US3704333A - Thermal decomposition of organic compounds - Google Patents
Thermal decomposition of organic compounds Download PDFInfo
- Publication number
- US3704333A US3704333A US65665A US3704333DA US3704333A US 3704333 A US3704333 A US 3704333A US 65665 A US65665 A US 65665A US 3704333D A US3704333D A US 3704333DA US 3704333 A US3704333 A US 3704333A
- Authority
- US
- United States
- Prior art keywords
- steam
- alloy steel
- silicon
- protective film
- alloy
- 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 - Lifetime
Links
- 150000002894 organic compounds Chemical class 0.000 title abstract description 23
- 238000005979 thermal decomposition reaction Methods 0.000 title abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052710 silicon Inorganic materials 0.000 abstract description 30
- 239000010703 silicon Substances 0.000 abstract description 30
- 230000001681 protective effect Effects 0.000 abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 150000000475 acetylene derivatives Chemical class 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 238000004326 stimulated echo acquisition mode for imaging Methods 0.000 abstract 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 30
- 229910045601 alloy Inorganic materials 0.000 description 29
- 239000000956 alloy Substances 0.000 description 29
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 14
- 239000000571 coke Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000004227 thermal cracking Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001647090 Ponca Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 2
- PXJQUUBMKNTLHO-UHFFFAOYSA-N ethane;sulfane Chemical compound S.CC PXJQUUBMKNTLHO-UHFFFAOYSA-N 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
- B01J19/0026—Avoiding carbon deposits
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/04—Thermal processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/949—Miscellaneous considerations
- Y10S585/95—Prevention or removal of corrosion or solid deposits
Definitions
- the present invention relates generally to the thermal decomposition of organic compounds, and more particularly, but not by wa'y of limitation, to the thermal decomposition of organic compounds in contact with a heatresistant alloy steel.
- the ethane is commonly charged to a pyrolysis furnace having alloy steel' heating tubes disposed thereinJWhile within the alloy steel heating tubes the ethane is subjected to high pyrolysis temperatures (1300 F. to '2000" F.) to yield the desired ethylene product.
- alloy steels containing nickel and chromium in varying proportions are useful in constructing highly heat-resistant heating tubes for thermal decomposition furnaces.
- heat-resistant alloy steel heating tubes ex'hibit longer performance lives than heating tubes formed of other materials, carburization and corrosion of the tubes and the deposition of coke therein has continued to be a problem.
- Carburization of the tubes which is the diffusion of carbon into the alloy steel causing the formation of carbides, brings about the embrittling thereof. Once the steel has become embrittled it is susceptible to high rates of corrosion and catalytic site formation which in turn leads to the deposition of carbon in the form of coke thereon.
- the present invention relates to the thermal decomposi- -tion of an organic compound in contact with a heatresistant alloy steel wherein the alloy steel is comprised of at least 1% by weight silicon and the alloy steel is pretreated prior to the thermal decomposition by contact with steam at a temperature and for a period of time effective to form a protective film comprised of silicon oxidation compounds thereon.
- a further object of the present invention is the provision of an improved process for the thermal decomposi- DESCRIPTION OF THE PREFERRED EMBODIMENTS It has been found by the applicants that the surfaces of heat-resistant alloy steel containing silicon in an amount of at least 1% by weight can be pretreated' by contact with steam at elevated temperatures, and that when such surfaces are subsequently placed inservice for'the thermal decomposition of organic compounds, such as cracking or: disproportionation, the' rate of J carburization and corrosion of such surfaces as well as the deposition of coke thereon are reduced.
- the present invention is based upon the discovery that contact of alloy steel surfaces containing silicon in an amount of at least about 1% by weight with an oxidizing agent such as steam brings about the formation of a protective film comprised of silicon oxidation compounds. Specifically, when contacted with steam, silicon contained in the alloy steel is oxidized and hydrated to form a protective film of hydrated silicon dioxide (SiO -nH O).
- Silicates of other elements contained in the'alloy steel are also formed which contribute to the protective film, such as manganese silicate (MnSiO Heat resistant iron-chromium-nickel alloys containing at least about 1% silicon by weight are preferred for use in the present inventionflHowever, other chromium or chromium-nickel type alloys may be utilized so long as silicon is'present' therein in an amount of at least about the silicon containing alloy can be used as a lining in another alloy which will provide the ductility and toughness required, the silicon liner can consist essentially of silicon only.
- MnSiO Heat resistant iron-chromium-nickel alloys containing at least about 1% silicon by weight are preferred for use in the present inventionflHowever, other chromium or chromium-nickel type alloys may be utilized so long as silicon is'present' therein in an amount of at least about the silicon containing alloy can be used as a lining in another alloy which will provide the ductility and toughness required,
- duration of the treatment is subject to variation, although lengthy periods are not advantageous. Thus, exposure of the alloy surface to steam contact for at least one minute is required. An exposure for an hour or more is-preferred.
- a protective film of silicon oxidation compounds may be formed during the thermal decomposition of an organic compound by combining small amounts of steam with the organic compound being processed.
- the thermal decomposition is carried out the surfaces of the silicon containing alloy steel will be contacted by the steam and the protective film of silicon oxidation compounds formed thereon.
- Large quantities of steam are not required for this purpose, and it has been found that traces of steam combined with the organic compound are suflicient to'inhibit carburization.
- steam is added to the organic compound in an amount of from about 0.01 pound steam per pound of organic compound to about 1.0 pound of steam per pound of organic compound.
- the alloy steel pretreatment described above may be advantageously combined with theaddition of small amounts of steam to the organic compound being thermally decomposed to reduce the carburization, corrosion, and deposition of coke on the alloy steel. That is, after the protective film of silicon oxidation compounds has.
- the film may be maintained during the carrying out of the decomposition reaction by the addition of small amounts of steam to the organic compound.
- the present invention is advantageously used for thermal, as opposed to catalytic processes.
- exemplary of such processes are thermal disproportionation and cracking, e.g., cracking of hydrocarbons such as ethane, propane, etc. to produce olefins or acetylenes.
- alloy steel is meant those steels which have become prevalent for furnaces recently because of the increased demand for metals capable of withstanding high temperatures and pressures.
- Such alloys generally, but not by way of limitation, include major portions of iron, chromium, and nickel, and can include minor amounts of such elements as aluminum, manganese, phosphorus, sulfur, molybdenum, tantalum, titanium, and zirconium in addition to silicon which, as hereinbefore described, must be present in an'amount of at least about 1% by weight.
- EXAMPLE 3 Five identical new cracking furnaces were erected, the tubes being formed of the HK alloy described as sample Number 3 in Table I above. The tubes of one furnace were pretreated with steam at about 1750 F. for about fifteen hours, while the other furnaces were not subjected to any treatment. All five furnaces were then placed on duty cracking ethane to produce ethylene. During the initial approximately five months of operation of these furnaces, the pretreated furnace was on stream about 82.3% of the time, while the average of the other four was about 74.7%.
- EXAMPLE 4 A cracking furnace having tubes being formed of the HK alloy described as sample Numbers 1 and 2 in Table I above was pretreated with steam at about 1750 F. for about 15 hours prior to placing in ethane cracking service. After approximately five months of operation these tubes were examined for carburization depth. In the HK alloy having 1.0% silicon the carburization depth was one-eighth of an inch and the HK alloy having 1.5% silicon showed no noticeable signs of carburization.
- said heat resisting alloy steel being comprised of at least 1% by weight silicon
- pretreating said alloy prior to said thermal cracking by contacting it with steam at a temperature and for a period of time effective to form a protective film thereon of hydrated silicon dioxide.
- said heat-resistant alloy steel containing at least 1% by weight silicon
- pretreating said alloy prior to said thermal cracking by contacting it with steam at a temperature and for -a period of time effective to form a protective film thereon comprised of hydrated silicon dioxide; and combining at least about 0.01 pound of steam per pound of hydrocarbon with said hydrocarbon so that during the thermal cracking thereof said alloy is contacted with said steam thereby maintaining said protective film of hydrated silicon dioxide thereon.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Chemical Vapour Deposition (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6566570A | 1970-08-20 | 1970-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3704333A true US3704333A (en) | 1972-11-28 |
Family
ID=22064290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US65665A Expired - Lifetime US3704333A (en) | 1970-08-20 | 1970-08-20 | Thermal decomposition of organic compounds |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3704333A (cs) |
| BE (1) | BE771594A (cs) |
| CA (1) | CA958037A (cs) |
| DE (1) | DE2141919A1 (cs) |
| FR (1) | FR2103387B1 (cs) |
| GB (1) | GB1332569A (cs) |
| NL (1) | NL7106789A (cs) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379745A (en) * | 1980-11-21 | 1983-04-12 | Exxon Research And Engineering Co. | Carburization resistance of austenitic stainless steel tubes |
| US4410418A (en) * | 1982-03-30 | 1983-10-18 | Phillips Petroleum Company | Method for reducing carbon formation in a thermal cracking process |
| US4424083A (en) | 1980-11-21 | 1984-01-03 | Exxon Research And Engineering Co. | Carburization resistance of austenitic stainless steel tubes |
| US4454021A (en) * | 1981-12-17 | 1984-06-12 | Showa Denko Kabushiki Kaisha | Method for thermal cracking of hydrocarbons in an apparatus of an alloy having alkali or alkaline earth metals in the alloy to minimize coke deposition |
| US4500364A (en) * | 1982-04-23 | 1985-02-19 | Exxon Research & Engineering Co. | Method of forming a protective aluminum-silicon coating composition for metal substrates |
| US5399257A (en) * | 1991-12-23 | 1995-03-21 | Uop | Coke inhibiting process using glass bead treating |
| US5520751A (en) * | 1993-09-24 | 1996-05-28 | Exxon Research And Engineering Company | Oxidation of low chromium steels |
| US6071563A (en) * | 1995-04-24 | 2000-06-06 | Corning Incorporated | Method of protecting metal |
| US6228253B1 (en) | 1997-06-05 | 2001-05-08 | Zalman Gandman | Method for removing and suppressing coke formation during pyrolysis |
| US6358618B1 (en) | 1999-09-22 | 2002-03-19 | Corning Incorporated | Protective coating on metal |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1483144A (en) * | 1975-04-07 | 1977-08-17 | British Petroleum Co | Protective films |
| JPS5684789A (en) * | 1979-12-13 | 1981-07-10 | Toyo Eng Corp | High-temperature treatment of hydrocarbon-containing material |
| GB2233672A (en) * | 1989-06-30 | 1991-01-16 | Shell Int Research | High temperature treatment of stainless steals used in high temperature reactors |
| US5208069A (en) * | 1991-10-28 | 1993-05-04 | Istituto Guido Donegani S.P.A. | Method for passivating the inner surface by deposition of a ceramic coating of an apparatus subject to coking, apparatus prepared thereby, and method of utilizing apparatus prepared thereby |
| DE19604844C2 (de) * | 1996-02-10 | 1998-02-26 | Forschungszentrum Juelich Gmbh | Verklebung von nichtoxidischen keramischen, keramometallischen oder metallischen Körpern sowie verfahrensgemäß hergestellte Körper |
-
1970
- 1970-08-20 US US65665A patent/US3704333A/en not_active Expired - Lifetime
-
1971
- 1971-05-18 NL NL7106789A patent/NL7106789A/xx unknown
- 1971-05-21 GB GB1621971*[A patent/GB1332569A/en not_active Expired
- 1971-05-25 FR FR7118917A patent/FR2103387B1/fr not_active Expired
- 1971-07-02 CA CA117,196A patent/CA958037A/en not_active Expired
- 1971-08-20 BE BE771594A patent/BE771594A/xx unknown
- 1971-08-20 DE DE19712141919 patent/DE2141919A1/de active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379745A (en) * | 1980-11-21 | 1983-04-12 | Exxon Research And Engineering Co. | Carburization resistance of austenitic stainless steel tubes |
| US4424083A (en) | 1980-11-21 | 1984-01-03 | Exxon Research And Engineering Co. | Carburization resistance of austenitic stainless steel tubes |
| US4454021A (en) * | 1981-12-17 | 1984-06-12 | Showa Denko Kabushiki Kaisha | Method for thermal cracking of hydrocarbons in an apparatus of an alloy having alkali or alkaline earth metals in the alloy to minimize coke deposition |
| US4410418A (en) * | 1982-03-30 | 1983-10-18 | Phillips Petroleum Company | Method for reducing carbon formation in a thermal cracking process |
| US4500364A (en) * | 1982-04-23 | 1985-02-19 | Exxon Research & Engineering Co. | Method of forming a protective aluminum-silicon coating composition for metal substrates |
| US5399257A (en) * | 1991-12-23 | 1995-03-21 | Uop | Coke inhibiting process using glass bead treating |
| US5520751A (en) * | 1993-09-24 | 1996-05-28 | Exxon Research And Engineering Company | Oxidation of low chromium steels |
| US6071563A (en) * | 1995-04-24 | 2000-06-06 | Corning Incorporated | Method of protecting metal |
| US6228253B1 (en) | 1997-06-05 | 2001-05-08 | Zalman Gandman | Method for removing and suppressing coke formation during pyrolysis |
| US6358618B1 (en) | 1999-09-22 | 2002-03-19 | Corning Incorporated | Protective coating on metal |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2103387B1 (cs) | 1975-01-17 |
| FR2103387A1 (cs) | 1972-04-14 |
| CA958037A (en) | 1974-11-19 |
| BE771594A (fr) | 1972-02-21 |
| NL7106789A (cs) | 1972-02-22 |
| GB1332569A (en) | 1973-10-03 |
| DE2141919A1 (de) | 1972-02-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: VISTA CHEMICAL COMPANY, 15990 NORTH BARKERS LANDIN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. SUBJECT TO TERMS OF AGREEMENT DATED JUNE 26,1984;ASSIGNOR:CONOCO INC.;REEL/FRAME:004349/0285 Effective date: 19840720 |