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
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen

Definitions

• Heavy hydrocarbons and residual stocks are of relatively low value as compared with the more volatile com ponents of petroleum.
• These lowvalue materials are usually employed as low grade fuels or are subjected to treatments such as visbreaking to'obtain a certain amount of more valuable components and tar-like residues which may be used for roof or road surfacing materials.
• these low grade fractions of petroleum 'have been subjected to hydrogenation under Various conditions in the presence of various catalysts. Although these procedures result in more or less improvement in yields or in the properties of certain portions of the material treated, there is still considerable room for lowering the cost of such treatments and upgrading of the products thus produced.
• This invention has for its object to provide improved procedure for preparing more valuable hydrocarbons from low grade petroleum or fractions thereof having a relatively low API gravity. Another object is to provide improved procedure for preparing higher quality fuel oils in higher yield from low quality residues having an API gravity below about 20. A still further object is to provide an improved combination process for upgrading of residual stocks by visbreaking followed by hydrogenation treatment of a type which results in formation of a substantial amount of lower boiling components with concomitant hydrodesulfurization. This procedure may be referred to as either destructive hydrogenation or hydrodesulfurization. A still further object is to improve the state of the art. Other objects will appear hereinafter.
• the residual feed stock used in our process may be any crude petroleum having an API gravity below about 20 or any residual fraction thereof having an API gravity of below about 20.
• most crudes are of higher gravity and with such crudes it is desirable to remove valuable portions thereof in conventional manner and 3,l93,487 Patented July 6, 1965 to obtain a residual fraction having a gravity below about 20.
• This residual fraction may be prepared by atmospheric or vacuum distillation.
• the visbreaking operation may be any such operation known in the prior art. These visbreaking operations are commonly carried out by passing the charge stock through a heating coil and heating the oil to thermal cracking temperature.
• the time of heating, the pressure and the temperature of heating control the amount of thermal cracking or conversion into lower boiling components such as gasoline.
• the temperature may be between about 850 and 975 F., the heating time between about 250 and 1,000 seconds, and the pressure between about 50 and 6,000 p.s.i.g.
• the conditions are selected so as to result in a moderate degree of cracking, i.e. so as to form less than 15 percent gasoline. It is advantageous to form between about 1 and 15 percent gasoline and preferably between about 5 and 12 percent gasoline.
• Visbreaking procedures are described in standard textbooks and reference is made thereto for further details on this procedure. See for instance Sachanen, Conversion of Petroleum, Second Edition, Reinhold Publishing Corporation, 1948, pages 252-254.
• the product is preferably subjected to distillation to remove lower boiling components. We prefer to remove all gasoline and lower boiling components formed during the visbreaking step. However such removal is not necessary and all of the visbroken material may be subjected to the subsequent destructive hydrogenation if desired. With sulfur containing stocks this is advantageous since the lower boiling components which contain sulfur will also be desulfurized during the subseqeunt destructive hydrogenation.
• the visbroken residual stock is contacted with hydrogen in the presence of a catalyst such as an oxide or sultide of a Group VI left-hand column metal of the Periodic System.
• a catalyst such as an oxide or sultide of a Group VI left-hand column metal of the Periodic System.
• metals of the iron group their oxides and sulfides may be employed as catalysts.
• These Group VI and iron group catalysts may be mixed with one another. For instance an advantageous mixture is a mixture of cobalt and molybdenum oxides or sulfides. Another advantageous mixture is a mixture of nickel and tungsten oxides or sulfides.
• These catalysts are deposited upon a porous catalyst carrier. Typical useful catalyst carriers are activated alumina, pumice, a silica-alumina cracking catalyst, etc.
• the pressure during the destructive hydrogenation is maintained between about 500 and 5,000 psi. and preferably is between about 1,000 and 2,000 psi.
• the temperature may be between about 650 and 820 F.
• a space velocity between about 0.2 and 10.0 volumes of charge stock per hour per volume of catalyst may be used.
• a vacuum residue obtained by vacuum distillation of a mixture of Kuwait and Venezuela crudes and having the properties shown in Table IV was subjected to visbreaking at three different severities to form gasoline in amounts of 3 percent, 11.8 percent and 20.5 percent re spectively.
• After removal of the gasoline a part of the residues from each visbreaking operation was contacted with the same nickel-cobalt-molybdenum catalyst mentionedv above in the presence of hydrogen under three different severities (temperatures of 700, 750 and 790 F.) and under the conditions given in Table V.
• the results of the visbreaking operations as well as the hydrogen treatments are given in Table V.
• a catalyst selected from the group consisting of oxides and sulfides ofGroup VI lefthand column and the iron group
• nickel oxides and sulfides deposited upon a porous carrier, at a pressure between about 500 and 5000 9 10 p.s.i., at a temperature of between about 750 and 790 2,666,022 154 Johnson 208-68 F., at a space velocity between about 0.5 and 4.0 volumes 3,008,895 11/61 Hansford et a1 20868 of charge per volume of catalyst per hour, and at a OTHER REFERENCES hydrogen recycle rate of between about 2000 and 10,000 standard cubic feet per barrel of visbroken hydrocarbon 5 Sachanen: Com/H5101! of Petroleum 2nd edltlon charge stock. (1948), pp. 252 and 253, Reinhold Pub. Corp., New York. The Petroleum Handbook, 4th edition, Shell Int. Pet. References Cited by the Examiner Co., Ltd., London, 1959.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)

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Citations (4)

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• 0
  • NL NL274915D patent/NL274915A/xx unknown
• 1961
  • 1961-02-16 US US89666A patent/US3193487A/en not_active Expired - Lifetime
• 1962
  • 1962-01-31 GB GB3780/62A patent/GB988470A/en not_active Expired
  • 1962-02-07 DE DEG34200A patent/DE1200459B/de active Pending
  • 1962-02-14 DK DK70162AA patent/DK104471C/da active

Patent Citations (4)

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