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 fluids is well known in the industry. This has caused considerable expense and efforts to be 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 nonlethal 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 US Patent 4,748,011.
• Other aldehyde derived scavengers include the reaction product of low molecular weight alkanolamines and aldehydes as disclosed in US Patent 4,978,512.
• PCT Application WO 92/01481 discloses a method of reducing sulfides in different applications using certain tri-substituted-hexahydro-s-triazines.
• German reference DE4027300 discloses a regenerative solvent for removing 3 ⁇ 4S and mercaptans.
• US Patent 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.
• US Patent 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..
• These prior art attempts however are frequently water-based chemicals and require significant mixing to allow the scavenger to effectively contact the hydrocarbon fluid and remove the hydrogen sulfide.
• 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 a composition comprising a hydrogen sulfide scavenger.
• the amount of hydrogen sulfide scavenger is sufficient to react with the hydrogen sulfide to reduce the amount hydrogen sulfide released into the vapor space .
• the reaction product of the hydrogen sulfide scavenger and the hydrogen sulfide remain soluble in the hydrocarbon fluid.
• the hydrogen sulfide scavenger contains at least one alpha-amino ether.
• composition may include one item selected from the list consisting of:
• the reaction product of the sulfide scavenging formulation and the hydrogen sulfide may not form a separate fluid layer.
• the method may also further comprise the step of reacting a secondary amine with a formaldehyde equivalent to form at least some of the scavenging formulation.
• the hydrocarbon fluid may be a liquid.
• Alpha-amino ether means a molecule according to the formula:
• R l9 R 2 , R 3 , R4 are carbon containing side chains containing 1 - 20 carbon atoms and includes cyclic and acyclic compounds.
• the cyclic compounds can be aromatic or non-aromatic. Examples include but are not limited to, methyl, ethyl, propyl, tert-butyl, cyclopentyl, cyclohexyl, morpholino, and phenyl, and they all can be the same group or one or more different groups.
• B is an ether group, which is either an oxygen atom or a group having an oxygen atom at both ends (such as -OCH 2 0- or-OCsUtO-).
• Formaldehyde equivalent means a composition of matter containing at least one group according to the formula: ( ⁇ 3 ⁇ 40) ⁇ in which n is an integer greater than or equal to 1, and/or a composition of matter including formaldehyde or related molecules such as
• Hydrocarbon fluid means a liquid or gas predominantly comprising organic material including but not limited to kerosene, crude oil, crude oil emulsions, oilfield condensate, petroleum residua, refined fuels, distillate fuels, fuel oil, heating oils, diesel fuel, gasoline, jet fuel, bunker fuel oils, and any combination thereof.
• 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.
• “Scavenger” means a composition of matter, such as but not limited to alpha- amino ethers, useful in reducing the amount of or mitigating the effects of some other composition of matter, such as but not limited to hydrogen sulfide, in a fluid medium.
• the hydrogen sulfide in a hydrocarbon fluid is reduced by the introduction of an alpha-amino ether scavenger into the fluid.
• the alpha-amino ether is a portion of a scavenging formulation is used in a hydrocarbon fluid.
• the formulation comprises alpha-amino ether and can consist of a carrier liquid as well.
• the formulation can be introduced into the hydrocarbon fluid by mechanical means including but not limited to injection pumps or any mechanism disclosed in US Patents 5,744,024 and 5,840,177.
• the gas may be passed through an absorption tower containing a scavenging formulation.
• alpha-amino ether scavenger is soluble in hydrocarbon fluids, since it is not a water-based product.
• the hydrogen sulfide scavenger is produced by reacting a secondary amine with formaldehyde or other formaldehyde equivalents such as paraformaldehyde or s-trioxane.
• formaldehyde or other formaldehyde equivalents such as paraformaldehyde or s-trioxane.
• the reaction product also comprises 10-25% of the non-ether diamine (compound A).
• Compound A is an unavoidable side product of the reaction mixture.
• the reaction can be performed by mixing the reactants in solvents such as but not limited to Naphtha (Petroleum) Heavy Aromatic Solvents (such as Aromatic 150 and Solvesso by ExxonMobil) or Naphtha Light Aromatic Solvents (such as (Aromatic 100 by Americhem Sales Corporation).
• solvents such as but not limited to Naphtha (Petroleum) Heavy Aromatic Solvents (such as Aromatic 150 and Solvesso by ExxonMobil) or Naphtha Light Aromatic Solvents (such as (Aromatic 100 by Americhem Sales Corporation).
• the ratio of amine to formaldehyde in the reaction mixture is inclusively within the range of 1.5:1 to 1:1.5 and is preferably between 1.2:1 and 1:1.2.
• any of the R and R' groups correspond to any of the Ri, R 2 , R , and R4, groups described in the definition of "alpha-amino ether".
• Compound A is ⁇ , ⁇ , ⁇ ', ⁇ '-tetrabutylmethanediamine
• Compound B is N,N'-oxybis(methylene)bis(N,N-dibutylene), and
• Compound C is N 5 N'-(methylenebis(oxy)bis(methylene))bis(N,N'-dibutylamine).
• compositions comprising:
• Table 1 compares the inventive composition in naphtha at 22 degrees C
• Table 2 kerosene at 22 degrees C, and Table 3 slurry oil (such as carbon black oil, decant oil, and clarified slurry oil produced in a refinery) at 97 degrees C.
• slurry oil such as carbon black oil, decant oil, and clarified slurry oil produced in a refinery
• Tat le 2 tes 22 °C
• the amount of H 2 S present in the vapor space was determined by measuring the vapor space hydrogen sulfide levels according to ASTM D5705-03. test procedure was modified by running at temperatures other than 60°C. A one-gallon sample was divided into multiple 500 milliliter samples for testing. The treated containers were pre-dosed with Compounds A-C and then the fluid being tested was poured into the container. In each example, the dose ratio was the number used to determine the ppm treat rate for the sample. For table 1 the untreated sample resulted in a vapor space

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Analytical Chemistry (AREA)
• Water Supply & Treatment (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Gas Separation By Absorption (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2010
  • 2010-07-14 US US12/836,037 patent/US20120012507A1/en not_active Abandoned
• 2011
  • 2011-07-13 MX MX2013000507A patent/MX2013000507A/es active IP Right Grant
  • 2011-07-13 WO PCT/US2011/043793 patent/WO2012009396A2/en not_active Ceased
  • 2011-07-13 JP JP2013519783A patent/JP5890409B2/ja active Active
  • 2011-07-13 KR KR1020137003671A patent/KR20130047739A/ko not_active Ceased
  • 2011-07-13 RU RU2013102414/04A patent/RU2563633C2/ru active
  • 2011-07-13 AR ARP110102515A patent/AR082165A1/es active IP Right Grant
  • 2011-07-13 CA CA2805404A patent/CA2805404C/en active Active
  • 2011-07-13 SG SG2013002993A patent/SG187078A1/en unknown
  • 2011-07-13 BR BR112013000890A patent/BR112013000890A2/pt not_active Application Discontinuation
  • 2011-07-13 CN CN201180034667.8A patent/CN103403129B/zh active Active
  • 2011-07-13 EP EP20110807425 patent/EP2593535A4/en not_active Ceased

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