US3600298A - Process for producing hydrogenated alkyl tars - Google Patents

Process for producing hydrogenated alkyl tars Download PDF

Info

Publication number
US3600298A
US3600298A US23962A US3600298DA US3600298A US 3600298 A US3600298 A US 3600298A US 23962 A US23962 A US 23962A US 3600298D A US3600298D A US 3600298DA US 3600298 A US3600298 A US 3600298A
Authority
US
United States
Prior art keywords
tar
catalyst
fraction
alkylation
alkylated
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
US23962A
Other languages
English (en)
Inventor
Osamu Mayumi
Masaaki 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 US3600298A publication Critical patent/US3600298A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • 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

  • the present invention is concerned with a novel process for the production of a mixture of alkylated naphthene compounds.
  • the process of this invention is also directed to the elficient utilization of heavy cracked oil by-products which are being produced in increasing amounts as the result of increased ethylene manufacturing operations.
  • the tar fraction employed as the feed material in this invention is obtained by thermally cracking petroleum hydrocarbons at a temperature of 700 C. to 2300 C., removing solid pitch from the heavy cracked oil, and is a fraction having a boiling range of 200 C. to 500 C calculated a normal atmospheric pressure.
  • the tar fractions after inspection of their physical properties by gas chromatography, infrared absorption analysis, nuclear magnetic resonance analysis, mass spectrographic analysis, etc. are primarily polycyclic aromatic compounds having a struc ture consisting mainly of 2 to 5 aromatic rings, particularly 2 to 4 condensed aromatic rings substantially free from side chains.
  • the intermediate alkylated tar of the present invention consists mainly of alkylated polycyclic aromatic compounds and the hydrogenated alkylated tar product of the present invention mainly consists of alkylated polycyclic naphthenes.
  • petroleum hydrocarbons are first thermally cracked at a temperature between 700 C. and 2300 C. to form olefins, such as acetylene, ethylene, propylene and butylene, together with heavy cracked oil.
  • the petroleum hydrocarbons employed as feed include gaseous hydrocarbons, naphtha, kerosene, light gas oil, heavy gas oil, residual oil, mixtures of two or more of these, as well as crude oil.
  • the thermal cracking may be carried out according to any conventional manner including flame cracking, high temperature steam cracking, ordinary steam cracking, etc.
  • the tar fractions to be used as the feed material to the process of this invention are those obtained from the heavy cracked oil after removal of the solid pitch contained therein, and have a boiling point range of from 200 C. to 500 C., preferably 250-450 C., calculated at normal atmospheric pressure.
  • This tar fraction has a hydrogen to carbon atomic ratio (H/C) of from 0.5 to 1.0 and a specific gravity of from 1.0 to 1.3.
  • the tar fraction may be directly reacted with olefin, it is more effective to carry out preliminary desulfurization of the tar fraction, so as to lengthen the life of the alkylation and hydrogenation catalysts.
  • the desulfurization may be conducted in any conventional manner using any known desulfurizing apparatus. Catalysts which may be employed in such desulfurizations include cobalt, molybdenum, or nickel as their metals, oxides, sulfides or combinations thereof, which may be employed on suitable carriers, such as alumina and silica-alumina.
  • the desulfurizing reaction may be carried out at a temperature of 350450 C. under a pressure of 20-100 l :g./cm.
  • the following alkylation reaction of the present invention may be conducted by mixing gaseous olefin with the tar fraction and reacting them in the presence of a suitable catalyst.
  • the catalyst employed is preferably a silicaalurnina type, or a catalyst comprising a Group III-B metal, such as lanthanum (La), cerium (Ce), thorium (Th), etc., employed on a zeolite carrier.
  • the olefin feed is preferably a lower olefin, generally having not more than 8 carbon atoms, preferably containing from- 2 to 4 carbon atoms.
  • Typical of such olefins which may be used in the present invention are ethylene, propylene and butylene and the use of these olefins is economically advantageous.
  • the reaction conditions which may be employed include a temperature of about 250 C. to 380 C., a pressure of about 1 to 50 -kg./cm. a feed ratio of about 0.2 to 10 mole of olefin per mole of the tar fraction and a liquid hourly space velocity of from 0.1 to 5.0 cc./ cc. of catalyst/hr. The reaction takes place readily over a prolonged period of time without substantial decrease of catalyst activity.
  • the amount of alkyl side chains introduced may be controlled as desired.
  • the length of the alkyl side chain added is dependent upon the kind of olefin used.
  • the degree of alkylation (the moles of olefin reacted per mole of the tar fraction components) can be increased by either employing high feed ratios or using a small liquid hourly space velocity.
  • the alkylated tar thus formed has a lower specific gravity, a lower refractive index, as well as higher H/ C values, viscosity, average molecular weight and boiling point than that of the feed tar fraction.
  • alkylated tar consists of condensed polycyclic aromatic compounds having from two to five, particularly from two to four, aromatic rings, which condensed ring compounds are combined with the added alkyl groups containing the same number of carbon atoms as that of the olefin used in the alkylation reaction.
  • the subsequent hydrogenation reaction is carried out by admixing the alkylated tar with hydrogen and reacting the mixture in the presence of a suitable catalyst.
  • the catalyst which may be used in the hydrogenation includes Group VI, VII and VII metals, oxides, sulfides and combinations thereof, or such materials on carriers, such as diatomaceous earth, alumina, bauxite, pumice stone, silica-alumina, activated carbon, etc. Typical examples of such catalysts are nickel-diatomaceous earth, molybdenum-alumina, platinum-alumina, cobalt-nickel-alumina, etc.
  • the reaction conditions which may be used include a temperature of 100-450 C., a pressure of 10-30 kg./cm.
  • the reaction in this step mainly involves the hydrogenation of the polycyclic aromatics and is not accompanied by side reactions such as dissociation of the alkyl side chain, ring opening of the napthene rings, decomposition, polymerization, etc.
  • the degree of hydrogenation can be controlled by varying the reaction conditions, such as the liquid hourly space velocity. The reaction takes place readily under the above conditions, without appreciable deactivation of the catalyst, which can therefore be used over a long period of time.
  • the hydrogenated alkyl tar so formed has a lower specific gravity, viscosity and refractive index and a higher H/ C than that of the alkylated tar before undergoing hydrogenation.
  • Measurement of the physical properties of the hydrogenated product by the use of the above-mentioned analytic methods shows that the product consists primarily of compounds in which the alkyl group is attached to naphthene rings having from two to five condensed rings, particularly from 2 to 4 condensed rings.
  • this invention provides a process whereby hydrogenated, alkylated tar can be produced by adding alkyl groups under controlled conditions to the tar fraction consisting of polycyclic aromatic compounds having a few side chains and by thereafter hydrogenating the aromatic nuclei. Accordingly, various hydrogenated alkylated tars having the most desirable properties depending upon the intended use can be freely produced by the process of this invention.
  • the hydrogenated, alkylated tar products of this invention can be used in a variety of industrial fields, for example, as electric insulating oils, rubber processing oils, plasticizers, lubricant oils, heat-transfer oils, high energy fuels, special solvents, paints and intermediates in the production of various chemicals and possess outstanding properties which have never before been obtained.
  • the alkylation catalyst was granular silica-alumina (SiO 87%, A1 0 13%).
  • the alkylation reaction was carried out by passing the tar fraction over the catalyst together with ethylene as a mixture.
  • the reaction conditions, the properties of the feed tar fraction and the properties of the resulting (ethylated) tar are shown in Table 1. The reaction took place with ease and no substantial lowering of the catalyst activity was observed. In this case, the degree of alkylation varied as shown in Table 2 depending upon the change in the material feed ratio or liquid hourly space velocity, holding other conditions unchanged. The degree of alkylation can be increased either by employing feed ratio or by employing a smaller liquid hourly spaced velocity.
  • the ethylated tar was then hydrogenated.
  • the hydrogenation reactor was a stainless steel tube of 2000 mm. in length and mm. in diameter and was packed with a catalyst comprising nickel by weight) supported on alumina (60% by weight).
  • the reaction was conducted by admixing the ethylated tar with hydrogen and passing the resulting mixture over the catalyst bed.
  • the reaction conditions and properties of the hydrogenated cth ylated tar are given in Table 1.
  • the reaction proceeded with ease and without appreciable lowering of catalyst activity. By dropping the liquid hourly space velocity as shown in Table 3, the H/ C became greater indicating the TABLE 1.-ETHYLA1ION AND I'IYDROGENATION OF TAR FRACTION Reaction conditions:
  • the desulfurized tar fraction was then subjected to alkylation and successive hydrogenation in the same manner as in Example 1.
  • the reaction conditions and the properties of the feed and the product are each given in Table 4. It will be noted that the hydrogenated ethylated tar can be readily produced from a high boiling tar fraction as well, and the reaction can be smoothly carried out Without substantial difficulty regarding the activity of either alkylation or hydrogenation catalyst even when using feed tar fractions containing a relatively high sulfur content, as long as preliminary desulfurization is conducted.
  • the properties of the tar fraction so obtained were as shown in Table 5.
  • the relatively large proportion of sulfur initially contained in the amount of 2.05% by weight was reduced to 0.005% by weight by the desulfurizing treatment carried out under the conditions given in Table 5.
  • the desulfurized tar fraction was then successively alkylated and hydrogenated in the same manner as in Example 1.
  • the reaction conditions and the properties of the feed materials and products used are given in Table 5.
  • the reaction proceeded smoothly to form hydrogenated ethylated tar.
  • the activity of the alkyl-' ation and hydrogenation catalysts was unaffected even when using the tar fraction with this relatively high sulfur content of 0.224% by Weight which was higher than that content so long as it is preliminarily desulfurized.
  • Example I of the tar fraction of Example I, which was obtained frompetroleurnnaphtha and contains 0.72% sulfur by weight.
  • the tar fraction of this example was subjected to desulfurization treatment.
  • the desulfurizing conditions I and results thereof are given in Table 4 which demonstrates the reduction of the sulfur content to below 0.001% by weight.
  • the lighter fraction of the hydrogenated propylated tar is especially suited for use as a heat transfer oil and TABLE 6.PROPYLATION AND HYDROGENATION OF TAR FRACTION Feed material Alkylation Hydro- (tar fraction) (propylation) genation Reaction conditions:
  • Feed ratio Alkylation (moles propylene/moles tar fraction); hydrogenation (moles hydrogen/moles alkylated tar.
  • a process for the production of hydrogenated alkylated tar which comprises desulfurizing a tar fraction in proceeded smoothly to produce hydrogenated butylated 25 the presence of hydrogen and a desulfurization catalyst,
  • tar fraction consisting essentially of polycyclic aromatic compounds and having been obtained by the thermal decomposition of petroleum hydrocarbons at a temperature of 700 C. to 2300 C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US23962A 1969-03-28 1970-03-30 Process for producing hydrogenated alkyl tars Expired - Lifetime US3600298A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2368269 1969-03-28

Publications (1)

Publication Number Publication Date
US3600298A true US3600298A (en) 1971-08-17

Family

ID=12117217

Family Applications (1)

Application Number Title Priority Date Filing Date
US23962A Expired - Lifetime US3600298A (en) 1969-03-28 1970-03-30 Process for producing hydrogenated alkyl tars

Country Status (5)

Country Link
US (1) US3600298A (enrdf_load_stackoverflow)
CA (1) CA926798A (enrdf_load_stackoverflow)
DE (1) DE2014895C3 (enrdf_load_stackoverflow)
GB (1) GB1306401A (enrdf_load_stackoverflow)
SU (1) SU454746A3 (enrdf_load_stackoverflow)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755143A (en) * 1969-04-25 1973-08-28 Kureha Chemical Ind Co Ltd Method for rearranging the structures of crude oil or crude oil fractions
US3844931A (en) * 1971-06-30 1974-10-29 Japan Gasoline Method of manufacturing special solvent
US3844932A (en) * 1969-12-11 1974-10-29 S Gomi Process for treating by-product heavy fractions formed in the production of olefins
US4101416A (en) * 1976-06-25 1978-07-18 Occidental Petroleum Corporation Process for hydrogenation of hydrocarbon tars
US4108788A (en) * 1977-07-21 1978-08-22 Gulf Research & Development Company Liquid dielectric composition derived from the alkylation product of benzene with ethylene
US4111824A (en) * 1977-07-21 1978-09-05 Gulf Research & Development Co. Liquid dielectric composition based on a fraction derived from the alkylation product of benzene with ethylene
US4111825A (en) * 1977-07-21 1978-09-05 Gulf Research & Development Co. Liquid dielectric composition based on a fraction derived from the alkylation product of benzene with ethylene
US4744882A (en) * 1987-01-02 1988-05-17 Domtar Inc Polycondensates of sulfonated coal tar fractions
US4909923A (en) * 1984-06-22 1990-03-20 Nippon Steel Chemical Co., Ltd. Method for hydrogenation of coal tar pitch
US10494577B2 (en) 2016-12-19 2019-12-03 Exxonmobil Research And Engineering Company Trim alkali metal desulfurization of refinery fractions
CN114456610A (zh) * 2021-12-14 2022-05-10 长安大学 一种环氧端基低分子量聚乙烯沥青改性剂及其制备方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755143A (en) * 1969-04-25 1973-08-28 Kureha Chemical Ind Co Ltd Method for rearranging the structures of crude oil or crude oil fractions
US3844932A (en) * 1969-12-11 1974-10-29 S Gomi Process for treating by-product heavy fractions formed in the production of olefins
US3844931A (en) * 1971-06-30 1974-10-29 Japan Gasoline Method of manufacturing special solvent
US4101416A (en) * 1976-06-25 1978-07-18 Occidental Petroleum Corporation Process for hydrogenation of hydrocarbon tars
US4108788A (en) * 1977-07-21 1978-08-22 Gulf Research & Development Company Liquid dielectric composition derived from the alkylation product of benzene with ethylene
US4111824A (en) * 1977-07-21 1978-09-05 Gulf Research & Development Co. Liquid dielectric composition based on a fraction derived from the alkylation product of benzene with ethylene
US4111825A (en) * 1977-07-21 1978-09-05 Gulf Research & Development Co. Liquid dielectric composition based on a fraction derived from the alkylation product of benzene with ethylene
US4909923A (en) * 1984-06-22 1990-03-20 Nippon Steel Chemical Co., Ltd. Method for hydrogenation of coal tar pitch
US4744882A (en) * 1987-01-02 1988-05-17 Domtar Inc Polycondensates of sulfonated coal tar fractions
US10494577B2 (en) 2016-12-19 2019-12-03 Exxonmobil Research And Engineering Company Trim alkali metal desulfurization of refinery fractions
CN114456610A (zh) * 2021-12-14 2022-05-10 长安大学 一种环氧端基低分子量聚乙烯沥青改性剂及其制备方法
CN114456610B (zh) * 2021-12-14 2022-11-29 长安大学 一种环氧端基低分子量聚乙烯沥青改性剂及其制备方法

Also Published As

Publication number Publication date
DE2014895A1 (de) 1970-10-01
DE2014895B2 (enrdf_load_stackoverflow) 1974-05-16
SU454746A3 (ru) 1974-12-25
DE2014895C3 (de) 1974-12-19
CA926798A (en) 1973-05-22
GB1306401A (en) 1973-02-14

Similar Documents

Publication Publication Date Title
US4585545A (en) Process for the production of aromatic fuel
US4180453A (en) Process for the steam-cracking of heavy feedstocks
CA1275064A (en) Process for improving octane by the conversion of fused multi-ring aromatics and hydroaromatics to lower molecular weight compounds
US3600298A (en) Process for producing hydrogenated alkyl tars
US3786107A (en) Method of producing alkyl aromatics
US3221078A (en) Selective hydrogenation of olefins in dripolene
KR970001188B1 (ko) 탄화수소성 공급원료의 전환 방법
US1932369A (en) Removal of sulphur compounds from crude hydrocarbons
JPS6132356B2 (enrdf_load_stackoverflow)
AU2016396601B2 (en) Method and catalyst for producing high octane components
US3317622A (en) Polycyclic aromatics for hydrodealkylation
CA1331864C (en) Process for hydrotreating olefinic distillate
US3691063A (en) Residual fuel oil hydrocracking process
GB2132107A (en) Catalyst material containing group IIB metal oxide and oxide of molybdenum or vanadium
JP2003520889A5 (enrdf_load_stackoverflow)
CA1216311A (en) Process for selective hydrogenation of dienes in pyrolysis gasoline
US3269937A (en) Hydroisomerization process
WO2015077045A1 (en) Process for hydrotreating a coal tar stream
Kinugasa et al. Removal of basic compounds and dealkylation of alkyl polycyclic aromatic hydrocarbons in vacuum gas oil
JP2520725B2 (ja) ジメチルナフタレン類の製造方法
JP2520723B2 (ja) メチルナフタレン類の製造方法
US3691248A (en) Selective hydrogenation of acetylenes
US20050234275A1 (en) Reduction of naphthalene concentration in aromatic fluids
JPS5821891B2 (ja) ノルマルパラフインノ セイゾウホウ
US3294857A (en) Process for producing high-pure aromatic hydrocarbons