US3794579A - Process for treating by-product oils produced in the production of olefins - Google Patents

Process for treating by-product oils produced in the production of olefins Download PDF

Info

Publication number
US3794579A
US3794579A US00319138A US3794579DA US3794579A US 3794579 A US3794579 A US 3794579A US 00319138 A US00319138 A US 00319138A US 3794579D A US3794579D A US 3794579DA US 3794579 A US3794579 A US 3794579A
Authority
US
United States
Prior art keywords
fractions
pitch
product oils
treating
olefins
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
Application number
US00319138A
Other languages
English (en)
Inventor
S Enomoto
M Takahashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kureha Corp
Original Assignee
Kureha Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kureha Corp filed Critical Kureha Corp
Application granted granted Critical
Publication of US3794579A publication Critical patent/US3794579A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
    • 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
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment

Definitions

  • Thermally stabilized oil fractions and pitch fractions are obtained from by-product oils in the production of olefins which comprises heating the by-product oils at 400-600 C. for 10-1200 seconds under a pressure of 20-2000 kg./cm. to form thermally stabilized oil fractions and residue fractions and then treating the residue fractions at 300480 C., under a pressure of from normal pressure to 50 kg./cm. for 1-10 hours to provide useful pitch fractions.
  • the present invention relates to a process of treating by-product oils having boiling points of higher than 150 C. obtained during the production of olefins, and more particularly, the invention relates to a process of recovering useful thermally stabilized oil fractions and pitch fractions from the by-product oils obtained during the production of olefins.
  • One object of this invention is to provide a process for effectively utilizing by-product oils obtained in the production of olefins as described above, i.e., the primary object of this invention is to provide a process of treating such by-product oils to provide thermally stabilized oil fractions mainly composed of low boiling fractions such as naphthalene and methyl naphthalene and pitch fractions mainly composed of polycyclic aromatics.
  • the above object of this invention has been attained according to the process of this invention wherein the by-product oils having boiling points of higher than 150 C. obtained in the production of olefins are initially treated at temperatures of from 400-600 C. for"10 1200 seconds under a pressure of 20-200 kg./cm. the by-product oils thus treated are then separated into thermally stabilized oil fractions and residue fractions by means of flashing or distillation, and then the residue fractions are treated at temperatures of 300-480 C. for 1-10 hours under a pressure of from normal pressure to 50 kg./cm. to provide pitch fractions or components.
  • FIG. 2 shows a gas chromatographic analysis of the oil fractions obtained by the process of this invention 1n the same boiling point range.
  • oils used as a starting material in this invention are by-product oils in the production of olefins which means so-called ethylene bottom oils obtained in the case of producing olefins such as ethylene, propylene, etc.,
  • the lay-product oils are heated at temperatures of 400-600 C. for 10-1200 secs. under a pressure of 20-200 kg./cm. whereby the unsaturated bond portions of the by-product oils are thermally decomposed and stabilized, and at the same time the various alkyl chains are removed to provide oil fraction highly enriched with aromatics.
  • the above heat treatment is more preferably conducted at temperatures of 440-580 C. for 30-500 seconds and under a pressure of 50-150 kg./cm.
  • the heat treatment By the heat treatment, the content of the unsaturated bond portions, the unstable portions in the by-product oils, is greatly reduced and, at the same time, the long alkyl side chains are decomposed to provide high aromaticity.
  • the heat treatment requires no specific equipment and can be conducted using a conventional reactor such as a flow-type reactor. If desired, the above heat treatment may be conducted in two to four stages.
  • the second step operation in this invention comprises removing gaseous materials formed in the previous heat treatment and, at the same time, separating the thermally stabilized oil fractions or components from the residue fractions or components by any acceptable separation 3 whereby pitch fractions having a polycyclic aromatic structure are obtained.
  • the thermal stability of the oil fractions formed is insufficient, and thus only the heretofore described undesirable results are obtained. Further, in certain cases, a carbonization or coking occurs during the reaction which makes it impossible to further continue the reaction.
  • alkyl side chains have been decomposed, they can be used as intermediate raw materials for insulating oils, various solvents, etc.
  • the oil fractions con tain mainly naphthalene and methyl naphthalene as the low boiling components thereof, and these components can be easily separated as compared with the original by-product oils.
  • the oil fraction obtained can be used as intermediate materials and excellent pitch fractions are obtained.
  • the process of this invention thus has great industrial significance.
  • EXAMPLE 1 The by-product oil (so-called ethylene bottom oil) having the properties shown in Table 2 which was obtained in the production of olefins was subjected to a series of the first step reactions at the conditions shown in Table 3 in a flow-type tubular reactor having a diameter of 3.35 mm. and a length of 8 meters.
  • Invention- 50 510 35 5. 0 13. 8 41. 0 16. 0 7. 0 36. 0 0. 70 150 510 35 3. 1 11. 0 46. 0 8. 0 11. 0 35. 0 0. 68 150 480 35 3. 7 13. 6 44. 0 10. 0 11. 0 35. 0 0. 70 150 550 35 20. 1 9. 0 52. 0 7. 0 14. 0 27. 0 0. 150 600 35 32. 0 7. 3 52. 0 5. 0 13. 0 30. 0 0. 63 160 510 1 35x2 6. 4 7. 9 50. 0 7. 0 11. O 32. 0 0. 65 150 510 3 X3 40. 0 6. 8 53. 0 5. 0 9. 0 33. 0 0. 62 150 510 600 190.
  • Run F was a two-stage operation in which the first heat treatment was conducted for 35 seconds and then the same procedure was conducted thereafter.
  • each product obtained from the first step of the process of the present invention was subjected to the second or the separation step of the present invention at the conditions described in Table 4 in order to remove low boiling materials and recover the oil fractions.
  • T hereafter the residue fractions were subjected to the heat treatment of the third step of the present invention at the conditions shown in Table 4.
  • the oil fractions recovered in the second or separation step had, although the properties were slightly influenced by the conditions for the separation, a boiling range of 70-350 C., a specific gravity range of 0.9-4.0, and a refractive index range of lower than 1.68. Various physical measurements confirmed that they were aromatic oils having no long side chains. Among the oil fractions, the fractions having a boiling point range of 210-250" C. were almost totally composed of naphthalene and methyl naphthalene, and the two components could be easily separated from each other. This feature will further be was a three-stage operation in which the first heat treatment was conducted for 70 seconds and the explained by referring to the accompanying drawings.
  • FIG. 1 is a gas chromatographic chart of the raw materials or the by-product oils in the same boiling point range and FIG. 2 is a gas chromatographic chart of the oil fractions obtained by the process of this invention in the same boiling point range.
  • the gas chromatographic measurements were carried out with a K-53 Type Gas Chromatographic Analyzer made by Hitachi Ltd. under the following conditions: the length of the capillary column was 45 meters, the filler was Q-45 (silicone oil), the measurement temperature was C., the carrier gas was nitrogen and a flame ion detector (FID) was used.
  • the yield of oil fractions in this invention depends upon the properties of the raw materials, the conditions for the first process step, the separation conditions etc., but in general the yield is 30-50% by weight based on the amount of the raw materials.
  • the yield of naphthalene and mcthylnapthalene fractions was 20-40% by weight based on the amount of raw materials and the content of the two components in the oil fractions was in the range of 40-90% by weight of the weight of the oil fractions.
  • the pitch obtained by the process of this invention had excellent properties, for example, the-carbonization yield was high, the content of benzene insoluble components was high, the content of quinoline insoluble components was low, and the softening point was high.
  • the comparison tests shown in Table 4 as the T-Series Runs which were conducted under conditions outside the scope of this invention, good results could not be obtained,
  • the yield of the pitch fractions by the process of this invention depends, as a matter of course, upon the properties of the raw materials and the treatment conditions, but it was generally in the range of 40-60% by weight based on the amount of the raw materials.
  • the yield of pitch from the pitch fraction was usually in the range of 50-80% by weight of the pitch fractions.
  • a mixture of 100 parts of needle coke was prepared by coking the pitch fraction of Run No. 7 of the process of this invention and further heating it to 1300 C. 35 parts of coal pitch was extrusion-molded in an ordinary manner and then subjected to graphitization.
  • the thermal expansion coefficient of the product was 1.6 l0- at 300-800 C. This value was similar to the thermal expansion coefficient of the articles prepared using an imported needle coke (1.6-2.0 l0- While this invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
  • a process of treating by-product oils obtained in the production of olefins which comprises treating the byproduct oils having boiling points of higher than 150 C. at temperatures of 400-600 C., for 10-1200 seconds tgider pressures of -200 kg./cm. separating said treated by-product oils into thermally stabilized oil fractions and residue fractions, and treating said residue fractions at temperatures of 300-480 C., for 1-10 hours under pressures of from normal pressure to 50 kg./cm. to provide pitch fractions.
  • thermally stabilized oil fractions are mainly composed of naphthalene and methyl naphthalene and the pitch fractions are mainly composed of polycyclic aromatics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00319138A 1971-12-29 1972-12-29 Process for treating by-product oils produced in the production of olefins Expired - Lifetime US3794579A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP47003584A JPS5117563B2 (de) 1971-12-29 1971-12-29

Publications (1)

Publication Number Publication Date
US3794579A true US3794579A (en) 1974-02-26

Family

ID=11561487

Family Applications (1)

Application Number Title Priority Date Filing Date
US00319138A Expired - Lifetime US3794579A (en) 1971-12-29 1972-12-29 Process for treating by-product oils produced in the production of olefins

Country Status (7)

Country Link
US (1) US3794579A (de)
JP (1) JPS5117563B2 (de)
CA (1) CA953312A (de)
DE (1) DE2264034C3 (de)
FR (1) FR2169896B1 (de)
GB (1) GB1386270A (de)
IT (1) IT974350B (de)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928170A (en) * 1971-04-01 1975-12-23 Kureha Chemical Ind Co Ltd Method for manufacturing petroleum pitch having high aromaticity
US3970542A (en) * 1971-09-10 1976-07-20 Cindu N.V. Method of preparing electrode pitches
US4017378A (en) * 1973-11-12 1977-04-12 The British Petroleum Company Limited Binders for electrodes
FR2370784A1 (fr) * 1976-11-12 1978-06-09 Nippon Oil Co Ltd Procede de production continue de brai de petrole
US4108798A (en) * 1976-07-06 1978-08-22 The Lummus Company Process for the production of petroleum coke
US4175278A (en) * 1977-04-13 1979-11-20 Nippon Petrochemicals Company, Limited Electric insulating oil compositions
US4199434A (en) * 1974-10-15 1980-04-22 The Lummus Company Feedstock treatment
US4219404A (en) * 1979-06-14 1980-08-26 Exxon Research & Engineering Co. Vacuum or steam stripping aromatic oils from petroleum pitch
US4225414A (en) * 1979-02-26 1980-09-30 The United States Of America As Represented By The United States Department Of Energy Process for hydrocracking carbonaceous material to provide fuels or chemical feed stock
US4240898A (en) * 1978-12-12 1980-12-23 Union Carbide Corporation Process for producing high quality pitch
DE3022910A1 (de) * 1979-06-19 1981-01-29 Nippon Petrochemicals Co Ltd Oelimpraegniertes starkstromkabel
FR2507199A1 (fr) * 1981-06-09 1982-12-10 British Petroleum Co Procede de production de brai a partir de fractions petrolieres et brai obtenu
EP0200965A1 (de) * 1985-04-18 1986-11-12 Mitsubishi Oil Company, Limited Pech für die Herstellung von Kohlenstoffasern
US4645781A (en) * 1983-03-29 1987-02-24 Union Carbide Corporation Blends of cyclic vinyl ether containing compounds and expoxides
US11248172B2 (en) 2019-07-23 2022-02-15 Koppers Delaware, Inc. Heat treatment process and system for increased pitch yields

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5944352B2 (ja) * 1978-02-28 1984-10-29 ユニオン・カ−バイド・コ−ポレ−シヨン ピツチの製造法
JPS5788016A (en) * 1980-11-19 1982-06-01 Toa Nenryo Kogyo Kk Optically anisotropic carbonaceous pitch for carbon material, its manufacture, and manufacture of carbonaceous pitch fiber and carbon fiber
JPS61103989A (ja) * 1984-10-29 1986-05-22 Maruzen Sekiyu Kagaku Kk 炭素製品製造用ピツチの製造法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT127822B (de) * 1931-02-13 1932-04-25 Eugen Karpati Dr Verfahren zur Überführung von kreosotreichen Teeren in Straßenbaupech, Benzin und hochwertige Phenole.
US3537976A (en) * 1968-09-30 1970-11-03 Monsanto Co Process for preparing binder pitches
DE1815568A1 (de) * 1968-12-19 1970-06-25 Ruetgerswerke Ag Verfahren zur Gewinnung von aromatischen Kohlenwasserstoffen aus aromatenreichen OElen mit einem hohen Gehalt an ungesaettigten Verbindungen
DE2016276A1 (de) * 1970-04-06 1971-11-11 Rütgerswerke AG, 6000 Frankfurt Verfahren zur Herstellung von anisotropen, leicht graphitierbaren Koksen durch Schwelen von Gemischen weitgehend aromatischer Kohlenwasserstoffe

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928170A (en) * 1971-04-01 1975-12-23 Kureha Chemical Ind Co Ltd Method for manufacturing petroleum pitch having high aromaticity
US3970542A (en) * 1971-09-10 1976-07-20 Cindu N.V. Method of preparing electrode pitches
US4017378A (en) * 1973-11-12 1977-04-12 The British Petroleum Company Limited Binders for electrodes
US4199434A (en) * 1974-10-15 1980-04-22 The Lummus Company Feedstock treatment
US4108798A (en) * 1976-07-06 1978-08-22 The Lummus Company Process for the production of petroleum coke
FR2370784A1 (fr) * 1976-11-12 1978-06-09 Nippon Oil Co Ltd Procede de production continue de brai de petrole
US4177132A (en) * 1976-11-12 1979-12-04 Nippon Oil Company, Ltd. Process for the continuous production of petroleum-derived pitch
US4175278A (en) * 1977-04-13 1979-11-20 Nippon Petrochemicals Company, Limited Electric insulating oil compositions
US4240898A (en) * 1978-12-12 1980-12-23 Union Carbide Corporation Process for producing high quality pitch
US4225414A (en) * 1979-02-26 1980-09-30 The United States Of America As Represented By The United States Department Of Energy Process for hydrocracking carbonaceous material to provide fuels or chemical feed stock
US4219404A (en) * 1979-06-14 1980-08-26 Exxon Research & Engineering Co. Vacuum or steam stripping aromatic oils from petroleum pitch
DE3022910A1 (de) * 1979-06-19 1981-01-29 Nippon Petrochemicals Co Ltd Oelimpraegniertes starkstromkabel
FR2507199A1 (fr) * 1981-06-09 1982-12-10 British Petroleum Co Procede de production de brai a partir de fractions petrolieres et brai obtenu
US4645781A (en) * 1983-03-29 1987-02-24 Union Carbide Corporation Blends of cyclic vinyl ether containing compounds and expoxides
EP0200965A1 (de) * 1985-04-18 1986-11-12 Mitsubishi Oil Company, Limited Pech für die Herstellung von Kohlenstoffasern
US11248172B2 (en) 2019-07-23 2022-02-15 Koppers Delaware, Inc. Heat treatment process and system for increased pitch yields
US11624029B2 (en) 2019-07-23 2023-04-11 Koppers Delaware, Inc. Heat treatment process for increased pitch yields

Also Published As

Publication number Publication date
FR2169896B1 (de) 1978-09-29
DE2264034A1 (de) 1973-07-05
CA953312A (en) 1974-08-20
JPS5117563B2 (de) 1976-06-03
DE2264034B2 (de) 1977-10-27
IT974350B (it) 1974-06-20
GB1386270A (en) 1975-03-05
DE2264034C3 (de) 1983-12-01
JPS4873405A (de) 1973-10-03
FR2169896A1 (de) 1973-09-14

Similar Documents

Publication Publication Date Title
US3794579A (en) Process for treating by-product oils produced in the production of olefins
US3487006A (en) Direct pyrolysis of non-condensed gas oil fraction
US2953513A (en) Hydrogen donor diluent cracking process
US3718709A (en) Process for producing ethylene
US1995136A (en) Production of hydrocarbons rich in carbon from those poorer in carbon
US4655904A (en) Thermal cracking process for selectively producing olefins and aromatic hydrocarbons from hydrocarbons
US3676519A (en) Quench process
AU2013301887B2 (en) Process for converting hydrocarbon feeds to olefin-containing product streams by thermal steamcracking
US3692663A (en) Process for treating tars
JP2015528820A (ja) 分解炉における熱水蒸気分解によってオレフィンを製造する方法
US2905622A (en) Production of fuel gas and liquid hydrocarbon fuels
US2453044A (en) Process for producing cyclopentadiene and its homologues
US3907920A (en) Two-stage hydropyrolysis-cracking process for producing ethylene
US3796768A (en) Combined wulff process and coking process
US4235702A (en) Hydrocarbon processing
US3326796A (en) Production of electrode grade petroleum coke
US4171345A (en) Method of manufacture of reinforcing carbon black
US4240898A (en) Process for producing high quality pitch
JPS6158514B2 (de)
US3436318A (en) Solvent purification by distillation with a hydrocarbon oil
US3537976A (en) Process for preparing binder pitches
US3023843A (en) Acetylene purification
GB929136A (en) Improvements in or relating to the production of acetylene and ethylene
SU470118A3 (ru) Способ переработки смол пиролиза с температурой начала кипени не ниже 150 с
CA1067106A (en) Process for producing ethylene from higher hydrocarbons