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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
  • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
• • 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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
  • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
  • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
• • 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
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/16—Metal oxides

Definitions

• the present invention relates to a novel process for removing organic sulfur compounds such as thiophenes and other impurities from liquid hydrocarbon streams.
• Sulfur and other impurities such as organic nitrogen compounds and olefins are present in a wide range of mostly organic forms in both straight run and refined hydrocarbon streams, including, for example, gasoline, diesel fuel, and kerosene.
• Sulfur contaminants while ubiquitous in hydrocarbon products, are suspected of causing adverse environmental effects when converted to sulfur oxides (SO x ) upon combustion. SO x emissions are believed to contribute to not only acid rain, but also to reduced efficiency of catalytic converters designed to improve motor vehicle exhaust quality.
• sulfur compounds are thought to ultimately increase the particulate content of combustion products.
• the present invention provides a process that is effective for the removal of organic sulfur compounds, organic nitrogen compounds and light olefins from liquid hydrocarbons and paraffins.
• the process more specifically addresses the removal of these contaminants from aromatic compounds including benzene and toluene and from naphtha.
• the liquid hydrocarbons are contacted at a temperature between 200 to 25O 0 C with a blend of at least one metal oxide and an acidic zeolite.
• the metal oxide comprises a mixture of NiO and MOO3 and the acidic zeolite is acid stabilized zeolite Y.
• This blend has a significant capacity for adsorption of impurities and can be regenerated by oxidative treatment.
• the feed to the process of the present invention comprises broadly any liquid hydrocarbon stream contaminated with an organic sulfur-containing compound. More particularly applicable, however, are straight run and cracked oil refinery streams including naphtha, gasoline, diesel fuel, jet fuel, kerosene, and vacuum gas oil. These petroleum distillates invariably contain sulfur compounds, the concentrations of which depend on several factors including the crude oil source, specific gravity of the hydrocarbon fraction, and the nature of upstream processing operations. [0010] The present invention has been found to be particularly effective for converting sterically hindered sulfur compounds such as thiophene derivatives that are known to be " essentially non-reactive in hydr ⁇ tf eating " (or hydrodesulfurization) reaction environments " .
• the method of the present invention may be practiced either before or after conventional hydrotreating is performed on any of the aforementioned feed stocks to significantly enhance overall sulfur removal efficiency.
• the liquid hydrocarbon feed stream to the present invention is a hydrotreated naphtha, hydrotreated gasoline, hydrotreated diesel fuel, hydrotreated jet fuel, hydrotreated kerosene, or hydrotreated vacuum gas oil.
• hydrotreating can also be performed after the oxidation and decomposition steps to yield a high quality sulfur-depleted product.
• Alkylated dibenzothiophenes include the various isomers of methyl-substituted dibenzothiophenes such as 4-methyldibenzothiophene; 2,8-dimethyldibenzothiophene; and 3,7- dimethyldibenzothiophene.
• the hydrocarbon streams treated may start with as much as 10,000 ppm sulfur and sulfur compounds and typically between 1 to 1,000 ppm.
• the present invention is effective in reducing the level of sulfur and sulfur compounds in the effluent feed after treatment of the hydrocarbon stream to between 0.1 to 50 ppm, preferably to between 0.1 to 25 ppm and most preferably to between 0.1 to 10 ppm.
• a hydrocarbon feed stream is first passed though a catalyst/adsorbent bed containing at least one metal oxide and one acidic zeolite.
• the metal oxide is NiO, MOO3 or mixtures thereof and the acidic zeolite is an acidic stabilized zeolite Y.
• This adsorbent bed is typically operated at a temperature between 200° and 25O 0 C and in the runs summarized in Table 1, at 24O 0 C.
• a hydrocarbon feed containing 250 ppm thiophene (93 ppm sulfur) was processed at this temperature over 20 ml of the catalyst/adsorbent blend at a liquid hourly space velocity (LHSV) of 1.
• LHSV liquid hourly space velocity
• a regeneration procedure is followed to remove the adsorbed sulfur from the adsorbent bed.
• a gas or liquid is sent through the bed, which is maintained at an elevated temperature for a sufficient period of time for the bed to be regenerated through the removal of the contaminants. Regeneration at 600°C for four hours under air was found to be effective. Other gases or liquids may be used.
• the bed may also be regenerated in accordance with the other procedures as known to those skilled in the art.
• Table 1 the use of the acidic stabilized zeolite Y was 10 to 20 times more effective in increased thiophene capacity as compared to the nonacidic Y zeolite. Some improvement in performance was found in the combination of the two metal oxides.
• a sample is dissolved in a titration solvent containing a catalyst that aids in the titration reaction.
• the solution is titrated potentiometrically at room temperature with either a 0.25 M or 0.001 M bromide- bromate solution depending upon whether bromine number or bromine index, respectively, is being determined.
• the titration uses a platinum indicating and a glass reference electrode in conjunction with a recording potentiometric titrator. Bromine number or index is calculated from the volume of titrant required to reach a stable endpoint.
• the nitrogen content is determined in accordance with ASTM test method D 4629-86 (also referred to as D6069).
• This method is entitled "Standard Test Method for Organically Bound Trace Nitrogen in Liquid Petroleum Hydrocarbons by Oxidative Combustion and Chemiluminescence Detection.”
• a sample of liquid petroleum hydrocarbon is injected into a stream of inert gas (helium or argon).
• the sample is vaporized and carried to a high temperature zone where oxygen is introduced and organic and bound nitrogen is converted to nitric oxide which contacts ozone and is converted to NO2-
• the light emitted as the NO2 decays is detected by a photomultiplier tube and the resulting signal is a measure of the nitrogen contained in the sample.

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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)
• Crystallography & Structural Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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Citations (4)

• 2006
  • 2006-09-29 CN CNA2006800559813A patent/CN101511972A/zh active Pending
  • 2006-09-29 BR BRPI0622019-3A patent/BRPI0622019A2/pt not_active IP Right Cessation
  • 2006-09-29 WO PCT/US2006/038636 patent/WO2008039205A1/en active Application Filing

Patent Citations (4)

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