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
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
  • C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
• • 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
  • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
• • 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
  • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
  • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
• • 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
  • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
  • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
  • C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates

Definitions

• This invention is concerned with improvements in or relating to the desulfurization of hydrocarbon oils and more particularly to the desulfurization of heavy hydrocarbon oils.
• fractional distillation extractive distillation, or a combination of such methods such that desulfurization is accomplished by loss of the hydrocarbon portions of the sulfur bearing molecules and result in low yields of treated product.
• The'present invention provides a new and improved process for reducing the sulfur content of heavy hydrocarbon oils without the concomitant loss of valuable hydrocarbon' oils.
• a heavy. petroleum oil is treated with an oxidant to form compounds containing'both oxygen and sulfur and then oil containing these compounds is subjected to a thermal treatment to rupture the sulfur-carbon bond, volatile sulfur compounds and a heavy hydrocarbon oil of low sulfur content are thereby produced with little loss of product.
• Y 1 The present invention is therefore particularly advantageous when applied to the treatment of hydrocarbon oils in which many of the molecules contain a sulfur atom.
• a further advantage of the present invention is that it can be applied to sulfur containing heavy hydrocarbon oils for which catalytic hydrodesulfurization processes (as may be'employed for the desulfurization of lighter hydrocarbon oils, for example gasolines, kerosenes, light fuel oils, lubricating oils, transformer oils) are either too costly or are unsuited to the particular sulfur compounds contained in the heavy hydrocarbon oil;
• the oxidative treatment should be suiiicient to form sulfones without further oxidationto sulfonic acid derivatives.
• the presence of such acid derivatives may be disadvantageous during the thermal after treatment due to sulfuric acid formation and resultant sludge and coke formation.
• heavy hydrocarbon oil it is meant a hydrocarbon A United States Patent 0 ddhhs Patented Eco. 29,, 1964 hydrogen peroxide with formic or acetic acids.
• suitable oxidizing agents are organic hydroperoxides, in-
• organic peracids and salts thereof organic peracids and salts thereof, aqueous hypochlorite solutions, nitrogen peroxide or air.
• Particularly suitable oxidizing agents are mixtures of hydrogen peroxide and lower alkyl mono carboxylic acids having from 1 to 2 carbon atoms, preferably formic acid, since such mixtures appear to be selective for sulfone formation and the thermal treatment of oils thus oxidized enables the total sulfur content of the heavy oils to be reduced significantly. It has beenffound that particularly satisfactory proportions of reactants to use in the oxidizing step are those where the molar ratio of acid to peroxide is less than 4:1 and greater than 1:10, preferably from about 1:1 to about 1:5. At the higher ratios of acid to peroxide, the by-product formation during the thermal after-treatment tends to increase, whereas at the lower ratios the degree of desulfurization achieved is less satisfactory.
• the molar ratio of peroxide employed to the sulfur present be greater than 1, and further it has been found that no significant increase in desulfurization is achieved using a molar ratio greater than 8. For economic reasons it is desirable to use as oil of which at least 50% by volume boils above 250;?C.
• the present invention is particularly applicable to sulfurcontaining hydrocarbon oils of which at least 90% by volume boils above 300" C.
• Exemplary ofoxidizing agents that have been found suitable for use in the present invention are the organic pe'racids, e.g., performic or peracetic acid or mixtures of little peroxide as is commensurate with effective desulfurization.
• the thermal after-treatment may be carried out in any manner Well-known in the art, the temperature being so chosen as to minimize the degree of thermal degradation ofthe hydrocarbons present in the oil and being suificient to rupture the sulfur-carbon bonds of the sulfur-containing molecules, which bonds, as mentioned above, have been weakened by the oxidation reaction. Generally temperatures in excess of 350 C. are sumcient for this purpose,
• the thermal treatment may take place in the rials such as dolomite or lime.
• the sequence of treating steps may be repeated with advantage and thereby the sulfur content of the heavy oil reduced still further.
• EXAMPLE H In this example the same reagent ratios and conditions as in Example I were employed, but 200 grams of the Kuwait Long Residue were used and 113 grams of the oxidized product thermally treated at 400 C. This treatment produced 90% yield of a residual oil having a sulfur content of 1.9% by weight and only 0.3% by weight of coke was formed.
• EXAMPLE III 100 grams of the same heavy oil as used in the above examples was dissolved in benzene and stirred for 6 hours in the presence of 176 milliliters of 29% w./v. hydrogen peroxide and 76 grams of 90% w. formic acid. After removing excess reagents and solvent, samples of the oxidized oil were heated at 350 C. and 400 C. respectively forv 1 /2 hours, and yielded residual oils with sulfur contents of 2.74% by weight and 1.71%. by weight respectively. The product from the thermal treatment at 350 C..was reoxidized using the same amount of hydrogen peroxide as in the first oxidation and a formic acid/ peroxide molar ratio of 2.0.
• the product was heated for 1 /2 hours at 350 C. to yield a residual oil having a sulfur content of 1.79% by weight, and this oil was heated further for 1 /2 hours at 400 C. to yield a residual oil having a sulfur content of 1.45% by weight.
• EXAMPLE VI In this example, a sample of the same Kuwait Long Residue as used in the previous examples was subjected to oxidation with a formic acid/ hydrogen peroxide oxidant system using a molar ratio of acid/peroxide/sulfur of 8:4:1 for 6 hours at 50 C. in the presence of benzene. 13.2 grams ofthe product was thermally treated in the presence of 2.7 grams of lime for 1 /2 hours at 400 C. A sample of the oxidation product was also cracked under the same conditions except there was no lime present. The following table illustrates the beneficial effect obtained when the thermal after-treatment iscarried out in the presence of lime.
• a sample of reduced crude is subjected to oxidation with an acetic acid/hydrogen peroxide oxidant system using a molar ratio of acid/peroxide/sulfur of 8:4:1 at 50 C. to form sulfones without further oxidation to sulfonic acid derivatives.
• the oil is separated from the oxidant system and is thermally treated for 1 /2 hours at 400 C.
• the resultant heavy petroleum oil has a lower sulfur content than the feed to the process.
• a process for reducing the sulfur content of a sulfurcontaining heavy hydrocarbon oil, at least 50% by volume of said oil boils above 250 C. which comprises treating the oil with an oxidant to form compounds containing both oxygen and sulfur, said oxygen and sulfur being chemically combined, heating the treated oil containing said compounds at a temperature from about 350 C. to about 450 C. under conditions to rupture the sulfurcarbon bond yielding volatile sulfur compounds, and recovering a heavy hydrocarbon oil of reduced sulfur content.
• a process for reducing the sulfur content of a sulfurcontaining heavy hydrocarbon oil, at least 50% by volume of said oil boils above 300 C. which comprises treating the oil with a peroxide-containing oxidant, the mol ratio of peroxide to the sulfur present being from about 1 :1 to about 8:1 to form sulfones without further oxidation to sulfonic acid derivatives, heating the treated oil containing sulfones at a temperature from about 350 C. to about 450 C. under conditions to rupture the sulfur-carbon bond yielding volatile sulfur compounds, and recovering a heavy hydrocarbon oil of reduced sulfur content.
• a process for reducing the sulfur content of a sulfur-containing heavy hydrocarbon oil, at least 90% of said oil boils above 300 C. which comprises treating the oil with a peroxide-containing oxidant consisting essentially of hydrogen peroxide and a lower alkyl monocarboxylic acid having from 1 to 2 carbon atoms, the mol ratio of 10 peroxide to the sulfur present being from about 1:1 to about 8:8 and the mol ratio of acid to peroxide being from about 1: 10 to about 4:1 to form sulfones without further oxidation to sulfonic acid derivatives, heating the treated oil containing sulfones of from about 350 C. to about 1 6 containing heavy hydrocarbon oil is dissolved in a low boiling organic solvent before treatment.
• a peroxide-containing oxidant consisting essentially of hydrogen peroxide and a lower alkyl monocarboxylic acid having from 1 to 2 carbon atoms, the mol ratio of 10 peroxide to the sulfur present being from about 1:1 to about 8:8 and the
• a process for reducing the sulfur content of a sulfur-containing heavy hydrocarbon oil, at least 90% by volume of the oil boils above 300 C. which comprises treating the oil with a peroxide-containing oxidant consisting essentially of hydrogen peroxide and formic acid, the mol ratio of peroxide to the sulfur present being from about 1:1 to about 8:1 and the mol ratio of acid to peroxide being from about 1:1 to about 1:5, to form sulfones without further oxidation to sulfonic acid derivatives, heating the treated oil containing sulfones at about 400" C. to rupture the sulfur-carbon bond yielding volatile sulfur compounds, and recovering a heavy hydrocarbon oil of reduced sulfur content.
• a peroxide-containing oxidant consisting essentially of hydrogen peroxide and formic acid

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

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Cited By (22)

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Citations (3)

• 0
  • NL NL276740D patent/NL276740A/xx unknown
• 1961
  • 1961-04-06 GB GB12373/61A patent/GB976707A/en not_active Expired
• 1962
  • 1962-03-30 US US183714A patent/US3163593A/en not_active Expired - Lifetime
  • 1962-04-04 FR FR893310A patent/FR1325139A/fr not_active Expired
  • 1962-04-04 DE DE19621470636 patent/DE1470636A1/de active Pending

Patent Citations (3)

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