US3654135A - Process for obtaining aromatic hydrocarbons from oils and/or their residues rich in aromatic hydrocarbons and having a high content of unsaturated compounds - Google Patents
Process for obtaining aromatic hydrocarbons from oils and/or their residues rich in aromatic hydrocarbons and having a high content of unsaturated compounds Download PDFInfo
- Publication number
- US3654135A US3654135A US883591A US3654135DA US3654135A US 3654135 A US3654135 A US 3654135A US 883591 A US883591 A US 883591A US 3654135D A US3654135D A US 3654135DA US 3654135 A US3654135 A US 3654135A
- Authority
- US
- United States
- Prior art keywords
- aromatic hydrocarbons
- oils
- compounds
- naphthalene
- oil
- 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
- 239000003921 oil Substances 0.000 title abstract description 50
- 150000001875 compounds Chemical class 0.000 title abstract description 23
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title abstract description 11
- 238000000034 method Methods 0.000 title description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 56
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 24
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 18
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 abstract description 16
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract description 14
- 238000002425 crystallisation Methods 0.000 abstract description 8
- 230000008025 crystallization Effects 0.000 abstract description 8
- 238000007669 thermal treatment Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000004508 fractional distillation Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000011280 coal tar Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- ANSIWEGOCFWRSC-UHFFFAOYSA-N 1,2-dimethyl-1h-indene Chemical compound C1=CC=C2C(C)C(C)=CC2=C1 ANSIWEGOCFWRSC-UHFFFAOYSA-N 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000009997 thermal pre-treatment Methods 0.000 description 3
- FIPKSKMDTAQBDJ-UHFFFAOYSA-N 1-methyl-2,3-dihydro-1h-indene Chemical compound C1=CC=C2C(C)CCC2=C1 FIPKSKMDTAQBDJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100168115 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) con-6 gene Proteins 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- LHEOFIBQZSRTNC-UHFFFAOYSA-N phenanthrene-3-carbaldehyde Chemical compound C1=CC=C2C3=CC(C=O)=CC=C3C=CC2=C1 LHEOFIBQZSRTNC-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 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
- 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
- Aromatic compounds e.g., naphthalene, phenanthrene, anthracene, durene, are obtained in increased yields from oils and/or residues rich in aromatic compounds and having a high content of unsaturated compounds, by pretreating said oils or residues by a thermal treatment at increased temperature in the range of 300-500 C. and at an excess pressure of 4-30 atmospheres, subjecting the pretreated material to fractional distillation and recovering the aromatic hydrocarbons from their fractions by cooling and crystallization.
- these oils and residues differ from coal tar, among other respects, by their relatively high content of unsaturated, olefinic and aromatic-olefinic compounds. These unsaturated components make the recovery of aromatic compounds from said oils according to conventional methods rather difi'icult, or prevent it entirely, essentially for the following reasons:
- Said oils and residues rich in aromatic compounds contain said unsaturated compounds in addition to the compounds found in coal tar and they are, therefore, with respect to hydrocarbons, more complex mixtures than coal tar.
- the unsaturated components have an excellent dissolving power for aromatic hydrocarbons, due to which the separation of crystalline material from the respective fractions is made difiicult and in some cases entirely prevented.
- nents form polymers, the presence of whichin contrast to the presence of monomersdoes not adversely influonce processing.
- said polymers remain in the sump product and can be easily separated from the hydrocarbons to be isolated.
- the hot sump product is immediately drawn off from the distillation column, because the polymers formed would be in part depolymerized again under the existing conditions of temperature and pressure. Said depolymerization is preferably permitted to take place subsequently in a separate equipment.
- the thermal polymerization of the unsaturated compounds present in oils and residues of varying origin can be carried out at temperatures between 300 and 500 C., preferably 350 to 400 C. and a pressure of 4 to 30 atmospheres.
- the reaction periods are relatively short. In most cases, the process is already completed after 10 to 60 minutes. Disturbing attendant phenomena, e.g., clogging of the apparatus by the polymeric ingredients formed, do not occur.
- the monomers polymerized by the thermal pre-treatment can be partially recovered from the pitch withdrawn from the distillation column, namely as unsaturated compounds, compounds saturated by addition of hydrogen or as compounds formed by cracking reactions.
- the pitch flows with a temperature of 300 to 320 C. through a waste pipe into a storage vessel provided with a vapor condenser.
- the polymers formed by the pressure and heat treatment and present in the pitch are here depolymerized at a pressure of 1 atmosphere and the secondary light oil distills off without additional sup ply of heat.
- the distillate is obtained in an amount of 1 to 2%, based on the crude residual oil and has the following composition:
- EXAMPLE 2 The naphthalene oil obtained from an oil residue treated at 380 C., has a crystallization point of 71 C. and the following composition:
- the naphthalene oil obtained from said oil residue treated at 280-290 C. only has a crystallization point of 60 C. and the following composition:
- Percent Phenanthrene 22 From said crystallized product phenanthrene and a n thracene can be isolated by conventional methods. For example, by two recrystallizations from the fourfold to fivefold amount of pyridine, anthracene is obtained in a yield of with a degree of purity of 98% (according to Montecatini). 13y redistillation of the mother liquor, the phenanthrene present therein is obtained with a degree of purity of (determined by gas-chromatography). The yield can be further increased by subjecting the anthracene oil once again to rectification, prior to crystallization.
- EXAMPLE 4 500 parts of a naphthalene-containing oil which has been obtained from a residual oil rich in aromatic compounds as filtrate oil, are treated under superatmospheric pressure at 350 C. for 40 minutes. Prior to the thermal treatment, the oil has the following compositions:
- composition is as follows:
- the oil, thermally pretreated in this manner, is distilled under normal atmospheric pres sure. From the fraction boiling between to 220 C., by centrifuging at ordinary room temperature, e.g., 18- 25 C., 49.5 parts by weight of durene having a melting point of 79 C. are obtained. This corresponds to a yield of 55%, based on the durene present in the material treated.
- the recitation oil residue rich in aromatic compounds derived from pyrolysis of benzine to ethylene is used to denote an oil residue obtained by pyrolysis of crude benzine, at temperatures of 750-1000 C. to form ethylene, propylene and other gaseous hydrocarbons, pyrolysis benzine boiling up to about 180 C. and a residual oil boiling above 180 C. and rich in aromatic compounds.
- K.S. stands for Kraemer-Sarnow whose method for measuring the softening point is Well known in the art, see e.g. DIN 1995, February 1960, p. 18.
- the vacuum distillation can be carried out in the range of 50 to 760 torr. The parts and percent are by weight, it not otherwise stated.
- the starting material, used in the above Examples 2-5, is a residue obtained in cracking and processing hydrocarbon oils rich in aromatic compounds, and having a high content of unsaturated olefinic and aromatic-olefinic compounds.
- any hydrocarbon oil or its residue rich in aromatic compounds, and having a high content of unsaturated olefinic and/or aromatic-olefinic compounds can be used as starting material in carrying out the invention.
- a process for obtaining aromatic hydrocarbons from a starting material selected from the group consisting of oils and residues of oils, rich in aromatic hydrocarbons and having a high content of unsaturated olefinic and aromatic-olefinic compounds consisting in subjecting said starting material to a non-catalytic heat treatment at temperatures in the range of 300 to 500 C., under a pressure of 4 to 30 atmospheres during to 60 minutes in order to convert the unsaturated compounds into polymers; causing the material thus treated in direct sequence by release of the pressure to evaporate from said polymers and separating the polymers formed; distilling and con- 6 densing the rest of the material and recovering the aromatic hydrocarbons by cooling and crystallization from the condensed fractions.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681815568 DE1815568A1 (de) | 1968-12-19 | 1968-12-19 | Verfahren zur Gewinnung von aromatischen Kohlenwasserstoffen aus aromatenreichen OElen mit einem hohen Gehalt an ungesaettigten Verbindungen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3654135A true US3654135A (en) | 1972-04-04 |
Family
ID=5716671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US883591A Expired - Lifetime US3654135A (en) | 1968-12-19 | 1969-12-09 | Process for obtaining aromatic hydrocarbons from oils and/or their residues rich in aromatic hydrocarbons and having a high content of unsaturated compounds |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3654135A (cs) |
| JP (1) | JPS4945862B1 (cs) |
| BE (1) | BE743300A (cs) |
| CS (1) | CS185556B2 (cs) |
| DE (1) | DE1815568A1 (cs) |
| FR (1) | FR2026543A1 (cs) |
| GB (1) | GB1261977A (cs) |
| NL (1) | NL160874C (cs) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3951780A (en) * | 1974-10-25 | 1976-04-20 | Exxon Research And Engineering Company | Aromatic oils by thermal polymerization of refinery streams |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5117563B2 (cs) * | 1971-12-29 | 1976-06-03 | ||
| JPS53768A (en) * | 1976-06-24 | 1978-01-06 | Tokai Seiki Kk | Filing wheel for lighter |
| JPS53110270U (cs) * | 1977-02-07 | 1978-09-04 | ||
| DE3227490A1 (de) * | 1982-07-23 | 1984-01-26 | EC Erdölchemie GmbH, 5000 Köln | Verfahren zur herstellung von rein-naphthalin |
| DE3334842A1 (de) * | 1983-09-27 | 1985-04-04 | Rütgerswerke AG, 6000 Frankfurt | Verfahren zur herstellung thermisch stabiler peche und oele aus hocharomatischen petrochemischen rueckstaenden und deren verwendung |
| CN114989850B (zh) * | 2022-06-06 | 2024-05-03 | 中建安装集团有限公司 | 一种重质乙烯焦油高效转化工艺及装置 |
-
1968
- 1968-12-19 DE DE19681815568 patent/DE1815568A1/de active Pending
-
1969
- 1969-11-14 JP JP44090883A patent/JPS4945862B1/ja active Pending
- 1969-12-05 CS CS6900008015A patent/CS185556B2/cs unknown
- 1969-12-09 US US883591A patent/US3654135A/en not_active Expired - Lifetime
- 1969-12-15 GB GB61047/69A patent/GB1261977A/en not_active Expired
- 1969-12-15 NL NL6918747.A patent/NL160874C/xx not_active IP Right Cessation
- 1969-12-17 FR FR6943750A patent/FR2026543A1/fr not_active Withdrawn
- 1969-12-17 BE BE743300D patent/BE743300A/xx not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3951780A (en) * | 1974-10-25 | 1976-04-20 | Exxon Research And Engineering Company | Aromatic oils by thermal polymerization of refinery streams |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2026543A1 (cs) | 1970-09-18 |
| NL6918747A (cs) | 1970-06-23 |
| BE743300A (cs) | 1970-05-28 |
| JPS4945862B1 (cs) | 1974-12-06 |
| NL160874C (nl) | 1979-12-17 |
| GB1261977A (en) | 1972-02-02 |
| CS185556B2 (en) | 1978-10-31 |
| DE1815568A1 (de) | 1970-06-25 |
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