EP0138286B1 - Verfahren zur Aufbereitung kohlenstoffhaltiger Teere - Google Patents
Verfahren zur Aufbereitung kohlenstoffhaltiger Teere Download PDFInfo
- Publication number
- EP0138286B1 EP0138286B1 EP84303407A EP84303407A EP0138286B1 EP 0138286 B1 EP0138286 B1 EP 0138286B1 EP 84303407 A EP84303407 A EP 84303407A EP 84303407 A EP84303407 A EP 84303407A EP 0138286 B1 EP0138286 B1 EP 0138286B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pitch
- mesophase
- raw material
- weight
- fibers
- 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
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
Definitions
- This invention relates to a method of preparing a carbonaceous pitch useful for use as a precursor material for carbon fibers.
- the general method for the production of carbon fibers from carbonaceous pitch includes melt spinning pitch into fibers, rendering the spun fibers infusible, and carbonizing the infusible fibers.
- the properties of the raw material pitch are very important. The most important requirement is that the pitch must have a good spinnability. It is also important that the pitch must have properties so that the spun fibers obtained therefrom may be rendered infusible and carbonized without difficulty.
- Pitch which can meet with the above criteria has been hitherto considered to be of a type which is obtained by carefully thermally treating a raw material oil, such as a naphtha cracking residue, a recycle oil in fluidized bed catalytic cracking processes or a coal tar, which has a high content of aromatic components and a low content of impurities such as metals, inorganic matters and sulfur components.
- a raw material oil such as a naphtha cracking residue, a recycle oil in fluidized bed catalytic cracking processes or a coal tar, which has a high content of aromatic components and a low content of impurities such as metals, inorganic matters and sulfur components.
- Example 4 of EP-A-0057108 a raw material oil having a boiling point of 480°-540°C and obtained by reduced pressure distillation of a tarry substance by-produced in the catalytic cracking of petroleum, is subjected to thermal cracking conditions while removing light hydrocarbon components, to form a pitch which, after further treatment to increase the mesophase, had almost 100% optically anisotropic phase (mesophase).
- the resulting pitch product is then suitable for spinning into fibers.
- naphthenic or intermediate raw material oil composed mainly of a residual oil having a boiling point of 350°C or more and being obtained from fractionation of a naphthene base and/or intermediate base petroleum crude
- the substantially mesophase-free carbonaceous pitch obtained as a filtrate is very thermally stable. When heated above its melting point, for example at a temperature of about 300°C, no mesophase is newly formed. Fine mesophase particles which failed to be removed during the filtration step and which may trace be present in the carbonaceous pitch never grow in size to the extent that they adversely affect the spinnability of the pitch. Further, the amount of the low molecular weight components in the carbonaceous pitch is small and the molecular weight of the pitch is distributed in relatively high and narrow range. All of the above properties of the carbonaceous pitch allow the use thereof as precursor materials for the production of carbon fibers.
- the rate at which the pitch is formed becomes low.
- the resulting pitch is not thermally stable and coking is liable to occur during the thermal cracking step.
- the mesophase spheres tend to coalesce with each other to form large mesophase particles having a diameter of between 200 and 1000 11 m.
- the mesophase particles which are heterogeneously distributed in the matrix of isotropic pitch are very difficult to separate from the matrix by filtration in the molten state.
- the fine particles of mesophase contained in the filtrate can coalesce with each other to form large mesophase particles which adversely affect the spinnability of the pitch.
- the raw material oil used in the process of the present invention is an oil composed mainly of a residual oil which has a boiling point of 350°C or more and which is derived from a naphthene base and/or intermediate base petroleum crude.
- the terms "naphthene base petroleum crude” and “intermediate base petroleum crude” used herein are defined by UOP characterization factor classification method as crude oil having characterization factor K of between 11.0 and 11.5 and between 11.5 and 12.0, respectively.
- the characterization factor K is expressed by: where T B stands for a molar average boiling point in terms of Rankine temperature (°F+460) and S stands for a specific gravity at 60°F of the distillate.
- naphthene base crude oils are California crude, Coalinga crude, Texas crude, Ba mangoro crude, Merey crude, Boscan crude, Maya crude, Klamono crude, Seria crude and Nigeria crude.
- suitable intermediate base crude oils are Egyptian Heavy crude, Murban crude, Sassan crude, Dovai crude, Midcontinent crude and North slope crude.
- residual oil from naphthene base or intermediate base petroleum crude is intended to mean a heavy fraction, such as an atmospheric residue, a vacuum residue, a vacuum distillate or asphalt from a solvent deasphalting process, having a boiling point of 350°C or more preferably 500°C or more.
- the asphalt from a solvent deasphalting process is that obtained by subjecting a residual oil such as an atmospheric residue to extraction treatment using as an extraction solvent propane, butane, pentane, etc.
- a residual oil containing at least 200 ppm, more preferably at least 500 ppm of metal components such as nickel and vanadium is used for the purpose of the present invention.
- Residual oils having a large residual carbon content (Conradson carbon residue) and/or a large amount of sulfur components may be used for the purpose of the present invention.
- the use of a residual oil having a large amount of residual carbon is rather preferred since the yield of pitch becomes higher with the increase of the residual carbon content.
- the above-described residual oils generally belong to poor grade heavy hydrocarbon oils and have been regarded as being unsuited for the production of carbon fibers.
- the raw material oil can contain other residual oils, such as those derived from Arabian crude, Arabian Heavy crude, Kuwait crude and Oman crude, than those derived from naphthene base or intermediate base petroleum crude.
- the content of the residual oil derived from naphthene base and/or intermediate base petroleum crude in the raw material oil is preferably 30 weight % or more, more preferably 50 weight % or more. It is especially preferred that the raw material oil always contains a residual oil derived from naphthene base petroleum crude in an amount of 45 weight % or more, most preferably 60 weight % or more. It is also preferred that the residual oil derived from naphthene base petroleum crude be contained in the raw material oil in an amount so that at least half of the pitch obtained by the thermal cracking step is composed of components derived from the naphthene base petroleum crude.
- the raw material oil is thermally cracked, while removing, generally continuously, cracked light hydrocarbons, at a temperature of between about 350 and 500°C, preferably between 400 and 440°C so that a pitch is formed by polycondensation and other reactions inherent to the thermal cracking. It is preferred that the removal of the cracked light hydrocarbon products be conducted by maintaining the reaction zone under a reduced pressure for the evaporation of the light hydrocarbons formed by the thermal cracking or by continuously feeding a gaseous heat transfer medium to the reaction zone for contact with the raw material oil.
- the heat transfer medium serves both to supply heat necessary for effecting the thermal cracking and to strip volatile cracked products and is preferably a substantially oxygen-free, non-oxidative gas such as steam, a hydrocarbon gas or vapor, a perfect combustion waste gas, nitrogen or hydrogen.
- the thermal cracking is performed in a liquid phase under a reduced pressure, generally at a pressure of between 5 and 500 mmHg (absolute) or under a partial pressure of hydrocarbon vapor of between 5 and 500 mmHg.
- the raw material oil contains relatively low boiling point fractions (boiling at 350 ⁇ 500°C) such as atmospheric residue or vacuum distillate (VGO)
- the early stage of the thermal cracking may be suitably effected under a pressure of generally between 1 and 10 Kg/cm 2 so as to increase the yield of the pitch.
- the reaction time is generally in the range of between 0.3 and 10 hours, though the reaction time varies according to the kind of the raw material oil to be thermally cracked.
- the thermal cracking may be carried out with the use of any known liquid phase cracking reactors in a continuous, batch or semi-batch (generally adopted in Eureka process) mode.
- the thermal cracking is conducted so that the pitch product contains at least 5 weight %, generally between 5 and 40 weight %, preferably between 10 and 25 weight % of mesophase and not more than 10 weight %, preferably not more than 5 weight % of light hydrocarbon components with a boiling point at 60 mmHg (absolute) of 300°C or less and has a softening point of between 140 and 220°C, preferably between 170 and 210°C.
- the thermal cracking should be conducted at a temperature and for a period of time so that at least 5 weight % of mesophase is formed. If the thermal cracking is stopped before the formation of mesophase, the molecular weight of the resulting pitch is too small to give spun fibers of a satisfactory strength. The formation of at least 5 weight % of mesophase is necessary to obtain a pitch suitable for spinning into fibers.
- the content of the light fraction is also important for the pitch to have a suitable spinnability.
- the content of light hydrocarbon components above 10 weight % is disadvantageous because the pitch fibers tend to be broken during spinning and because it becomes difficult to render the spun fibers infusible.
- the content of the light hydrocarbon components in the pitch can be controlled by adjusting the feed rate of the gaseous heat transfer medium or the degree of vacuum pressure.
- softening point of the pitch product When the softening point of the pitch product is below 140°C, the stability of the carbonaceous pitch obtained by removal of mesophase therefrom becomes poor and it becomes also difficult to render the spun fibers infusible. A softening point of the pitch product above 220°C is also undesirable because the pitch product will have a greater amount of mesophase, resulting in the decrease in yield of the carbonaceous pitch. Too high a softening point also makes the spinning operation difficult to perform.
- the term "softening point" used in the present specification is measured by means of a Koka-type flow tester manufactured by Shimadzu Seisakusho Co. Ltd., and is a temperature at which the sample commenced to flow through a nozzle having a diameter of 1 mm when heated at a rate of 6°C/min under a pressure of 10 Kg/ cm 2 .
- the thus obtained pitch product containing mesophase dispersed in the matrix of isotropic pitch is then subjected to a solid-liquid separation treatment for the removal of the mesophase and to obtain substantially mesophase-free carbonaceous pitch.
- substantially mesophase-free herein is intended to mean that the pitch contains no mesophase having a particle size of 10 11m or more. Mesophase particles having a particle size of less than 10 11m do not adversely affect the spinnability of the carbonaceous pitch and, therefore, the presence of such fine mesophase particles in the carbonaceous pitch can be ignored for the purpose of the present invention.
- a polarized light microscopy reveals that the mesophase contained in the pitch product has a mosaic structure composed of very fine particle units having a diameter of between 1 and 5 11m.
- the fine particle units aggregate during the thermal cracking to form botryoidal, aggregated particles with a size of between 25 and 150 11m homogeneously dispersed in the matrix of isotropic pitch.
- the mesophase particles or their aggregated particles do not coalesce with each other. Therefore, at a temperature above the melting point of the isotropic matrix but below the softening point of the mesophase, generally at a temperature of between 250 and 400°C, the mesophase can be easily separated by filtration in the form of a cake.
- the formation of such easily separable mesophase is considered to be ascribed to the use of the specific raw material oil.
- the mesophase pitch particles or their aggregated particles obtained in accordance with the present invention have a relatively small particle size and are homogeneously dispersed in the matrix of isotropic pitch which, in molten state, has a relatively high viscosity.
- the mesophase obtained from the paraffin base petroleum crude has a large particle size, generally of between 200 and 1000 ⁇ m and does not form a cake when filtered.
- the filtrate will contain mesophase particles having a particle size of 30 um or more as well as fine mesophase particles. Thus, it is not possible to obtain a substantially mesophase-free carbonaceous pitch by filtration of the pitch product obtained from the paraffin base petroleum crude.
- the mesophase separated by filtration from the pitch product contains a large amount of quinoline insolubles and, further, a larger amount of nickel, vanadium and other metal components than the filtrate does.
- the metal components contained in the raw material oil are caught by or bound to mesophase, such as in the form of organo-metallic salts or porphyrin complexes, to form fine, quinoline insoluble-rich, higher softening point (than the isotropic matrix), solid-like mesophase particles.
- mesophase such as in the form of organo-metallic salts or porphyrin complexes
- the removal of mesophase from the pitch product may be suitably performed by filtration, by application of a pressure or under reduced pressure, at an elevated temperature.
- Other solid-liquid separation methods such as centrifuge and sedimentation may also be used.
- a high gradient magnetic separation method or an electrical method may be adopted for the separation of the mesophase.
- the presence of mesophase particles having a diameter of less than 10 um does not adversely affect the subsequent spinning operation, oxidation treatment for rendering the spun fibers infusible and carbonizing treatment. Therefore, it is not necessary to remove such fine mesophase particles. However, it is of course desirable to remove as much mesophase as possible.
- the carbonaceous pitch do not contain mesophase particles having a diameter of 5 11m or more.
- the filtrate obtained by the removal of mesophase contains about 2 weight % or less of fine mesophase particles.
- the substantially mesophase-free carbonaceous pitch obtained by the method of the present invention has a H/C (a hydrogen to carbon atomic ratio) of between 0.55 and 1.2, a high molecular weight, a narrow molecular weight distribution and a good thermal stability.
- the pitch In the molten state, the pitch is in a single phase.
- the pitch is soluble in quinoline and is isotropic in nature. The pitch has thus a very excellent spinnability and can be spun into fibers at a high spinning rate.
- the carbonaceous pitch obtained by the method of the present invention is latently optically anisotropic and can give carbon fibers having a high mechanical strength.
- the carbonaceous pitch thus obtained can be subjected once or more times to thermal cracking and subsequent mesophase removal treatments to control the molecular weight of the carbonaceous pitch and to reduce the amount of metal components in the carbonaceous pitch.
- the carbon fibers can be up-graded by such repeated treatments.
- the substantially mesophase-free pitch obtained by the method of this invention can be spun into fibers at a temperature of between 250 and 310°C at a high spinning rate in any known manner.
- the spun fibers are then heat-treated, generally at a temperature of up to 300°C in the conventional manner in the oxidizing atmosphere such as in the atmosphere of air or N0 2 -containing air for rendering the spun fibers infusible.
- the infusible fibers are then carbonized in the conventional manner, generally at a temperature of 1000°C or more to obtain carbon fibers.
- the substantially mesophase-free pitch as obtained is optically isotropic in nature, it becomes optically anisotropic during the spinning step because of the orientation of latently optically anisotropic components in the pitch in the direction parallel to the fiber axis. Therefore, the resultant carbon fibers exhibit both a high tensile strength and a high modulus as compared with the conventional isotropic pitch.
- the pitch of the present invention is especially suited as precursor materials for carbon fibers, it is also utilizable in the same way as the conventional pitch, for example, as a raw material for graphite.
- Venezuelan Ba Ceialica being a naphthene base petroleum crude, was distilled at atmospheric pressure and the bottom was subjected to vacuum distillation to obtain, with a yield of 45.3 vol %, a residual oil whose physical properties are shown in Table 1.
- the pitch was found, by polarized light microscopy, to contain mesophase in an amount of 20% in terms of the area of polarized domain.
- the mesophase had a mosaic structure composed of very fine mesophase particle units having a diameter of 1-6 iam.
- the mesophase units formed aggregated particles of a botyroidal shape having a size of 50-100 pm.
- 100 g of the mesophase pitch was heated to 300°C in the atmosphere of nitrogen and filtered using 500 mesh metal sieve having an effective area of 25 cm 2 under a reduced pressure of 10 mmHg (absolute), whereby 55 g of a filtrate was obtained.
- the filtration was able to be conducted easily and within a short period of time.
- the filtrate was found by polarized light microscopy to contain almost no mesophase and to be optically isotropic.
- the pitch had a softening point of 179°C and contained 46.5 weight % of volatile matters, 0.1 weight % of quinoline insoluble matters and 2030 wt-ppm of metal components (Ni and V).
- aromatic hydrogen aliphatic hydrogen
- naphthenic hydrogen are intended to refer to hydrogen atoms bonded to an aromatic carbon atom, an aliphatic carbon atom and a naphthenic carbon atom, respectively, and the greek letters are assigned to non-aromatic carbon atoms, i.e. aliphatic and naphthenic carbon atoms, in which the enumeration starts with each of the aliphatic and naphthenic carbon atoms located adjacent to aromatic carbon atoms.
- the filtrate was spun into fibers through a nozzle having a diameter of 0.3 mm and a UD of 3.
- the spinning was performed at a temperature of 280°C and a spinning pressure of 1.8 Kg/cm 2 G. Fibers having a diameter of about 15 ⁇ m were obtained at a rate of 500 m/min in an extremely stable manner.
- the spun fibers were then heated from 100 to 150°C at a heating rate of 1°C/min in the atmosphere of air containing 1% of NO 2 . After being maintained at 150°C for 30 min, the fibers were heated up to 250°C at a heating rate of 1°C/min in the air and finally maintained at 250°C for 30 min so that the fibers were rendered infusible.
- the infusible fibers were then heated at a rate of 5°C/min to 1000°C and maintained at that temperature for 30 min for carbonization.
- the resultant carbon fibers had a diameter of 14 pm, a tensile strength of 13 ton/cm 2 , a modulus of 340 ton/cm 2 and an elongation of 3.0%.
- the yield of the carbon fibers on the basis of the pitch was about 72 weight %.
- the pitch was found, by polarized light microscopy, to contain mesophase of a mosaic structure.
- the particle units constituting the mesophase were found to contain those having a diameter of over 10 pm.
- the mesophase particles were aggregated with each other to form botryoidal particles having a size of 200-1000 ⁇ m and being dispersed in the pitch.
- the pitch was found to contain about 30% of mesophase by polarized light microscopy.
- the pitch was spun using the same nozzle as used in Example 1 at a spinning temperature of 285°C, a spinning pressure of 1.5 Kg/cm 2 G and a spinning rate of 400 m/min.
- the spinning operation was very difficult to perform because of frequent breakage of the spun fibers.
- the spun fibers were then rendered infusible and carbonized in the same manner as that in Example 1 to obtain carbon fibers having a diameter of 24 pm, a tensile strength of 6 ton/cm 2 , a modulus of 371 ton/cm 2 and an elongation of 1.9%.
- a mixed oil having the formulation shown in Table 7 was distilled at atmospheric pressure and the bottom was subjected to vacuum distillation to obtain a residual oil having a boiling point of above 538°C with a yield of 34 vol %.
- One Kg of the residual oil obtained from the mixed oil was thermally cracked in the same manner as that in Example 1 to obtain 5 weight % of cracked gases, 60 weight % of cracked oils and 33 weight % of pitch. The cracking was performed for 75 min.
- the pitch had the properties shown in Table 10.
- Polarized light microscopy of the pitch revealed the presence of fine mesophase particles in the mosaic structure.
- the fine particles having a diameter of 1-6 um formed botryoidal, aggregated particles having a diameter of 50-100 pm homogeneously dispersed in the pitch.
- the mesophase content was about 25% when determined by polarized light microscopy.
- Example 2 100 g of the pitch was then filtered in the same manner as in Example 1 to obtain 50 g of a filtrate.
- the solids phase (mesophase) separated formed a cake with a thickness of about 10 mm on the metal sieve. The separation by filtration was able to be carried out smoothly and easily.
- the filtrate was found to contain almost no mesophase as a result of polarized light microscopic observation.
- the filtrate was substantially isotropic in nature and had a softening point of 179°C, a volatile matter content of 43.8 weight %, a quinoline insoluble content of 0.8 weight % and a metal content (Ni and V) of 1200 ppm.
- the filtrate was then spun into fibers with the use of the same spinning device as used in Example 1.
- the spinning was performed at a spinning temperature of 280°C, a spinning pressure of 1.8 Kg/cm 2 and a spinning rate of 500 m/min.
- the spun fibers had a diameter of about 15 pm and were thermally stable.
- the spun fibers were then rendered infusible and carbonized in the same manner as in Example 1 to obtain carbon fibers having a diameter of 14 pm, a tensile strength of 9.2 ton/cm 2 , a modulus of 360 ton/cm 2 and an elongation of 2.8%.
- the yield of the carbon fibers was about 75 weight % based on the pitch.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
- Inorganic Fibers (AREA)
Claims (8)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP88775/83 | 1983-05-20 | ||
JP58088775A JPS59216921A (ja) | 1983-05-20 | 1983-05-20 | 炭素繊維の製造方法 |
JP24679/84 | 1984-02-13 | ||
JP59024679A JPS60168787A (ja) | 1984-02-13 | 1984-02-13 | ピツチの製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0138286A1 EP0138286A1 (de) | 1985-04-24 |
EP0138286B1 true EP0138286B1 (de) | 1988-01-13 |
Family
ID=26362234
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84303407A Expired EP0138286B1 (de) | 1983-05-20 | 1984-05-18 | Verfahren zur Aufbereitung kohlenstoffhaltiger Teere |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0138286B1 (de) |
DE (1) | DE3468696D1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8141636B2 (en) | 2007-08-17 | 2012-03-27 | ExxoonMobil Upstream Research Company | Method and system integrating thermal oil recovery and bitumen mining for thermal efficiency |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112852464B (zh) * | 2021-01-13 | 2022-05-10 | 中国石油大学(华东) | 一种可纺中间相沥青和高性能沥青基碳纤维制备用原料油的预处理方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4219404A (en) * | 1979-06-14 | 1980-08-26 | Exxon Research & Engineering Co. | Vacuum or steam stripping aromatic oils from petroleum pitch |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5930192B2 (ja) * | 1980-12-15 | 1984-07-25 | 富士スタンダ−ドリサ−チ株式会社 | 潜在的異方性ピツチ |
US4363715A (en) * | 1981-01-14 | 1982-12-14 | Exxon Research And Engineering Co. | Production of carbon artifact precursors |
JPS57125289A (en) * | 1981-01-28 | 1982-08-04 | Toa Nenryo Kogyo Kk | Preparation of optically anisotropic carbonaceous pitch |
US4427530A (en) * | 1982-02-08 | 1984-01-24 | Exxon Research And Engineering Co. | Aromatic pitch derived from a middle fraction of a cat cracker bottom |
JPS58164687A (ja) * | 1982-03-24 | 1983-09-29 | Toa Nenryo Kogyo Kk | 光学的異方性ピツチの製造方法 |
US4518482A (en) * | 1982-07-19 | 1985-05-21 | E. I. Du Pont De Nemours And Company | Pitch for direct spinning into carbon fibers derived from a coal distillate feedstock |
-
1984
- 1984-05-18 EP EP84303407A patent/EP0138286B1/de not_active Expired
- 1984-05-18 DE DE8484303407T patent/DE3468696D1/de not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4219404A (en) * | 1979-06-14 | 1980-08-26 | Exxon Research & Engineering Co. | Vacuum or steam stripping aromatic oils from petroleum pitch |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8141636B2 (en) | 2007-08-17 | 2012-03-27 | ExxoonMobil Upstream Research Company | Method and system integrating thermal oil recovery and bitumen mining for thermal efficiency |
Also Published As
Publication number | Publication date |
---|---|
DE3468696D1 (en) | 1988-02-18 |
EP0138286A1 (de) | 1985-04-24 |
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