US3663428A - Process for producing alkylated tars - Google Patents

Process for producing alkylated tars Download PDF

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Publication number
US3663428A
US3663428A US11904A US3663428DA US3663428A US 3663428 A US3663428 A US 3663428A US 11904 A US11904 A US 11904A US 3663428D A US3663428D A US 3663428DA US 3663428 A US3663428 A US 3663428A
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United States
Prior art keywords
tar
fraction
catalyst
reaction
alkylation
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Expired - Lifetime
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US11904A
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English (en)
Inventor
Masaaki Takahashi
Osamu Mayumi
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Kureha Corp
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Kureha Corp
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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
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C10C3/026—Working-up pitch, asphalt, bitumen by chemical means reaction with organic compounds
    • 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
    • C10C1/00—Working-up tar
    • C10C1/19—Working-up tar by thermal treatment not involving distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/16—Dielectric; Insulating oil or insulators
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/17—Electric or magnetic purposes for electric contacts

Definitions

  • ABSTRACT OF THE DISCLOSURE A process for the production of alkylated tars comprising reacting a lower olefin, in the presence of a silicaalumina or zeolite type catalyst, with a tar fraction obtained by the thermal decomposition of a petroleum hydrocarbon at 700-2300 C., and if desired, following a desulfurization reaction.
  • the tar fraction presently employed is obtained from the heavy cracking oil obtained by thermally cracking petroleum hydrocarbons at a temperature above 700" C. and below 2300 C., and subsequently removing solid pitch from the heavy cracked oil, and which consists of a fraction boiling at 200 C.-500 C., calculated at normal pressure.
  • fractions are determined by gas chromatography, infrared absorption analysis, nuclear magnetic resonance analysis, mass spectrograph etc. It has been found that the main component structure of the fractions consists mainly of from two to five benzene nuclei, particularly from two to four condensed benzene rings having short side chains, such as methyl groups, attached thereto, i.e., polycyclic aromatic compounds substantially free from side chains.
  • This structure differs from that of petroleum asphalt, usually called tars, and also from that of coal tar obtained by the dry distillation of coal, by the following points:
  • Petroleum asphalt consists of a mixture of polycyclic aromatic compounds having a plurality of long alkyl side chains, long chain parafiinic compounds and naphthenic compounds having aromatic or alkyl groups attached thereto; due to the fact that petroleum asphalt does not undergo a heat treatment at a high temperature, as is the case with the present invention.
  • coal tar is highly aromatic and resembles the tar fraction of this invention, since it undergoes a heat treatment at high temperatures, but it contains greater amounts of impurities, i.e., oxygen, sulfur, nitrogen metals etc., and has more of a heterocyclic structure in the coal than is contained in petroleum oil.
  • the tar fraction utilized in the present invention is clearly a special type of tar.
  • the alkylated tar products of this invention are unique and can be obtained only by reacting a lower olefin with the above-described tar fraction.
  • the present invention provides a process for producing alkylated tars by reacting a lower olefin with certain tar fractions, in the presence of a silica-alumina or zeolite type catalyst; the tar fractions being polycyclic aromatic compounds produced by the thermal decomposition of petroleum hydrocarbons at a temperature of from 700 to 2300 C.
  • the thermal cracking of the petroleum hydrocarbons may involve flame cracking, high temperature steam cracking, coil cracking, sand cracking etc., that is, any process by which the feed petroleum oil is thermally cracked at a temperature above 700 C. and below 2300 C. to form acetylene and olefins such as ethylene, propylene, butylene, together with heavy cracking oil formed as a byproduct.
  • the feed olefin is a lower olefin generally having a carbon number of not higher than 8, preferably those having from 2 to 4 carbon atoms.
  • Typical olefins to be used are therefore ethylene, propylene and butylene. The use of these last-mentioned olefins is economically advantageous.
  • the desulfurization may be conducted in a conventional desulfurizing apparatus and is operated by reacting hydrogen with the tar fraction in the presence of a catalyst to thereby remove sulfuric compounds in the tar fraction as hydrogen sulfide.
  • the catalyst employed in the desulfurization may contain cobalt, molybdenum or nickel in the form of free metal, oxides, sulfides or combinations thereof, supported by a suitable carrier such as silicaalumina.
  • the desulfurizing reaction is carried out at a temperature of 350-450" C., under a pressure of 20-100 kg./cm.
  • the alkylation reaction is conducted by mixing the gaseous olefin with the tar fraction which has been (or has not been) previously desulfurized, and passing the mixture over a solid catalyst bed under specified reaction conditions.
  • the alkylation apparatus may be a conventional fixed bed type reactor. The reaction conditions will be more fully described below.
  • the catalyst to be used is preferably a solid acid type catalyst including, for example, silica-alumina, or a group III-B metal of the Periodic Table such as lanthanum (La), cerium (Ce), thorium (Th) etc. supported on a zeolite carrier.
  • a solid acid type catalyst including, for example, silica-alumina, or a group III-B metal of the Periodic Table such as lanthanum (La), cerium (Ce), thorium (Th) etc. supported on a zeolite carrier.
  • the liquid hourly space velocity (L.H.S.V.) is the liquid volume of flowing tar fraction per unit hours per unit catalyst volume, and the decrease of L.H.S.V. from a higher to a lower value will increase both the reaction conversion and the degree of alkylation but will reduce the product yield.
  • the preferred reaction conditions as follows: a temperature between 250 C. and 380 C., a pressure between 1 and 50 kg./cm. a feed ratio between 0.2 and 10, and a L.H.S.V. between 0.1 and 50 cc./cc.-catalyst/hr.
  • the degree of alkylation is varied by varying the L.H.S.V. while the length of the alkyl group in the tar fraction is varied by varying the particular olefin fed into the system.
  • neither the decomposition nor the polycondensation reaction occurs and the loss in material balance is minimal.
  • the decrease in catalyst activity due to carbon deposition is greatly minimized so that the catalyst may be used over a prolonged period.
  • the alkylated tar thus formed has a lower specific gravity and a lower refractive index as well as a higher H/C, viscosity, average molecular weight and boiling point than that of the feed tar fraction.
  • the alkylated tar is estimated to have a chemical structure consisting of condensed polycyclic aromatic rings having from two to five, particularly from 2 to 4, benzene rings, which are combined with alkyl groups having the same carbon number as that of the olefin used in the reaction.
  • ethylene, propylene or butylene is used as the olefin
  • the resulting alkylated tar has as its main component an ethylated, propylated or butylated polycyclic aromatic compound, respectively.
  • this invention provides a process for synthetically producing novel alkylated tar fractions having various alkyl group side chains, from polycyclic aromatic compounds substantially free from side chains. Accordingly, various alkylated tars having desirable properties can be produced depending upon their desired uses.
  • the alkylated tar produced by the process of the present invention is used as an electric insulating oil, a rubber processing oil, a heat transfer oil, a plasticizer and as an intermediate material in organic synthesis, etc.
  • the present invention will be more fully illustrated by reference to the following examples, which are merely illustrative, and not intended to be limiting, in nature.
  • Example 1 Petroleum naphtha was thermally cracked according to a flame cracking process at a temperature of 1200" C. for a contact period of 0.003 second to obtain a heavy cracking oil from which a relatively lower boiling tar fraction having a boiling point of 250350 C. (calculated at normal pressure) was taken for use as a feed stock.
  • the physical properties of this fraction were measured by gas chromatography, infrared absorption analysis, nuclear magnetic resonance, mass spectrograph analysis, etc. in order to determine its chemical structure.
  • the result of the analysis indicated that the tar fraction consisted mainly of aromatic compounds having two or three condensed aromatic rings to which a few methyl side chains were attached, and was substantially free from naphthenic and paraffinic components.
  • Table 1 The other physical properties are given in Table 1 below.
  • Ethylene having a commercial grade purity of 99% was used as the olefin feed.
  • the reactor used was a stainless steel tube 1000 mm. in length and 25 mm. in diameter.
  • the catalyst used was granular silica-alumina (SiO 87%, A1 0 13%).
  • the reaction was started by preheating the tar fraction, without desulfurizing treatment, to 200 C., then mixing it with the ethylene and passing the mixture to the reactor after adjusting the feed molar ratio (ethylene to tar fraction) to 5.
  • the reaction was carried out at a reaction temperature of 300 C., a pressure of 30 kg./cm.
  • Example 2 --Petroleum naphtha was thermally decomposed according to a high temperature steam cracking process at a temperature of 1,500 C. for a contact time of 0.002 second to form a heavy cracking oil from which a relatively high boiling tar fraction, boiling at 350-450 C. (calculated at normal pressure), was collected and used as the feed material.
  • the reaction apparatus and the manner of operation were the same as employed in Example 1, and the reaction conditions and the properties of the product are given in Table 4. From these results, it is noted that the ethylation reaction takes place readily when using a higher boiling tar in place of the lower boiling tar fraction as the feed.
  • the alkylation was then conducted using an alkylation catalyst containing 1.5% by weight of cerium supported on a zeolite carrier.
  • the reactor and operation were the same as in Example 1.
  • the reaction conditions and properties of feed and products are given in Table 5. From these results, it is noted that the alkylation reaction takes place smoothly by using a ceriumzeolite catalyst as well, and the life of the alkylation catalyst is extended by preliminarily desulfurizing the crude tar which contains a relatively large amount of sulfur compounds.
  • the reactor and operation were the same as in Example 1.
  • the reaction conditions and the properties of feed and product 5 are given in Table 6 ,(reaction No. (5)). This shows that the process of this invention can be readily performed using propylene as well as ethylene.
  • Example 5 The tar fraction used in Example 1 was alkylated with butylene (mixture of butylene-1 and butylene-2).
  • the reaction apparatus and operation were the same as in Example 1, except that a different olefin was employed as the starting material.
  • the reaction conditions and the properties of the material and product are shown in Table 6 (reaction No. 6)). It is obvious from the results obtained that the alkylation of the tar fraction with butylene also proceeds easily.
  • Example 6 Petroleum naphtha was thermally cracked at 800 C. for a contact time of 0.5 second to produce ethylene and propylene. A fraction having a boiling point of 250 C. to 350 C. was extracted from the bottom oil occurring as the byproduct during the thermal cracking procedure. The fraction obtained was desulfurized with a cobalt/molybdenum/alumina type catalyst using the same apparatus as used in Example 3, and then propylated with propylene. The results obtained are shown in Table r e I v 0 7, together with the reaction conditions.
  • a process for the production of alkylated tar which comprises:
  • said alkylation catalyst comprises a zeolite' support having catalytic material comprising a Group III-B metal thereon.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Organic Insulating Materials (AREA)
US11904A 1969-02-14 1970-02-16 Process for producing alkylated tars Expired - Lifetime US3663428A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44010488A JPS4927401B1 (enrdf_load_stackoverflow) 1969-02-14 1969-02-14

Publications (1)

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US3663428A true US3663428A (en) 1972-05-16

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US (1) US3663428A (enrdf_load_stackoverflow)
JP (1) JPS4927401B1 (enrdf_load_stackoverflow)
BE (1) BE746031A (enrdf_load_stackoverflow)
CA (1) CA923446A (enrdf_load_stackoverflow)
DE (1) DE2006675C3 (enrdf_load_stackoverflow)
FR (1) FR2031431B1 (enrdf_load_stackoverflow)
GB (1) GB1250736A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844931A (en) * 1971-06-30 1974-10-29 Japan Gasoline Method of manufacturing special solvent

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE550494C (de) * 1927-12-09 1932-05-25 I G Farbenindustrie Akt Ges Verfahren zur Herstellung von Kondensationsprodukten aus mehrkernigen aromatischen Verbindungen oder deren Derivaten
US2570263A (en) * 1948-06-08 1951-10-09 Koppers Co Inc Production of beta-ethylnaphthalene

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844931A (en) * 1971-06-30 1974-10-29 Japan Gasoline Method of manufacturing special solvent

Also Published As

Publication number Publication date
FR2031431B1 (enrdf_load_stackoverflow) 1973-04-06
BE746031A (fr) 1970-07-31
CA923446A (en) 1973-03-27
GB1250736A (enrdf_load_stackoverflow) 1971-10-20
DE2006675A1 (de) 1970-10-15
DE2006675C3 (de) 1974-12-05
JPS4927401B1 (enrdf_load_stackoverflow) 1974-07-17
DE2006675B2 (enrdf_load_stackoverflow) 1974-05-02
FR2031431A1 (enrdf_load_stackoverflow) 1970-11-20

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