (% by weight) 6.28 10.70 11.10 Sulphur content (.% by weight) 3-65 3.38 3-54 Viscosity cSt (50 C) 43000 4200 3300 Stability 1) - 2.0 2.1 1) The concept of stability is described more in detail in: van Kerkvoort, W.J., Nieuwstad, A.J.J. IV: E Congres Intern, du Chauffage Industriel, paper number 220, Paris, 1952.
Claims (6)
1. A process for thermal cracking of hydrocarbon oils, in which the hydrocarbons are heated to reaction temperature and conducted as a gas/fluid mixture into a reaction zone in the form of a pressure vessel, where the flow is upward from below, the fluid/gas mixture being set in substantially tangential rotation in the pressure vessel about a vertical axis of said vessel and flowing uniformly upward without any return causing non-uniform delay times.
2. A process according to claim 1, wherein the fluid/gas mixture is set in rotation by the aid of at least one helix-like member.
3. A process according to claim 2, wherein a helix system is disposed on the entire length of the pressure vessel.
4. A process according to claim 2, wherein a helix system is disposed on part of the length of the pressure vessel, or merely in an entrance and/or exit section of said vessel. 5. A process according to any one of claims 2 to 4 with two or more helix systems which may reverse the rotation of the fluid/gas mixture. 6. A process according to claim 1, wherein the fluid/gas mixture is set in rotation by the aid of nozzles. 7. A process according to claim 6, wherein the nozzles communicate tangentially with an entrance section of the pressure vessel. 8. A process according to claim 6 or 7, wherein the nozzles are in the pressure vessel on an extension of a feed pipe for the hydrocarbons. 9. A process according to any one of claims 6 to 8, wherein the fluid/gas mixture is set in rotation by the aid of a nozzle system, wherethrough part of the supply, or steam or another fluid, is 8- conducted into the pressure vessel. 10. A process according to any one of claims 1 to 9, wherein the . thermal cracking is accomplished in the pressure vessel at a 5 temperature of 410 to 470°C, under pressure 2 to 20 bar and with an average delay time from 5 to 100 minutes. 11. A process according to any one of claim 1 to 10, wherein the pressure vessel comprises an upwardly expanding conical pressure vessel. 10 12. A process for thermal cracking of hydrocarbon oils substantially as described herein with reference to Figure 1 and/or 3A and 3B and/or 4A and 4B of the accompanying drawings. 13. Hydrocarbon oils whenever treated by a process as claimed in any preceding claim. Dated this the 13th day of June, 1983. 20 BY: TOMKINS & CO., Applicants' Agents, (Signed) 1-®^-* 25
5. , Dartmouth Road, DUBLIN
6. 30 -9- 35
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI822119A FI65274C (en) | 1982-06-14 | 1982-06-14 | FOERFARANDE FOER TERMISK KRACKNING AV KOLVAETEOLJA |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE831379L IE831379L (en) | 1983-12-14 |
| IE55266B1 true IE55266B1 (en) | 1990-07-18 |
Family
ID=8515691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE1379/83A IE55266B1 (en) | 1982-06-14 | 1983-06-13 | Procedure for thermal cracking of hydrocarbon oils |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS59501068A (en) |
| BE (1) | BE896901A (en) |
| CA (1) | CA1209943A (en) |
| CS (1) | CS241059B2 (en) |
| DE (1) | DE3390051T1 (en) |
| FI (1) | FI65274C (en) |
| FR (1) | FR2528444B1 (en) |
| GB (1) | GB2133034B (en) |
| HU (1) | HU202573B (en) |
| IE (1) | IE55266B1 (en) |
| IT (1) | IT1163501B (en) |
| NL (1) | NL8320167A (en) |
| WO (1) | WO1984000035A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0232772B1 (en) * | 1986-02-05 | 1989-12-27 | Siemens Aktiengesellschaft | Process for preparing a pulverulent amorphous material by way of a milling process |
| FI85598C (en) * | 1989-09-13 | 1992-05-11 | Antero Ollila | FOERFARANDE OCH ANORDNING FOER TERMISK KRACKNING AV KOLVAETEOLJOR OCH FOER ANDRA VAETSKE / -GASREAKTIONER. |
| LT3884B (en) | 1994-06-22 | 1996-04-25 | Akcine Bendrove Mazeikiu Nafta | Reactor of thermal cracking |
| FR2741889B1 (en) * | 1995-12-04 | 1999-01-29 | Total Raffinage Distribution | IMPROVEMENTS IN PROCESSES AND DEVICES FOR VISCOREDUCING HEAVY HYDROCARBON LOADS |
| EP1628586B1 (en) | 2003-05-15 | 2011-07-06 | Covidien AG | Tissue sealer with non-conductive variable stop members |
| JP4951302B2 (en) * | 2006-09-28 | 2012-06-13 | 千代田化工建設株式会社 | Pyrolysis treatment method, pyrolysis reaction tank, and pyrolysis treatment apparatus for heavy petroleum oil |
| JP5038674B2 (en) | 2006-09-28 | 2012-10-03 | 千代田化工建設株式会社 | Pyrolysis treatment method and pyrolysis treatment equipment for heavy petroleum oil |
| US8512371B2 (en) | 2009-10-06 | 2013-08-20 | Covidien Lp | Jaw, blade and gap manufacturing for surgical instruments with small jaws |
| US8852186B2 (en) | 2011-08-09 | 2014-10-07 | Covidien Lp | Microwave sensing for tissue sealing |
| US8864795B2 (en) | 2011-10-03 | 2014-10-21 | Covidien Lp | Surgical forceps |
| US8968308B2 (en) | 2011-10-20 | 2015-03-03 | Covidien Lp | Multi-circuit seal plates |
| US9713493B2 (en) | 2012-04-30 | 2017-07-25 | Covidien Lp | Method of switching energy modality on a cordless RF device |
| US9713491B2 (en) | 2013-02-19 | 2017-07-25 | Covidien Lp | Method for manufacturing an electrode assembly configured for use with an electrosurigcal instrument |
| US9717548B2 (en) | 2013-09-24 | 2017-08-01 | Covidien Lp | Electrode for use in a bipolar electrosurgical instrument |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE27692C (en) * | G. SCHRADßR in Ehrenfeld, Venloerstr. 168 | Automatic protective device fMT joining and dressing machines | ||
| GB178734A (en) * | 1921-05-09 | 1922-04-27 | Frederick Southwell Cripps | Improvements in apparatus for evaporating paraffin or other liquids, and mixing the vapours produced with coal gas |
| DE749498C (en) * | 1942-05-29 | 1944-11-24 | Standing cracking and distillation kettle with feed nozzles for hot flame gases and atomized oil | |
| US2460463A (en) * | 1946-11-07 | 1949-02-01 | Phillips Petroleum Co | Process for the noncatalytic cracking of a hydrocarbon oil |
| US2717865A (en) * | 1951-05-17 | 1955-09-13 | Exxon Research Engineering Co | Coking of heavy hydrocarbonaceous residues |
| US2759880A (en) * | 1951-10-31 | 1956-08-21 | Exxon Research Engineering Co | Short-time contacting of fluids with solids in hydrocarbon conversion |
| US3498753A (en) * | 1966-07-04 | 1970-03-03 | Nippon Zeon Co | Apparatus for thermal cracking of hydrocarbon |
| US3652451A (en) * | 1968-12-20 | 1972-03-28 | Universal Oil Prod Co | Fluid distribution for fluid-solids contacting chambers |
| FR2229757A1 (en) * | 1973-05-14 | 1974-12-13 | Union Carbide Corp | Hydrocarbon cracker using hot gases - for naphtha, gas oil or crude feedstock |
| JPS5247007A (en) * | 1975-10-14 | 1977-04-14 | Kureha Chem Ind Co Ltd | Method and apparatus for preventing deposition of coke to vessels for thermal cracking of heavy hydrocarbons |
| DE2645649C2 (en) * | 1975-10-14 | 1982-09-02 | Chiyoda Chemical Engineering & Construction Co. Ltd., Yokohama, Kanagawa | Process for the thermal cracking of heavy hydrocarbons |
| JPS5247006A (en) * | 1975-10-14 | 1977-04-14 | Kureha Chem Ind Co Ltd | Method for preventing deposition of coke to vessels for thermal cracki ng of heavy hydrocarbons |
| CA1137434A (en) * | 1978-07-11 | 1982-12-14 | Mohammed Akbar | Process for the continuous thermal cracking of hydrocarbon oils |
| EP0027692B1 (en) * | 1979-10-18 | 1984-05-30 | Imperial Chemical Industries Plc | A process and reactor for the pyrolysis of a hydrocarbon feedstock |
-
1982
- 1982-06-14 FI FI822119A patent/FI65274C/en not_active IP Right Cessation
-
1983
- 1983-05-31 BE BE0/210892A patent/BE896901A/en not_active IP Right Cessation
- 1983-05-31 CA CA000429300A patent/CA1209943A/en not_active Expired
- 1983-06-10 HU HU832320A patent/HU202573B/en not_active IP Right Cessation
- 1983-06-10 DE DE19833390051 patent/DE3390051T1/en not_active Ceased
- 1983-06-10 JP JP58501848A patent/JPS59501068A/en active Granted
- 1983-06-10 NL NL8320167A patent/NL8320167A/en unknown
- 1983-06-10 IT IT21574/83A patent/IT1163501B/en active
- 1983-06-10 WO PCT/FI1983/000044 patent/WO1984000035A1/en active Application Filing
- 1983-06-10 GB GB08401584A patent/GB2133034B/en not_active Expired
- 1983-06-13 CS CS834231A patent/CS241059B2/en unknown
- 1983-06-13 IE IE1379/83A patent/IE55266B1/en unknown
- 1983-06-14 FR FR8309824A patent/FR2528444B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2133034B (en) | 1986-05-29 |
| FR2528444B1 (en) | 1987-06-19 |
| IT1163501B (en) | 1987-04-08 |
| IT8321574A0 (en) | 1983-06-10 |
| HU202573B (en) | 1991-03-28 |
| WO1984000035A1 (en) | 1984-01-05 |
| DE3390051T1 (en) | 1984-06-14 |
| FR2528444A1 (en) | 1983-12-16 |
| NL8320167A (en) | 1984-04-02 |
| FI822119A0 (en) | 1982-06-14 |
| FI65274C (en) | 1984-04-10 |
| JPS59501068A (en) | 1984-06-21 |
| FI65274B (en) | 1983-12-30 |
| BE896901A (en) | 1983-09-16 |
| HUT34535A (en) | 1985-03-28 |
| CS241059B2 (en) | 1986-03-13 |
| CS423183A2 (en) | 1985-07-16 |
| JPS6362557B2 (en) | 1988-12-02 |
| GB8401584D0 (en) | 1984-02-22 |
| IE831379L (en) | 1983-12-14 |
| GB2133034A (en) | 1984-07-18 |
| CA1209943A (en) | 1986-08-19 |
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