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
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
  • C10G29/24—Aldehydes or ketones
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/40—Mixing liquids with liquids; Emulsifying
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4075—Limiting deterioration of equipment

Definitions

• This invention relates generally to processing heavy oil, and more particularly, to methods for removing hydrogen sulfide in heavy oil with an aqueous- based scavenger/oil emulsion.
• H 2 S hydrogen sulphide
• Hydrogen sulfide scavengers can be used to remove hydrogen sulfide from heavy oil. It is known to be possible to reduce the hydrogen sulphide content present in aqueous mediums by using aqueous solutions of aldehydes such as formaldehyde, glyoxal, and glutaraldehyde (see for example the U.S. Pat. Nos. 4,680, 127 and 5,284,635). However, simple addition of water-based hydrogen sulfide scavengers to heavy oil provides poor results.
• aldehydes such as formaldehyde, glyoxal, and glutaraldehyde
• water-based scavengers such as glyoxal will eventually settle out of the heavy oil into an acidic aqueous phase and settle to the bottom of processing equipment.
• This aqueous phase may run along the bottom of the processing or refinery equipment as small tributaries in pipelines or stagnate at the bottom of holding tanks.
• This acidic aqueous phase is highly corrosive and can cause troughing in the processing or refinery equipment.
• the invention is directed to a method for reducing the amount of hydrogen sulfide present in heavy oil and reducing the amount of corrosion in processing equipment contacting the heavy oil.
• the method includes the steps of adding an aqueous-based scavenger containing one or more aldehydes to the heavy oil using a static mixer injection system and creating an aqueous-based scavenger/heavy oil emulsion using a high shear/high velocity pump.
• the method further includes diverting a portion of the heavy oil into a scavenger addition branch, adding the aqueous-based scavenger to the portion of the heavy oil and forming the emulsion in the addition branch, and adding the aqueous-based scavenger/oil emulsion to the heavy oi l in the processing equipment.
• the aqueous-based scavenger is glyoxal.
• FIG. 1 is a schematic diagram of an aqueous-based scavenger addition system for use with hydrocarbon media processing equipment.
• a hydrogen sulfide scavenger addition system 10 is fluidically connected to processing equipment 12 for hydrocarbon media.
• the scavenger system 10 reduces the amount of hydrogen sulfide present in the hydrocarbon media, such as heavy oils, by adding an aqueous-based scavenger in a manner so as to desirably avoid causing significant corrosion to processing equipment 1 2.
• Aqueous- based scavengers are useful for the elimination of hydrogen sulphide present in various fluids and notably are particularly effective at eliminating the hydrogen sulphide present in heavy oi ls which can ex ist in the form of water in oi l or oil in water emulsions.
• the processing equipment 12 in contact with the heavy oi l may be any type of equipment that can be used for processing the hydrocarbon media, such as pipelines and holding tanks. Processing equipment 1 2 subject to corrosion is general ly processing equipment made of carbon steel, but any type of processing equipment may be protected.
• the heavy oi l may be any type of heavy oi l containing hydrogen sulfide.
• the heavy oil includes, but is not limited to, gas oi l, naphtha, FCC slurry, diesel fuel, fuel oi l, jet fuel, gasoline, kerosene or vacuum residua.
• the heavy oil may be at an elevated temperature to aid in transport in the processing equipment 1 2. For example, the heavy oil may be at a temperature of from about ambient to about 1 50 °C. Typically, the temperatures required to move the heavy oil in the processing equipment 12 is about 80 °C.
• a portion of the heavy oil flowing through the processing equipment 12 is diverted from the processing equipment 12 into the scavenger addition system 10 via a scavenger addition branch 14.
• a static mixer 1 6 is used to initially mix the scavenger with the portion of heavy oil flowing through the system 10.
• the static mixer 16 comprises an injection quill dispersion system 18.
• the scavenger is added to the diverted heavy oil flow in a continuous manner with the injection quill 1 8 located generally at the center of the addition branch 14 in the direction of the heavy oil flow.
• the injection quill 18 desirably has an open-ended tube (not shown) cut at about a 45° angle with a slot.
• the scavenger injection rate is controlled with an injection pump 20 or shut-off valve 22 in addition line 24.
• a suitable injection quill 1 8 is available from Metal Samples Corrosion Monitoring Systems of Munford, AL.
• the scavenger may be injected into the heavy oil by any conventional inline injection system and may be injected at any point in-line suitable to allow the scavenger to mix with the heavy oil.
• an aqueous-based scavenger/oil micro-emulsion is formed using a high shear/high velocity mixer or pump 30.
• a high shear/high velocity mixer or pump 30 such as one available from Silverson Machines, Inc. of East Longmeadow, MA.
• the diverted portion of the heavy oil flow in the scavenger addition system 10, now containing the micro-emulsion, is then returned to the heavy oil flow in the processing equipment 12.
• the scavenger may be added to the heavy oil flowing through the processing equipment without diverting a portion of the flow such that the entire heavy oil flow flows through the scavenger addition system 10.
• the scavenger is a dispersed aqueous phase containing about 20 to 70% of one or more aldehydes chosen from the group constituted by formaldehyde, glyoxal, glutaraldehyde, glycolaldehyde or glyoxylic acid.
• the water-based scavenger added to the heavy oil to reduce the hydrogen sulfide is Glyoxal.
• Glyoxal is a water-soluble aldehyde and may include oligomers of glyoxal.
• Glyoxal is commercially available as a 40 weight percent aqueous solution.
• the scavenger may also contain an enhancing additive to catalyze the reaction of actives with the hydrogen sulfide.
• the enhancing catalyst is a quaternary ammonium salt.
• the quaternary ammonium salt desirably is added in an amount of about 2.5 wt %.
• the glyoxal is added to the heavy oil in an amount sufficient to reduce the levels of hydrogen sulfide in the heavy oil.
• glyoxal may be added in an amount of from about I ppm to about 2000 ppm, and desirably between about I ppm and about 500 ppm by volume, based on the velocity of the heavy oil through the processing equipment and the concentration of hydrogen sulfide.
• glyoxal may be added in an amount of from about 10 ppm to about 200 ppm by volume. Any amount of hydrogen sulfide in the heavy oil may be reduced and the actual amount of residual hydrogen sulfide will vary depending on the starting amount.
• the hydrogen sulfide levels are reduced to 1 50 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil. In another embodiment, the hydrogen sulfide levels are reduced to 100 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil. In another embodiment, the hydrogen sulfide levels are reduced to 50 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil. In another embodiment, the hydrogen sulfide levels are reduced to 20 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil.

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

Applications Claiming Priority (2)

Publications (1)

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• 2009
  • 2009-12-23 US US12/646,432 patent/US20110147272A1/en not_active Abandoned
• 2010
  • 2010-10-21 AU AU2010341783A patent/AU2010341783A1/en not_active Abandoned
  • 2010-10-21 WO PCT/US2010/053457 patent/WO2011087540A2/en active Application Filing
  • 2010-10-21 MX MX2012007493A patent/MX2012007493A/es unknown
  • 2010-10-21 CN CN2010800646589A patent/CN102762696A/zh active Pending
  • 2010-10-21 EP EP10770692A patent/EP2516596A2/en not_active Withdrawn
  • 2010-10-21 CA CA2785532A patent/CA2785532A1/en not_active Abandoned
  • 2010-10-21 SG SG2012047007A patent/SG181925A1/en unknown
  • 2010-10-21 JP JP2012545940A patent/JP2013515818A/ja not_active Withdrawn
  • 2010-10-21 RU RU2012127278/04A patent/RU2012127278A/ru unknown
  • 2010-10-21 BR BR112012015563A patent/BR112012015563A2/pt not_active IP Right Cessation
  • 2010-10-21 KR KR1020127019030A patent/KR20120123348A/ko not_active Application Discontinuation
  • 2010-12-21 AR ARP100104815A patent/AR079659A1/es unknown
  • 2010-12-23 TW TW099145621A patent/TW201137108A/zh unknown
• 2012
  • 2012-06-22 CL CL2012001711A patent/CL2012001711A1/es unknown

Non-Patent Citations (1)

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