GB472538A - Improvements in the manufacture and production of aromatic hydrocarbon compounds of low boiling point - Google Patents

Improvements in the manufacture and production of aromatic hydrocarbon compounds of low boiling point

Info

Publication number
GB472538A
GB472538A GB492236A GB492236A GB472538A GB 472538 A GB472538 A GB 472538A GB 492236 A GB492236 A GB 492236A GB 492236 A GB492236 A GB 492236A GB 472538 A GB472538 A GB 472538A
Authority
GB
United Kingdom
Prior art keywords
hydrogen
effected
dehydrogenation
catalysts
destructive hydrogenation
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
Application number
GB492236A
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.)
IG Farbenindustrie AG
Original Assignee
IG Farbenindustrie AG
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 IG Farbenindustrie AG filed Critical IG Farbenindustrie AG
Priority to GB492236A priority Critical patent/GB472538A/en
Publication of GB472538A publication Critical patent/GB472538A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils

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)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Aromatic hydrocarbons of low boiling point are produced from liquid or solid bituminous materials, such as coals, tars, mineral oils, asphalts or their distillation residues, by the following process. The bituminous material or a fraction thereof is subjected to destructive hydrogenation, and the portion of the products boiling above 250 DEG C. is, in either order, (a) dehydrogenated, and (b) treated with a halide having a splitting action or with an oxidizing agent at a raised temperature, whereby side chains are removed; finally, the product is cracked. The destructive hydrogenation products may be freed in known manner from paraffin wax and asphalt before further treatment; the separated asphalt may be subjected to destructive distillation and the distillate added to the destructive hydrogenation product before or after the latter is cracked. The dehydrogenation may be effected at 350--600 DEG C. and atmospheric, reduced or raised pressure in the presence of a catalyst. Specified dehydrogenation catalysts are metals of the platinum group, silver, magnesium, zinc, aluminium, silicon, titanium, tin, lead, vanadium, chromium, molybdenum, tungsten, uranium, manganese, iron, nickel, cobalt, and rare earth metals, preferably in the form of mixtures of their compounds; the catalysts may be applied to carriers, or they may be suspended in the material to be treated and led through the reaction vessel. Halogens, hydrogen halides, non-metallic halides or acids may be used in association with the catalysts. The dehydrogenation may be effected in the presence of hydrogen, and other gases or vapours, e.g. steam, nitrogen, oxides of carbon, methane or water gas, may also be added; when hydrogen is present, the preferred catalysts are the oxides or sulphides of the metals of the 5th or 6th periodic group, with or without other metal compounds, and when sulphides are used a volatile sulphur compound, such as hydrogen sulphide, is preferably added. The dehydrogenation may be effected in stages at increasing temperatures and varying pressures. Dehydrogenation may also be effected (a) by passing the material with air or oxygen over copper at 350 DEG C., (b) by heating the material with sulphur or another reagent capable of combining with hydrogen, e.g. selenium, tellurium, nitrogen oxides or dilute nitric acid, (c) by halogenating the material and then removing hydrogen halide, or (d) by distilling the material in the presence of a metal such as sodium. The treatment for the removal of side chains may be effected (a) by heating the material to 50--300 DEG C. with aluminium chloride, boron fluoride, ferric chloride or titanium chloride, with or without hydrochloric acid, or (b) by treating the material at 50--150 DEG C. with potassium permanganate or chromic acid. The cracking stage is effected at a higher temperature than the dehydrogenation stage, suitably at 400--700 DEG C. and atmospheric or raised pressure, and preferably in the presence of a catalyst; specified catalysts are ferrosilicon or other metal containing silicon, active carbon, which may be impregnated with a metal salt solution, or metal halides or finely divided metals in association with acids or organic halogen compounds. Cracking is preferably effected in the presence of a small proportion of hydrogen, and other gases or vapours, e.g. nitrogen, carbon dioxide or steam, may also be present. In the example, a fraction of coal destructive hydrogenation products boiling at 250--350 DEG C. is led with hydrogen under 300 atm. pressure first over tungsten sulphide at 340 DEG C. and then at 370 DEG C. over active carbon which has been impregnated with molybdenum and cobalt salts and after-treated with hydrogen sulphide under pressure; the dehydrogenated product is freed from crystalline hydrocarbons and then heated to 150 DEG C. with aluminium chloride, and finally passed, with addition of hydrogen, at 530 DEG C. over a catalyst comprising molybdic acid, zinc oxide and magnesia. Specification 435,254 is referred to. The Provisional Specification refers to the treatment of destructive hydrogenation products of resins, and states that the removal of side chains may be effected simultaneously with the dehydrogenation at a temperature up to 1000 DEG C.ALSO:Aromatic hydrocarbons of low boiling point are produced from liquid or solid bituminous materials, such as coals, tars, mineral oils, asphalts or their distillation residues, by the following process. The bituminous material or a fraction thereof is subjected to destructive hydrogenation, and the portion of the products boiling above 250 DEG C., is, in either order, (a) dehydrogenated and (b) treated with halide having a splitting action or with an oxidizing agent at a raised temperature, whereby side-chains are removed; finally the product is cracked. The destructive hydrogenation products may be freed in known manner from paraffin wax and asphalt before further treatment; the separated asphalt may be subjected to destructive distillation and the distillate added to the descructive hydrogenation product before or after the latter is cracked. The dehydrogenation may be effected at 350--600 DEG C. and atmospheric reduced or raised pressure in the presence of a catalyst. Specified dehydrogenation catalysts are metals of the platinum group, silver magnesium, zinc, aluminium, silicon, titanium, tin, lead, vanadium, chromium, molybdenum tungsten, uranium manganese, iron, nickel, cobalt, and rare earth metals, preferably in the form of mixtures of their compounds the catalysts may be applied to carriers, e.g. activated acid-neutralized lignite coke, or they may be suspended in the material to be treated and led through the reaction vessel. Halogens, hydrogen halides, non-metallic halides or acids may be used in association with the catalysts. The dehydrogenation may be effected in the presence of hydrogen, and other gases or vapours, e.g. steam, nitrogen, oxides of carbon, methane or water gas, may also be added; when hydrogen is present, the preferred catalysts are the oxides or sulphides of the metals of the 5th or 6th periodic group, with or without other metal compounds, and when sulphides are used a volatile sulphur compound, such as hydrogen sulphide, is preferably added. The dehydrogenation may be effected in stages at increasing temperatures and varying pressures. Dehydrogenation may also be effected (a) by passing the material with air or oxygen over copper at 350 DEG C., or (b) by heating the material with sulphur or another reagent capable of combining with hydrogen, e.g. selenium, tellurium, nitrogen oxides or dilute nitric acid, or (c) by halogenating the material and then removing hydrogen halide, or (d) by distilling the material in the presence of a metal such as sodium. The treatment for the removal of side chains may be effected (a) by heating the material to 50--300 DEG C. with aluminium chloride, boron fluoride, ferric chloride or titanium chloride, with or without hydrochloric acid, or (b) by treating the material at 50--150 DEG C. with potassium permanganate or chromic acid. The cracking stage is effected at a higher temperature than the dehydrogenation stage, suitably at 400--700 DEG C. and atmospheric or raised pressure, and preferably in the presence of a catalyst; specified catalysts are ferrosilicon or other metal containing silicon, active carbon, which may be impregnated with a metal salt solution, or metal halides or finely divided metals in association with acids or organic halogen compounds. Cracking is preferably effected in the presence of a small proportion of hydrogen, and other gases or vapours, e.g. nitrogen, carbon dioxide or steam, may also be present. The portion boiling below 250 DEG C. of the original destructive hydrogenation product may be subjected again to destructive hydrogenation, as described in Specifications 281,298, 302,253, [both in Class 32], and 354,181, to increase the yield of aromatic hydrocarbons. In the example, a paste of coal and heavy oil is subjected to destructive hydrogenation at 460 DEG C. and 400 atmos. after addition of specified proportions of tin oxalate and chlorine; the fraction of the products boiling at 250--350 DEG C. is led with hydrogen under 300 atmos. pressure first over tungsten sulphide at 340 DEG C. and then at 370 DEG C. over active carbon which has been impregnated with molybdenum and cobalt salts and after-treated with hydrogen sulphide under pressure; the dehydrogenated product is freed from crystalline hydrocarbons and then heated to 150 DEG C. with aluminium chloride, and finally passed, with addition of hydrogen, at 530 DEG C. over a catalyst comprising molybdic acid, zinc oxide and magnesia. Specification 435,254 also is referred to. The Provisional Specification refers to the treatment of destructive hydrogenation products if resins, and states that the removal of side chains may be effected simultaneously with the dehydrogenation at a temperature up to 1000 DEG C.
GB492236A 1936-02-18 1936-02-18 Improvements in the manufacture and production of aromatic hydrocarbon compounds of low boiling point Expired GB472538A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB492236A GB472538A (en) 1936-02-18 1936-02-18 Improvements in the manufacture and production of aromatic hydrocarbon compounds of low boiling point

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB492236A GB472538A (en) 1936-02-18 1936-02-18 Improvements in the manufacture and production of aromatic hydrocarbon compounds of low boiling point

Publications (1)

Publication Number Publication Date
GB472538A true GB472538A (en) 1937-09-20

Family

ID=9786384

Family Applications (1)

Application Number Title Priority Date Filing Date
GB492236A Expired GB472538A (en) 1936-02-18 1936-02-18 Improvements in the manufacture and production of aromatic hydrocarbon compounds of low boiling point

Country Status (1)

Country Link
GB (1) GB472538A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2920116A (en) * 1957-08-16 1960-01-05 United States Steel Corp Method of making naphthalene and lower-boiling compounds from creosote oil
JP2008050338A (en) * 2006-08-22 2008-03-06 Hyosung Corp Method for producing dimethylnaphthalene using metal catalyst

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2920116A (en) * 1957-08-16 1960-01-05 United States Steel Corp Method of making naphthalene and lower-boiling compounds from creosote oil
JP2008050338A (en) * 2006-08-22 2008-03-06 Hyosung Corp Method for producing dimethylnaphthalene using metal catalyst
EP1897863A1 (en) 2006-08-22 2008-03-12 Hyosung Corporation Method for producing dimethylnaphthalene using a metal catalyst
US7718835B2 (en) 2006-08-22 2010-05-18 Hyosung Corporation Dehydrogenation process of dimethylnaphthalene using metal catalyst

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