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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles

Definitions

• This invention is concerned with improvements in or relating to the treatment of mineral oils to produce light and middle oils.
• the invention is more particularly concerned with the hydrogenation of asphalt-containing raw mineral oils and similar hydrocarbon liquids rich in asphalt and/or poor in hydrogen which, upon hydrogenation yield light and middle oils, and which for convenience are hereinafter termed hydrocarbon oils of the type described.
• hydrocarbon oils of the type described in particular brown coal tar
• the asphalt content of the raw material cannot conveniently exceed .a certain limit and is advantageously not greater than 4-5%
• the starting material is diluted with an organic diluent consisting preferably of cyclic hydrocarbons.
• the asphalt content of asphalt-rich mineral oils, of heavyhydroca'rbon residues and other similar hydrocarbon materials rich in asphalts and/or poor in hydrogen, for instance of coal tars can 'be decomposed in high yield (generally of 80-90% or 'more) and with generally only slight coke production by carrying out the hydrogenation under conditions at which the 'material is present in the reaction space substantially in the gas or vapour phase.
• the starting material is mixed with sufiicient light oil and/or middle oil distillates (or witha' mixture contain- 2,939,835 Patented June 7, 1960 ing the same) that in the resulting mixture the constituents boiling below 350 C. amount to 20-95%, preferably 30-80%, whereafter this mixture is reacted with hydrogen or gas mixtures rich in hydrogen in presence of a moving catalyst, at temperatures above 420 C. and under pressures upto 110 atmospheres, preferably at 10-70 atmospheres.
• the plant required for carrying out the process may be more simple and substantially more economical as those required for high pressure hydrogenation processes
• the distillate of low boiling point range which in the process of this invention is added to the asphalt-containing raw material (and which for convenience is called in the following description low boiling diluent) should be so selected as to be present under the given reaction conditions substantially in the vapour phase.
• Suitable admixtures are light and/or middle oils. Mixtures of hydrocarbon materials consisting substantially of light and middle oils but containing some higher boiling constituents too are equally suitable.
• the amount of the low boiling diluent to be used depends on the asphalt or hydrogen content of the starting material and further on the extent to which the decomposition of the asphalts is to be carried.
• the process according to the invention can be eflected in the temperature range between 420 and 550, preferably between 430 and 480 C. l
• the reaction can be conducted so that the reaction components are present substantially in the gas or vapour phase.
• the oxygen, sulphur and nitrogen compounds present in the starting material are in general substantially eliminated in the course of the reaction.
• the sulphur may be eliminated to the extent of from 40-70%.
• any convenient hydrogenation catalyst is suitable, such as hydrogenation catalysts selected from themetals of groups 5, 6, 7 and 8 of the periodic system, their compounds, alone or in mixtures with each other, whether dispersed on a carrier substance or not.
• Particularly effective catalysts are active coke and carbon powder and catalysts comprising iron oxide dispersed on coke or carbon powder.
• the catalyst must be fed continuously into the reaction space with the feed and be discharged with the efiluentmaterial togetherrwith which the fine coke produced from the asphalts is also discharged too.
• the catalyst may also be kept floating dues thereof can also be converted into lubricants or gasolines in good yield.
• the hydrogen. consumption calculated with respect to the starting material does not, in general, amount to more than about 1 to 2.5% and is consequently smaller than that of the known high pressure hydrogenations.
• a further advantage of the present process consists in the possibility of using gas mixtures with a lower hydrogen content in place of pure hydrogen; such mixtures are for instance industrial gases with a content of 40-70% H e.g. synthesis gas and coke oven gas.
• the asphalt-containing material is mixed with the low boiling diluent (mineral oil distillate, a gas oil containing light and middle oils or the like) of known composition and fed with a calculated amount of a hydrogen containing gas (0.2-4 cub. m. preferably 0.5-2 cub. m./kg. starting material) and with the cata- 'lyst under a pressure of 1-100 atmospheres, preferably 10-70 atmospheres into an oven.
• a hydrogen containing gas (0.2-4 cub. m. preferably 0.5-2 cub. m./kg. starting material
• the efliuent stock can be passed through one or more reactors connected in series behind the pipe-still.
• the efiluent stock is then passed to any convenient fractionators, thecatalyst and the heavy residue, as usual, and if desired recycled and the stock recovered in the usual way.
• the process according to the invention can be efiected in a reactor containing a fluidised catalyst, similar to the method usual in fluid catalyst cracking processes.
• Example 1 100 kg. raw mineral oil of specific gravity 0.924 (at 60 C.) with acontent of:
• hydrocarbon oils consisting of:
• Example 3 7 kg. raw asphalt-containing material according to Example 1' are mixed with an equal amount of th'elow boiling diluent used in that example. The mixture is hydrogenated at 445 C. under a pressure of 15 atmospheres but otherwise under the conditions set forth in Example 1.
• the treated starting material yields 90.0 kg. hydrocarbon oils consisting of Fractions boiling within the range up to 350 C. V p 45.9 kg. Heavy oils boiling above 350 44.1 'kg.
• specific gravity 0.904 comprises aasasss 8
• the 200 kg. mixture is treated at 430-440 C. under a pressure of 70 atmospheres but otherwise substantially under the conditions and in the installations set forth in Example 1.
• Heavy oils boiling range above 350 C 60.8 kg. Total liquid 92.0 kg.
• Example 6 Kg. Starting material 100 Low boiling diluent 100 both identical with those set forth in Example 1. After addition of 2% by weight of iron oxide activated active carbon powder catalyst, the mixture is preheated and conducted into a pipe-still (without the use of a connected reactor) together with a gas mixture containing 70% H under a pressure of 70 atmospheres and treated at 475 C. Volume-space-velocityz 6 kg./litres of pipestill volume/hours.
• Example 7 100 kg. brown coal tar of specific gravity 0.971 with a content of 35.5% by weight of fractions distilling in the range up to 325 C., sulphur content 2.67% by weight and containing 6.8% by weight hard asphalts are -mixed with an equal amount of the distillate used as low boiling diluent in Example 1.
• Example 8 Starting asphalt-containing" material: 100 kg. asphalt and sulphur containing raw'mineral oil set forth in Example'l. Low boiling diluent: 100 kg. heavy gas oil of the. following characteristics:
• Boiling point range C 180-440 Fractions distillable up to 325 C.
• Example 10 100 kg. of the starting material and 100 kg. of the low boiling diluent set forth in Example 1 are treated according to the same example, but mixed with 2% by weight of a catalyst consisting of activated silica in powder form. After recovery of the 100 kg. low boiling diluent, one obtains from the 100 kg. starting material 90 kg. liquid consisting of Fractions boiling up to 350 C About 70 kg. Heavy oils boiling above 350 C About 15 kg. Total liquid About kg. Hard asphalt decomposition eifect About Desulphurizing effect About 60%.
• Example 11 Starting asphalt containing material: kg. asphalt and sulphur containing raw mineral oil set forth in Example l.
• Low boiling diluent 100 kg. petroleum distillate as set forth in the same example.
• Catalyst 4 kg. silica-alumina catalyst. The mixture is treated as set forth in Example 1. After recovery of the 100 kg. low
• the hydrogenating catalyst is selected from the group consisting of active coke, active carbon powder and carbon powder activated with iron OXideJ V 6.

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• 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)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Working-Up Tar And Pitch (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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Cited By (9)

Citations (6)

Family Cites Families (5)

• 0
  • NL NL98723D patent/NL98723C/xx active
  • BE BE533923D patent/BE533923A/xx unknown
• 1954
  • 1954-11-07 DE DEN9699A patent/DE977520C/de not_active Expired
  • 1954-12-22 GB GB37060/54A patent/GB778421A/en not_active Expired
  • 1954-12-30 US US478912A patent/US2939835A/en not_active Expired - Lifetime
  • 1954-12-30 FR FR1120530D patent/FR1120530A/fr not_active Expired

Patent Citations (6)

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