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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
  • C07C7/152—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by forming adducts or complexes
• • 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
• • 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
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • 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

Definitions

• This invention relates generally to the treatment of sour gas and liquid hydrocarbon to remove or reduce the levels of hydrogen sulfide therein.
• the toxicity of hydrogen sulfide in hydrocarbon streams is well known in the industry and considerable expense and efforts are expended annually to reduce its content to a safe level.
• a regenerative system for treating sour gas streams.
• These systems typically employ a compound used in an absorption tower to contact the produced fluids and selectively absorb the hydrogen sulfide and possibly other toxic materials such as carbon dioxide and mercaptans. The absorption compound is then regenerated and reused in the system.
• Typical hydrogen sulfide absorption materials include alkanolamines, PEG, hindered amines, and other species that can be regenerated.
• Nonregenerative scavengers for small plant hydrogen sulfide removal fall into four general categories: 1) aldehyde based, 2) metallic oxide based, 3) caustic based, and 4) other processes.
• the scavenger reacts with the hydrogen sulfide to form a nontoxic compound or a compound, which can be removed from the hydrocarbon.
• a chemical compound known as formthionals e.g., trithiane
• Prior Art aldehyde scavengers typically include low molecular weight aldehydes and ketones and adducts thereof.
• the low molecular weight aldehydes may also be combined with an alkyl or alkanolamine as disclosed in U.S. Pat. No. 4,748,011.
• Other aldehyde derived scavengers include the reaction product of low molecular weight alkanolamines and aldehydes as disclosed in U.S. Pat. No. 4,978,512.
• PCT Application WO 92/01481 discloses a method of reducing sulfides in a sewage gas using certain tri-substituted-hexahydro-s-triazines.
• German reference DE4027300 discloses a regenerative solvent for removing H 2 S and mercaptans.
• U.S. Pat. No. 5,347,004 discloses the use of 1,3,5 alkoxyalkylene hexahydro triazines.
• PCT Application WO 91 US 5232 discloses hydroxyalkyl triazine scavengers, specifically an N,N′,N′′-tris(2-hydroxyethyl)hexahydro-s-triazine.
• U.S. Pat. No. 5,774,024 discloses the combination of an alkyl triazine scavenger and quaternary ammonium salt, where the quaternary ammonium salt enhances the effectiveness of the alkyl-triazine.
• At least one embodiment of the invention is directed towards a method for removing hydrogen sulfide from a hydrocarbon fluid.
• the method comprises contacting the fluid with an effective amount of sulfide scavenger formulated with a nitroxide promoter.
• the amount of nitroxide promoter is sufficient to accelerate the scavenging action of the scavenger in comparison to the scavenging action of the scavenger in the absence of the nitroxide promoter.
• Alkyl-triazine means a molecule according to the formula:
• R 1 , R 2 , R 3 are Alkyl groups such as methyl, ethyl, propyl, isopropyl, t-butyl, etc. or are substituted alkyl groups such as CH 2 CH 2 OH, and R 1 , R 2 , R 3 can all be the same group or one or more different groups.
• Alkyl-triazines include but are not limited to the triazines disclosed in U.S. Pat. No. 5,744,024.
• Hydrocarbon fluid means a liquid or gas predominantly comprising organic material including but not limited to kerosene, crude oil, distillate fuels, fuel oil, heating oils, diesel fuel, gasoline, jet fuel, bunker fuel oils, and any combination thereof.
• Metaltriazine means an alkyl-triazine in which R 1 , R 2 , and R 3 are all methyl groups.
• Non-Regenerative Scavenger means a scavenger, which is consumed by the process of scavenging.
• Regenerative Scavenger means a scavenger, which is not consumed by the process of scavenging.
• Promoter means a composition of matter that in and of itself does not scavenge, but when combined with a known scavenger, significantly increases the effectiveness of the scavenger.
• Salt means a compound comprising an anion and a cation which usually ionizes in solution.
• “Scavenger” means a composition of matter, such as but not limited to alkyl triazines, useful in reducing the amount of some other composition of matter, such as but not limited to hydrogen sulfide, in a fluid medium.
• the amount of hydrogen sulfide in a hydrocarbon fluid is reduced by the introduction of an alkyl-triazine scavenger with a nitroxide promoter.
• the promoter increases the effectiveness of the alkyl-triazine scavenger.
• Nitroxide is superior to the prior art quarternay ammonium salt promoters because nitroxide is a single component and does not contain halides such as chloride.
• the effectiveness of a nitroxide as a promoter is unexpected because it is a single neutral compound.
• the promoter is from 1-25% of the scavenger-promoter containing composition.
• At least a portion of the triazines are synthesized according to the process described in U.S. Pat. No. 5,744,024.
• the ntiroxide is mixed with a solution of alkyl triazine where the solvent can be water and the nitroxide bearing solution is introduced into the hydrocarbon fluid.
• the nitroxide introduction is simultaneous to the alkyl-triazine introduction.
• nitroxide promoter with a scavenger over the prior art scavengers is that the nitroxide promoter is not a salt (it is not a combination of an anion and a cation) and therefore lacks halides and in particular lacks chloride.
• a scavenging formulation is used in a hydrocarbon stream.
• the formulation comprises a solvent, alkyl-triazine, and nitroxide.
• the solvent is selected from the list consisting of water, alcohol, aromatic solvent, a solvent that mutually solvates alkyl-triazine, and nitroxide and any combination thereof.
• the formulation can be introduced into the hydrocarbon stream by mechanical means including but not limited to injection pumps or any mechanism disclosed in U.S. Pat. Nos. 5,744,024 and 5,840,177.
• the gas may be passed through an absorption tower containing a scavenging formulation.
• the hydrocarbon fluid is in a liquid state. In at least one embodiment the hydrocarbon fluid is in a gaseous state.
• Samples of sour hydrocarbon streams (fuel oils) were tested to determine the efficiency of the triazine formulated with promoter versus the triazine formulated without a promoter.
• the samples were comparatively treated with various dosages of methyltriazine scavenger, methyltriazine scavenger with a promoter, and the amounts of residual H 2 S for the various samples were recorded.
• Table 1 compares the inventive composition at different concentrations
• Table 2 compares promoted scavenger with non-promoted scavenger
• table 3 compares methyltriazine with and without promoter over time.
• the vapor space hydrogen sulfide levels were measured according to the procedure described by ASTM D5705-03.
• the test procedure was modified for tables 2 and 3 by performing the test in kerosene at room temperature, which was approximately 22° C. instead of 60° C.

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

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• 2010
  • 2010-07-14 US US12/835,805 patent/US20120012506A1/en not_active Abandoned
• 2011
  • 2011-07-13 AR ARP110102527A patent/AR082847A1/es active IP Right Grant
  • 2011-07-13 SG SG2013003025A patent/SG187080A1/en unknown
  • 2011-07-13 EP EP11807421.0A patent/EP2593534A4/en not_active Withdrawn
  • 2011-07-13 BR BR112013000887A patent/BR112013000887A2/pt not_active Application Discontinuation
  • 2011-07-13 JP JP2013519782A patent/JP5815699B2/ja active Active
  • 2011-07-13 CN CN2011800347098A patent/CN103003395A/zh active Pending
  • 2011-07-13 KR KR1020137003668A patent/KR20130047738A/ko not_active Ceased
  • 2011-07-13 CA CA2805402A patent/CA2805402C/en active Active
  • 2011-07-13 RU RU2013102415/04A patent/RU2562610C2/ru active
  • 2011-07-13 WO PCT/US2011/043780 patent/WO2012009391A2/en not_active Ceased
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