WO2002034863A1 - Elimination de mercaptans de flux d'hydrocarbures a l'aide de liquides ioniques - Google Patents

Elimination de mercaptans de flux d'hydrocarbures a l'aide de liquides ioniques Download PDF

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Publication number
WO2002034863A1
WO2002034863A1 PCT/US2001/032211 US0132211W WO0234863A1 WO 2002034863 A1 WO2002034863 A1 WO 2002034863A1 US 0132211 W US0132211 W US 0132211W WO 0234863 A1 WO0234863 A1 WO 0234863A1
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Prior art keywords
ionic liquid
disulfides
mercaptans
hydrocarbon
ionic liquids
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PCT/US2001/032211
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English (en)
Inventor
Dennis J. O'rear
Laura C. Boudreau
Michael S. Driver
Curtis L. Munson
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Chevron U.S.A. Inc.
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Priority to AU2002216629A priority Critical patent/AU2002216629A1/en
Priority to CA002426770A priority patent/CA2426770A1/fr
Priority to EP01988754A priority patent/EP1337605A1/fr
Publication of WO2002034863A1 publication Critical patent/WO2002034863A1/fr

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    • 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas

Definitions

  • the present invention is in the field of organic chemistry, in particular removal of mercaptans from hydrocarbon streams.
  • Mercaptans are commonly removed using a “sweetening” or “extractive sweetening” process.
  • This type of process generally involves reacting mercaptans (RSH) with caustic solutions (NaOH) to form water and mercaptides (NaSR).
  • the mercaptides are then oxidized, usually with air, to form disulfides (RSSR 1 ), which regenerates the caustic.
  • the disulfides are for the most part immissible in the caustic and can be separated by density differences.
  • the disulfides can either be disposed of or, in some cases, blended with the original product stream.
  • the caustic is generally recycled until it reaches a low enough concentration where it is no longer effective at adsorbing the mercaptans.
  • the concentration of caustic decreases in part because the water formed in the reaction of the mercaptan with caustic generates water, which remains with the caustic. Dissolved water in the crude oil can also cause a decline in the concentration of the caustic. The result is that the caustic must continuously be disposed of and replaced. It is particularly difficult to remove low molecular weight mercaptans such as ethyl and methyl mercaptan from crude oils. These mercaptans must be reduced to a few ppm for them to be acceptable for shipping on tankers.
  • the oxidation of the mercaptides to disulfides and regenerated caustic can be done with a variety of oxidants (air, pure oxygen, enriched air, chemical oxidants such as hydrogen peroxide) or mixtures thereof. However, air is the most commonly used oxidant because of its low cost.
  • the oxidation of the mercaptides can be done without a catalyst, but the reaction tends to be slow. It is generally preferred to incorporate a catalyst to accelerate the oxidation of the mercaptides.
  • These catalysts are typically metals, and the most common metals are lead (typically as PbS), copper (typically as a copper chloride), or a phthalocyanine complex of copper, iron, nickel or cobalt, preferably cobalt.
  • a particularly effective pthalocyanine complex involves cobalt phthalocyanine complexes with electron withdrawing substituents on the phthalocyanine ring.
  • Particularly effective electron withdrawing substituents include a halogen (preferably chlorine) and sulfate groups as described in U.S. Pat. No. 5,880,279.
  • the extraction of the mercaptans and the oxidation of the mercaptides can be done in one or two stages.
  • the advantage of the use of one stage is primarily lower cost, but the disadvantages include the mixing of the oxidant and petroleum product, and the blending of the mercaptan reaction product disulfides with the petroleum product.
  • the advantages of use to two separate stages is the avoidance of mixing the oxidant and the petroleum product, and the separation of the disulfide reaction product, but the disadvantage is higher cost.
  • Mercaptans can be removed from whole crudes by contacting the crude oil with a caustic mixture that includes a cobalt phthalocyanine complex and air, as described in U.S. Pat No. 5,683,574.
  • the cobalt phthalocyanine complexes are selected to avoid formation of emulsions.
  • the caustic/cobalt phthalocyanine solution simultaneously adsorbs the mercaptans and reacts them to form disulfides, which remain in the crude.
  • the caustic and phthalocyanine complexes can be partially recovered using a separation system.
  • this technology has various technical limitations.
  • Methods for removing mercaptans from hydrocarbon streams, preferably crude oil involve forming a solution of a basic metal salt such as sodium hydroxide in an ionic liquid, preferably a non-water reactive ionic liquids, and contacting the ionic liquid solution with a hydrocarbon stream in a manner which contacts mercaptans in the hydrocarbon stream with the basic metal salt.
  • the resulting mercaptide salts are either dissolved or dispersed in the ionic liquid, dissolved in the reaction water, or precipitated. Generally they are dissolved in the ionic liquid.
  • the resulting de-sulfurized hydrocarbon feedstream can be separated from the ionic liquid, for example by distillation, decantation or gravity separation.
  • the caustic can be recovered by oxidizing the mercaptides to form disulfides, preferably using air or oxygen.
  • the oxidation can be promoted by a catalyst, preferably a metal phthalocyanine complex where the metal is preferably cobalt and the phthalocyanine ring includes halogens, preferably chlorine, as described in U.S. Pat. No. 5,880,279.
  • the catalyst can be fixed on a solid support or, alternatively, dissolved or dispersed in the ionic liquid.
  • the disulfides are non-ionic and tend to be insoluble in the ionic liquids. Accordingly, the disulfides can be readily removed, for example via distillation, decantation or gravity separation. Additionally, the disulfides can be removed by stripping with steam, air or other suitable gas streams, or by extraction in a suitable solvent, for example a hydrocarbon solvent. The de- sulfurized ionic liquid can then be recycled.
  • the reaction water produced by the reaction of caustic and mercaptans tends to be insoluble in the ionic liquids.
  • the water can also be removed by distillation, decantation or gravity separation. If the mercaptide is not particularly soluble in the reaction water, the water can be removed by decantation or gravity separation before the oxidation step.
  • the basic metal salt can be kept reasonably concentrated in the ionic liquid without unwanted dilution in water using the methods described herein.
  • the mercaptan-containing hydrocarbon stream can be in the gas phase or in the liquid phase.
  • the flow of hydrocarbon stream over/through the ionic liquid can be, for example, co- current, counter-current, or staged in stirred tanks, with countercurrent being preferred.
  • Figure 1 is a schematic illustration of a mercaptan removal process using the method described herein.
  • adsorption is used to describe the movement of mercaptans out of hydrocarbon streams and into ionic liquids in the form of mercaptides.
  • Mercaptans are . 50 mercaptans (carbon-containing compounds that contain a -SH group), more preferably C MO (cyclic, linear, branched and aromatic) mercaptans. They may include other functional groups, such as hydroxy groups, carboxylic acid groups, heteroatoms, and the like, provided that such groups do not react with either the base (typically sodium hydroxide) or the ionic liquid.
  • C MO cyclic, linear, branched and aromatic
  • the hydrocarbon feeds-reams include crude oil feedstreams and natural gas feedstreams.
  • the hydrocarbon stream can include a C 6 - fraction.
  • the hydrocarbon stream can include more than about 50% by weight methane, ethane, propane, butane or combinations thereof.
  • hydrocarbon feedstreams include relatively high levels of sulfur impurities
  • the feedstream is amenable to hydrotreatment or other means well known to those of skill in the art, such as extractive Merox
  • such methods can be used to reduce the level of sulfur impurities, and residual mercaptans can be removed using the methods described herein.
  • the basic salts can be virtually any base capable of reacting with mercaptans to form mercaptides. Examples include alkali metal and alkaline earth hydroxides, carbonates and bicarbonates. Sodium hydroxide is a preferred basic salt.
  • the concentration of the basic salt in the ionic liquid is typically at least about 0.5 moles of salt per liter of solvent, and preferably at least about 2 moles of salt per liter of solvent.
  • the salts are able to react with the mercaptans at a variety of concentrations. At relatively high concentrations, the mercaptides may precipitate from solution. If this precipitation is not desirable, more dilute solutions/dispersions should be used. However, this precipitation may be desirable and allow one to separate various mercaptides by precipitation and subsequent filtration.
  • the extent of mercaptan removal is a least 10%, preferably more than 50% and most preferably more than 90%.
  • the product disulfides can be either produced as a separate stream or blended with the hydrocarbon product.
  • Methods of measuring mercaptans in petroleum products include gas chromatography (especially when coupled with a sulfur sensitive elemental detector).
  • ASTM D3227 can also be used to measure mercaptans in gasoline, jet and distillate boiling range products. If quantitative measurements of mercapans are not possible (for example in heavy crude oils), the extent of mercaptan removal can be judged by an improvement in the copper strip corrosion test (ASTM Dl 30) of at least one value.
  • Ionic liquids are organic compounds that are liquid at room temperature. They differ from most salts in that they have very low melting points. They tend to be liquid over a wide temperature range, and are not soluble in non-polar hydrocarbons. Depending on the anion, they tend to be immiscible with water, and are highly ionizing (but have a low dielectric strength).
  • Ionic liquids have essentially no vapor pressure. Most are air- and water-stable, and they are used herein as a catalyst and/or solvent for the Diels-AIder reaction between the diene and the dienophile.
  • the properties of the ionic liquids can be tailored by varying the cation and anion. Ionic liquids and their commercial applications are described, for example, in J. Chem. Tech.
  • ionic liquids are formed by reacting a nitrogen-containing heterocyclic ring, preferably a heteroaromatic ring, with an alkylating agent (for example, an alkyl halide) to form a quaternary ammonium salt, and performing ion exchange or other suitable reactions to form ionic liquids.
  • alkylating agent for example, an alkyl halide
  • suitable heteroaromatic rings include pyridine, substituted pyridines, imidazole, substituted imidazoles, pyrrole and substituted pyrroles.
  • Suitable substituents include, for example, straight, branched, or cyclic alkyl groups, preferably a methyl group, alkyl chains containing a terminal alcohol group, alkyl groups containing heteroatoms such as oxygen, nitrogen and/or sulfur.
  • the substituents can be in any position on the heteroaromatic ring, but in the case of pyridine, is preferably in the para (or 4) position.
  • These rings can alkylated with virtually any straight, branched or cyclic C ⁇ . 2 o alkyl group, but preferably the alkyl groups are -i ⁇ groups, since groups larger than this tend to produce low melting solids rather than ionic liquids.
  • Various triarylphosphines, thioethers, and cyclic and non- cyclic quaternary ammonium salts have also been used.
  • Counterions which have been used include chloroaluminate, bromoaluminate, gallium chloride, tetrafluoroborate, tetrachloroborate, hexafluorophosphate, nitrate, frifluoromethane sulfonate, methylsulfonate, p-toluenesulfonate, hexafluoroantimonate, hexafluoroarsenate, tetrachloroaluminate, tetrabromoaluminate, perchlorate, hydroxide ion, copper dichloride anion, iron trichloride anion, zinc trichloride anion, as well as various lanthanum, potassium, lithium, nickel, cobalt, manganese, and other metal ions.
  • low melting solids can also be used in place of ionic liquids, depending on the particular separation to be effected.
  • Low melting solids are generally similar to ionic liquids but have melting points between room temperature and about 212°C or are liquid under the process conditions. The use of low melting solids can be preferred if the density of the products and the ionic liquid are similar and it becomes difficult to phase separate products from the ionic liquids. In such a case, the low melting solid can be crystallized and separated from the products.
  • the term "ionic liquid" is intended to include low melting solids unless otherwise specified.
  • the ionic liquids can either be neutral, acidic or basic.
  • ionic liquids chloroaluminate salts
  • neutral ionic liquids for example, tetrafluoroborate or hexafluorophosphate salts
  • water is generated, it can be preferable to use non-water reactive ionic liquids, particularly if large amounts of mercaptans are to be removed.
  • Neutral ionic liquids are also preferred if the hydrocarbon stream includes acid-sensitive components, for example normal alpha olefins, which are prone to isomerization.
  • a library of ionic liquids is prepared, for example by preparing various alkyl derivatives of the quaternary ammonium cation, and/or varying the associated anions.
  • the acidity of the ionic liquids can be adjusted, for example by varying the molar equivalents and combinations of Lewis acids.
  • the methods involve forming a solution of a basic metal salt such as sodium hydroxide in an ionic liquid, preferably a non-water reactive ionic liquids, and contacting the ionic liquid solution with a hydrocarbon stream in a manner which contacts mercaptans in the hydrocarbon stream with the basic metal salt.
  • the resulting mercaptide salts are either dissolved or dispersed in the ionic liquid, dissolved in the reaction water or precipitated. Preferably they are dissolved in the ionic liquid.
  • the resulting de-sulfurized hydrocarbon feedstream can be separated from the ionic liquid, for example by distillation, decantation or gravity separation.
  • the hydrocarbon stream, the ionic liquid incorporating the basic metal salt, and an oxidant can be contacted simultaneously.
  • the product disulfide will be incorporated into the product.
  • a catalyst to promote generation of the basic metal salt can also be incorporated as well (either dissolved in the ionic liquid, dispersed in the ionic liquid or supported on a solid).
  • low melting solids are used in place of ionic liquids, and the desulfurized hydrocarbon feedstream is recovered following precipitation of the low melting solid.
  • the low melting solid must be a liquid at the temperature at which the mercaptans are adsorbed, to pennit contact of the mercaptans with the basic salt.
  • the caustic can be recovered by oxidizing the mercaptides to form disulfides, preferably using air or oxygen.
  • the oxidation can be promoted by a catalyst, preferably a metal phthalocyanine complex where the metal is preferably cobalt and the phthalocyanine ring includes halogens, preferably chlorine.
  • the preferred catalyst is described in U.S. Pat. No. 5,880,279.
  • the catalyst can be fixed on a solid support or, alternatively, dissolved or dispersed in the ionic liquid.
  • the disulfides are non-ionic, and tend to be insoluble in the ionic liquids. Accordingly, the disulfides can be readily removed, for example via distillation, decantation or gravity separation. Additionally, the disulfides can be removed by stripping with steam, air or other suitable gas streams, or by extraction in a suitable solvent, for example a hydrocarbon solvent. The resulting de-sulfurized ionic liquids can be recycled.
  • the water formed by reacting hydroxide ions with mercaptans tends to be insoluble in the ionic liquids.
  • the water can also be removed by distillation, decantation or gravity separation. Decantation and gravity separation may tend to remove caustic and/or mercaptide salts from the ionic liquid. Accordingly, distillation, preferably under reduced pressure, is a preferred method for removing the water.
  • distillation preferably under reduced pressure, is a preferred method for removing the water.
  • the reaction water can be removed before the oxidation step.
  • the basic metal salt can be kept reasonably concentrated in the ionic liquid without unwanted dilution in water using the methods described herein.
  • the mercaptan-containing hydrocarbon stream can be in the gas phase or in the liquid phase.
  • the flow of hydrocarbon stream over/through the ionic liquid can be, for example, co- current, counter-current, or staged in stirred tanks, with countercurrent being preferred.
  • the method is shown in more detail in Figure 1.
  • a hydrocarbon with mercaptan (RSH) impurities is introduced to a contactor (10) that contains a non-water reactive ionic liquid and caustic.
  • the resulting mercaptide is then either dispersed or dissolved in the ionic liquid, precipitated, or dissolved in the resulting aqueous phase.
  • the reaction mixture is sent to a separator (20) where a purified hydrocarbon stream can be separated.
  • the ionic liquid and, optionally, reaction water are sent to an oxidation reactor (30) where disulfide is formed and caustic is regenerated.
  • the disulfide and reaction water can then be removed, regenerating the ionic liquid and caustic.
  • the regenerated ionic liquid and caustic are then recycled to the contactor (10).
  • a combinatorial approach can be used to identify optimum ionic liquids and/or basic salts for removing mercaptans from various hydrocarbon streams.
  • An advantage to the combinatorial approach is that the choice of ionic liquid, basic salt and the like can be tailored to specific applications.
  • the scale of the mercaptan removal in combinatorial chemistry is preferably in the range of about 1 mg to 200 g, more preferably between one mg and 10 g, although the scale can be modified as desired depending on the equipment used. Those of skill in the art can readily determine appropriate sets of reactions and reaction conditions to generate and/or evaluate the libraries of interest.
  • the ionic liquids can be laid out in a logical fashion in multi-tube arrays or multi-well plates in the form of arrays of ionic liquids.
  • the ionic liquids all have a central core structure and have various modifications that permit the identification of structure-activity relationships with which to determine optimum compounds for a particular use.
  • the basic metal salts or combinations thereof can also be laid out in a logical fashion, for example in arrays.
  • an A x B array is prepared with various combinations of ionic liquids and basic metal salts.
  • the ability of the particular combination of ionic liquid and metal salt at performing a desired mercaptan removal can be measured and correlated to specific combinations.
  • the array can be ordered in such a fashion as to expedite synthesis and/or evaluation, to maximize the informational content obtained from the testing and to facilitate the rapid evaluation of that data.
  • Methods for organizing libraries of compounds are well known to those of skill in the art, and are described, for example, in U.S. Patent No. 5J12J71 to Zambias et al. Such methods can readily be adapted for use with the ionic liquids and basic metal salts described herein.
  • the selection of the optimal candidate is more a function of the data collection method than the "rational" basis for selecting a useful ionic liquid and/or metal salt.
  • the desired physical and chemical properties for the ionic liquid when used as a solvent or dispersing agent for a particular metal salt, and for removing a particular mercaptan from a particular hydrocarbon stream, can be rapidly optimized, and directly correlated with the structural changes within a particular array or sub-array.
  • the ionic liquids are typically fonned by first forming a desired (cyclic, non-cyclic or aromatic) quaternary ammonium salt, and then combining the salt with an appropriate anion precursor (typically a metal salt such as aluminum chloride, zinc chloride, sodium hexafluorophosphate, sodium tetrafluoroborate, hexafluorophosphoric acid, tefrafluoroboric acid and the like).
  • an appropriate anion precursor typically a metal salt such as aluminum chloride, zinc chloride, sodium hexafluorophosphate, sodium tetrafluoroborate, hexafluorophosphoric acid, tefrafluoroboric acid and the like.
  • Side products salts can be removed, for example by filtration or, in cases where the anion precursor was an acid, the acid side products such as HC1 can be removed by extraction or by gently heating the ionic liquid under vacuum.
  • the mercaptan removal using the ionic liquids/metal salts in the libraries generally involve contacting appropriate mixtures of mercaptans and hydrocarbons with the ionic liquids/basic metal salts in the tubes or wells in the multi-tube rack or multi-well plate, and allowing the mercaptide formation to take place.
  • the formation of the mercaptide, and desulfurization of the hydrocarbon stream can be analyzed, for example by GC by following mercaptan removal.
  • the presence or absence of mercaptans can be evaluated, for example using GC, to determine the success of the particular combination of ionic liquid and basic metal salt.
  • Robotic arms and multi-pipet devices are commonly used to add appropriate reagents to the appropriate tubes in multi-tube racks or wells in multi-well plates.
  • the chemistry is performed in an inert atmosphere to avoid oxidation of mercaptides to form disulfides before the desulfurized hydrocarbon stream is removed. This can be done, for example, by covering the tubes with a rubber septum to avoid contamination, and adding the reagents via injection.
  • the mercaptan removal is carried out via computer control.
  • the identity of each of the ionic liquids and basic metal salts can be stored in a computer in a "memory map" or other means for correlating the data regarding the chemical reactions to the ionic liquids in the multi-tube racks or multi-well plates.
  • the chemistry can be performed manually, preferably in multi-tube racks or multi-well plates, and the infonnation stored, for example on a computer.
  • any type of multi-well plate or multi-tube array commonly used in combinatorial chemistry can be used.
  • the number of wells or tubes is in excess of 30, and there is a tube in at least 60 percent of the positions in each multi-tube array.
  • the shape of the rack is not important, but preferably, the rack is square or rectangular.
  • the tubes can be made, for example, from plastic, polymers, glass or metal such as stainless steel, depending on the type of anions used in the ionic liquid or in the metal salt.
  • Any type of liquid handler that can add reagents to, or remove reagents from, the wells and/or tubes can be used. Suitable liquid handlers are prepared, for example by Tecan. Many involve the use of robotic arms and robotic devices.
  • Suitable devices are well known to those of skill in the art of combinatorial chemistry, and include those by Zymart, Gilson, Hamilton, Bodhan and Tecan. Any device that can take samples from the individual wells and/or tubes and analyze the resulting hydrocarbon phase can be used.
  • the device is a chromatographic device such as an analytical or preparative scale HPLC, GC or column chromatography, although other devices can be envisioned depending on the chemistry performed. Since the ionic liquid is non-volatile, the sample is preferably taken from the hydrocarbon phase, which is immiscible with the ionic liquid.
  • the device has the ability to identify when the compound of interest is eluting from the column.
  • Various means have commonly been used to identify when compounds of interest are eluting from a column, including UN, IR, TLC, GC-MS, FED, ⁇ MR, ELSD, nitrogen detection and the like. Any of these means and others known to those of skill in the art can be used, alone or in combination.
  • the analytical equipment preferably includes an ELSD detector.
  • the entire eluent from the chromatographic columns described above can be sent through an appropriate detector and then to a mass spectrometer.
  • sample collection it can begin when the UN or mass spectrometry signal indicates the presence of the eluting compound, and can end when the UN signal indicates that the compound has finished eluting from the column.
  • Mass spectrometry can verify that the eluted compound is really the compound of interest.
  • the device preferably includes a computer system capable of storing information regarding the identity of the ionic liquids, metal salts and the product streams obtained when combinations of ionic liquids and basic metal salts are used to remove the mercaptans.
  • Software for managing the data is stored on the computer. Relational database software can be used to correlate the identity of the ionic liquids, the metal salts, and the analytical data from each product stream. Numerous commercially available relational database software programs are available, for example from Oracle, Tripos, MDL, Oxford Molecular (“Chemical Design”), IDBS ("Activity Base”), and other software vendors.
  • Relational database software is a preferred type of software for managing the data obtained during the processes described herein. However, any software that is able to create a "memory map" of the ionic liquids in the tubes and correlate that information with the information obtained from the chemical reactions can be used. This type of software is well known to those of skill in the art.
  • 1-Methylimidazole was measured into a stainless-steel autoclave along with a slight molar excess of 1-chlorobutane.
  • the autoclave was sealed, pressurized with 75 psig of nitrogen, and heated to 90°C for 18 h.
  • the autoclave was then cooled to room temperature and the contents were placed on a rotary evaporator at 95°C for several hours to remove any unreacted chlorobutane and 1- methylimidazole.
  • a ] H NMR of the product indicated the formation of l-butyl-3- methylimidazolium chloride (bmim + Cl " ).
  • a neutral ionic liquid Two different procedures were used for conducting an anion exchange reaction to give a neutral ionic liquid.
  • the precursor is dissolved in acetone and reacted with the sodium salt of the desired anion (NaBF or NaPF ⁇ ).
  • the precursor is dissolved in water and reacted with the acid form of the anion (HBF or HPF 6 ).
  • the precursor hmim + Cr was used make the ionic liquid hmim + PF 6 " by both procedures.
  • the miscibility of the resulting ionic liquid with water was greatly influenced by the route of synthesis.
  • the ionic liquid made by the acid route was immiscible with water, while the ionic liquid made using the sodium salt was miscible with water. While not wishing to be bound to a particular theory, it is believed that this change in miscibility with water is due to the presence of residual NaCl in the liquid made via the salt route.
  • hexPPh 3 hexylfriphenylphosphonium

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Abstract

L'invention concerne des procédés permettant d'éliminer les mercaptans de flux d'hydrocarbures, par exemple, du pétrole brut ou du gaz naturel. Ces procédés utilisent des sels métalliques basiques qui réagissent avec les mercaptans de façon à former des mercaptides. Lesdits sels métalliques sont dissous ou en suspension dans des liquides ioniques qui virtuellement ne possèdent pas de pression de vapeur. Une fois que les mercaptides sont adsorbés dans lesdits liquides ioniques, le flux d'hydrocarbures démercaptanisés peut être éliminé, par exemple, par distillation, décantation, ou séparation par gravité. Puis les mercaptides peuvent être oxydés, par exemple, par exposition à l'air afin de former des disulfides. Ces disulfides sont insolubles dans les liquides ioniques, et peuvent donc facilement être éliminés. L'hydroxyde de sodium est le sel préféré, et les liquides ioniques non réactifs à l'eau sont les liquides préférés. Le flux d'hydrocarbures contenant des mercaptans peut être en phase gazeuse ou en phase liquide. L'écoulement du flux d'hydrocarbures sur/à travers le liquide ionique peut, par exemple, s'effectuer dans le sens du courant, à contre-courant, ou par étapes dans des réservoirs avec agitation mécanique, l'écoulement à contre courant étant l'écoulement préféré.
PCT/US2001/032211 2000-10-26 2001-10-16 Elimination de mercaptans de flux d'hydrocarbures a l'aide de liquides ioniques WO2002034863A1 (fr)

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AU2002216629A AU2002216629A1 (en) 2000-10-26 2001-10-16 Removal of mercaptans from hydrocarbon streams using ionic liquids
CA002426770A CA2426770A1 (fr) 2000-10-26 2001-10-16 Elimination de mercaptans de flux d'hydrocarbures a l'aide de liquides ioniques
EP01988754A EP1337605A1 (fr) 2000-10-26 2001-10-16 Elimination de mercaptans de flux d'hydrocarbures a l'aide de liquides ioniques

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Cited By (31)

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WO2003070667A1 (fr) * 2002-02-19 2003-08-28 Oxeno Olefinchemie Gmbh Procede de separation de substances par extraction ou lavage par des liquides ioniques
FR2840916A1 (fr) * 2002-06-17 2003-12-19 Inst Francais Du Petrole Procede d'elimination des composes soufres et azotes de coupes hydrocarbonees
FR2840917A1 (fr) * 2002-06-17 2003-12-19 Inst Francais Du Petrole Procede d'elimination des composes soufres et azotes de coupes hydrocarbonees
WO2005019137A1 (fr) * 2003-07-21 2005-03-03 Basf Aktiengesellschaft Procede pour extraire des impuretes au moyen de liquides ioniques
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DE102009022284A1 (de) 2008-05-26 2010-03-25 Instituto Mexicano Del Petroleo Entschwefelung von Kohlenwasserstoffen durch ionische Flüssigkeiten und Herstellungsverfahren
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WO2010116165A3 (fr) * 2009-04-06 2010-12-16 Petroliam Nasional Berhad (Petronas) Procédé d'élimination de métaux à partir d'hydrocarbures
WO2013098056A1 (fr) 2011-12-28 2013-07-04 Lanxess Deutschland Gmbh Purification de caoutchouc nitrile éventuellement hydrogéné
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WO2003070667A1 (fr) * 2002-02-19 2003-08-28 Oxeno Olefinchemie Gmbh Procede de separation de substances par extraction ou lavage par des liquides ioniques
FR2840916A1 (fr) * 2002-06-17 2003-12-19 Inst Francais Du Petrole Procede d'elimination des composes soufres et azotes de coupes hydrocarbonees
FR2840917A1 (fr) * 2002-06-17 2003-12-19 Inst Francais Du Petrole Procede d'elimination des composes soufres et azotes de coupes hydrocarbonees
US7198712B2 (en) 2002-06-17 2007-04-03 Institut Francais Du Petrole Processing for eliminating sulfur-containing compounds and nitrogen-containing compounds from hydrocarbon
US7732494B2 (en) * 2003-03-27 2010-06-08 Japan Science And Technology Agency Method of concentrating fine particle dispersion and method of recovering fine particle
WO2005019137A1 (fr) * 2003-07-21 2005-03-03 Basf Aktiengesellschaft Procede pour extraire des impuretes au moyen de liquides ioniques
US7605297B2 (en) 2003-07-21 2009-10-20 Basf Aktiengesellschaft Method for extracting impurities using ionic liquids
US7718586B2 (en) 2004-02-11 2010-05-18 Baker Hughes Incorporated Hydrocarbons having reduced levels of mercaptans and method and composition useful for preparing same
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WO2005097749A1 (fr) * 2004-04-06 2005-10-20 Lonza Ag Dicyanamides d'alkylpyridinium et procede pour leur production
JP2007531783A (ja) * 2004-04-06 2007-11-08 ロンザ ア−ゲ− アルキルピリジニウムジシアナミドおよびそれらの製造方法
US7303607B2 (en) 2004-06-14 2007-12-04 Air Products And Chemicals, Inc. Liquid media containing Lewis acidic reactive compounds for storage and delivery of Lewis basic gases
FR2873711A1 (fr) * 2004-08-02 2006-02-03 Inst Francais Du Petrole Procede de capture des mercaptans contenus dans une charge gazeuse
US7192565B2 (en) 2004-08-02 2007-03-20 Institut Francais Du Petrole Method of collecting mercaptans contained in a gaseous feed
US7563308B2 (en) 2004-09-23 2009-07-21 Air Products And Chemicals, Inc. Ionic liquid based mixtures for gas storage and delivery
US7404845B2 (en) 2004-09-23 2008-07-29 Air Products And Chemicals, Inc. Ionic liquid based mixtures for gas storage and delivery
US8202446B2 (en) 2004-09-23 2012-06-19 Air Products And Chemicals, Inc. Ionic liquid based mixtures for gas storage and delivery
CN100453622C (zh) * 2005-03-24 2009-01-21 北京化工大学 一种用离子液体萃取脱除汽柴油中硫化物的方法
US7585415B2 (en) 2005-04-07 2009-09-08 Matheson Tri-Gas Fluid storage and purification method and system
US7638058B2 (en) 2005-04-07 2009-12-29 Matheson Tri-Gas Fluid storage and purification method and system
US7670490B2 (en) 2005-04-07 2010-03-02 Matheson Tri-Gas, Inc. Fluid storage and purification method and system
US8083945B2 (en) 2005-04-07 2011-12-27 Matheson Tri-Gas, Inc. Fluid storage and purification method and system
US7938968B2 (en) 2005-04-07 2011-05-10 Matheson Tri Gas Fluid storage and purification method
US7896954B2 (en) 2005-04-07 2011-03-01 Matheson Tri-Gas, Inc. Fluid storage and purification method and system
US7678263B2 (en) 2006-01-30 2010-03-16 Conocophillips Company Gas stripping process for removal of sulfur-containing components from crude oil
WO2007096345A1 (fr) * 2006-02-22 2007-08-30 Shell Internationale Research Maatschappij B.V. Procede d'elimination de composes disulfure
EA014246B1 (ru) * 2006-02-22 2010-10-29 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ удаления дисульфидных соединений
US7803339B2 (en) 2006-02-22 2010-09-28 Shell Oil Company Method for disposal of di-sulphide compounds
US9908093B2 (en) 2008-04-09 2018-03-06 Velocys, Inc. Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology
DE102009022284A1 (de) 2008-05-26 2010-03-25 Instituto Mexicano Del Petroleo Entschwefelung von Kohlenwasserstoffen durch ionische Flüssigkeiten und Herstellungsverfahren
US8821716B2 (en) 2008-05-26 2014-09-02 Instituto Mexicano Del Petroleo Desulfurization of hydrocarbons by ionic liquids and preparation of ionic liquids
US8999151B2 (en) 2008-08-29 2015-04-07 Instituto Mexicano Del Petroleo Halogen-free ionic liquids in naphtha desulfurization and their recovery
DE102009039176A1 (de) 2008-08-29 2010-03-04 Instituto Mexicano Del Petroleo Halogenfreie ionische Flüssigkeiten in der Naphtha-Entschwefelung und ihre Rückgewinnung
US9850197B2 (en) 2008-08-29 2017-12-26 Instituto Mexicano Del Petroleo Halogen-free ionic liquids in naphtha desulfurization and their recovery
US9695368B2 (en) 2008-10-10 2017-07-04 Velocys, Inc. Process and apparatus employing microchannel process technology
US9926496B2 (en) 2008-10-10 2018-03-27 Velocys, Inc. Process and apparatus employing microchannel process technology
US10626335B2 (en) 2009-04-06 2020-04-21 Petroliam Nasional Berhad (Petronas) Process for removing metals from hydrocarbons
WO2010116165A3 (fr) * 2009-04-06 2010-12-16 Petroliam Nasional Berhad (Petronas) Procédé d'élimination de métaux à partir d'hydrocarbures
EA035879B1 (ru) * 2009-04-06 2020-08-26 Петролиам Насьональ Берхад (Петронас) Способ удаления металлов из углеводородов
WO2010129238A1 (fr) * 2009-04-27 2010-11-11 Saudi Arabian Oil Company Désulfuration et désazotation avec des liquides ioniques et des systèmes d'ions métalliques
US8540871B2 (en) 2010-07-30 2013-09-24 Chevron U.S.A. Inc. Denitrification of a hydrocarbon feed
US9157034B2 (en) 2011-07-27 2015-10-13 Instituto Mexicano Del Petroleo Denitrogenation of hydrocarbons by liquid-liquid extraction using ionic liquids
WO2013098056A1 (fr) 2011-12-28 2013-07-04 Lanxess Deutschland Gmbh Purification de caoutchouc nitrile éventuellement hydrogéné
US9676623B2 (en) 2013-03-14 2017-06-13 Velocys, Inc. Process and apparatus for conducting simultaneous endothermic and exothermic reactions
US9475997B2 (en) 2014-11-24 2016-10-25 Uop Llc Contaminant removal from hydrocarbon streams with carbenium pseudo ionic liquids
US9574139B2 (en) 2014-11-24 2017-02-21 Uop Llc Contaminant removal from hydrocarbon streams with lewis acidic ionic liquids
US11124692B2 (en) 2017-12-08 2021-09-21 Baker Hughes Holdings Llc Methods of using ionic liquid based asphaltene inhibitors
US11254881B2 (en) 2018-07-11 2022-02-22 Baker Hughes Holdings Llc Methods of using ionic liquids as demulsifiers

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