WO2007082785A1 - Procédé d'élimination de composés fluorés ou chlorés de flux d'hydrocarbures c4 techniques - Google Patents

Procédé d'élimination de composés fluorés ou chlorés de flux d'hydrocarbures c4 techniques Download PDF

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Publication number
WO2007082785A1
WO2007082785A1 PCT/EP2007/050029 EP2007050029W WO2007082785A1 WO 2007082785 A1 WO2007082785 A1 WO 2007082785A1 EP 2007050029 W EP2007050029 W EP 2007050029W WO 2007082785 A1 WO2007082785 A1 WO 2007082785A1
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fluorine
technical
chlorine
isobutene
removal
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PCT/EP2007/050029
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German (de)
English (en)
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Phillip Hanefeld
Hans Peter Rath
Thomas Wettling
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Basf Se
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00Purification; Separation; Use of additives
    • C07C7/12Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00Purification; Separation; Use of additives
    • C07C7/12Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers

Definitions

  • the present invention relates to a process for the removal of fluorine- or chlorine-containing compounds from technical C4 hydrocarbon streams, in particular from those technical C4 hydrocarbon streams from which isobutene was partially or largely removed by polymerization reaction by means of a fluorine- or chlorine-containing catalyst.
  • the polymerization of isobutene, which can be used as pure isobutene or in the form of technical C4 hydrocarbon streams, to polyisobutenes is usually carried out as cationic polymerization using fluorine-containing catalysts such as boron trifluoride or boron trifluoride adducts such as boron trifluoride etherates or boron trifluoride alcoholates.
  • fluorine-containing catalysts such as boron trifluoride or boron trifluoride adducts such as boron trifluoride etherates or boron trifluoride alcoholates.
  • polyisobutenes having a high content of terminal double bonds so-called highly reactive polyisobutenes, are preferably produced.
  • This technology is described, for example, in WO 94/20554, WO 96/40808, WO 99/31 151 and WO 99/64482.
  • German Application No. 10 2004 033988.0 discloses a process for the preparation of highly reactive polyisobutenes having a low fluorine content, in which special moderators are used in the polymerization or the liquid reaction mixture after completion of the polymerization in the presence of such a moderator with an inorganic adsorbent such as a zeolite or Alumina is brought into contact.
  • an inorganic adsorbent such as a zeolite or Alumina
  • maximum fluorine contents of 10 ppm by weight and maximum chlorine contents of 50 ppm by weight are desirable. This generally applies to reusable C4 hydrocarbon streams containing fluorochemical compounds.
  • the fluorine- or chlorine-containing compounds, if they remain in the streams, can lead to severe corrosion problems in the plant components and later to problems of the quality of the products resulting at the end of a value-added chain, due to later release of hydrogen fluoride or hydrogen chloride.
  • the object of the present invention was therefore to provide a process for the removal of fluorine- or chlorine-containing compounds from technical C 4 hydrocarbon streams, in particular from those technical C 4 hydrocarbon streams from which isobutene has been partly or substantially removed by a polymerization reaction using a fluorine- or chlorine-containing catalyst, provide.
  • the technical C4 hydrocarbon streams to be treated are, based on their technical origin, in particular C4 raffinate streams such as raffinate 1, raffinate 1 P or raffinate 2, C4 cuts from isobutane dehydrogenation, C4 cuts from steam cultivators according to US Pat Butadiene extraction, C4 cuts from steam crackers after TeN hydrogenation (HC4) or C4 cuts from Fluid Catalyst Cracking (FCC).
  • C4 raffinate streams such as raffinate 1, raffinate 1 P or raffinate 2
  • C4 cuts from isobutane dehydrogenation
  • C4 cuts from steam cultivators according to US Pat Butadiene extraction
  • C4 cuts from steam crackers after TeN hydrogenation (HC4) or C4 cuts from Fluid Catalyst Cracking (FCC).
  • Such streams are largely exempt from contained 1, 3-butadiene, they contain in usually less than 1000 ppm by weight, preferably less than 200 ppm by weight of butadiene.
  • the content of 1-butene is 10 to 50% by weight
  • 2-butene is 10 to 40% by weight
  • isobutene is 30 to 50% by weight
  • butanes 2 to 35% by weight is typically, in a raffinate 1 stream, the content of 1-butene is 10 to 50% by weight, 2-butene is 10 to 40% by weight, isobutene is 30 to 50% by weight, and butanes 2 to 35% by weight.
  • the content of 1-butene is 1 to 15% by weight, 2-butene is 15 to 50% by weight, isobutene is 35 to 60% by weight, and butanes 2 are to 40% by weight.
  • the content of 1-butene is typically 15 to 60% by weight, 2-butene 5 to 50% by weight, isobutene 0.5 to 10% by weight and butanes 5 to 45 wt .-%.
  • the content of 1-butene is less than 1 wt%, 2-butene is less than 1 wt%, isobutene is 20 to 70 wt%, and butanes From 30 to 80% by weight.
  • the content of 1-butene is 10 to 30 wt .-%, of 2-butene 10 to 30 wt .-%, of isobutene 30 to 50 wt .-% and butane 5 to 20 wt .-%.
  • the content of 1-butene is 15 to 60% by weight, 2-butene is 5 to 50% by weight, and isobutene is 10 to 45% by weight. % and butanes 5 to 45 wt .-%.
  • the content of 1-butene is 5 to 25% by weight, 2-butene 10 to 40% by weight, isobutene 10 to 30% by weight, and butanes 30 to 70% by weight. -%.
  • the fluorine-containing compounds to be removed by the process according to the invention may be inorganic compounds such as hydrogen fluoride or metal fluorides, for example sodium fluoride, or organic compounds such as the mono- and polyisobutyl fluorides already mentioned.
  • Typical mono- or polyisobutyl fluorides can be represented by the following general formula:
  • Corresponding chlorine-containing compounds to be removed by the process according to the invention are structured or built up analogously to this.
  • such fluorine- or chlorine-containing compounds are completely or at least for the most part removed from technical C 4 hydrocarbon streams.
  • the maximum fluorine content in the streams treated by the process according to the invention is significantly lower than before treatment and is usually 10 ppm by weight, in many cases it is even lower, for example at a maximum of 5 ppm by weight.
  • the maximum chlorine content in the streams treated by the process according to the invention is also significantly lower than before treatment and is usually 50 ppm by weight, in many cases even lower, for example at a maximum of 20 ppm by weight.
  • the inventive method for the removal of fluorine- or chlorine-containing compounds is applied to such technical C4 hydrocarbon streams from which isobutene was partially or largely removed by polymerization reaction using a fluorine- or chlorine-containing catalyst.
  • the treated C4 hydrocarbon stream (after isobutene removal) is typically a raffinate 2 stream.
  • C4 hydrocarbon stream isobutene was partially or largely removed by polymerization reaction using a fluorine- or chlorine-containing catalyst, the current largely freed from fluorine- or chlorine-containing compounds according to the invention is preferably attributed to the polymerization reaction of isobutene.
  • a further technical possibility for the use of the process of the invention of fluorine- or chlorine-containing compounds substantially freed technical C4 hydrocarbon streams is the production of isooctene by dimerization reaction.
  • Isooctene is suitable, for example, as an additive for petrol for octane number improvement.
  • isooctene serves as starting material for the oxo synthesis of nonanols, which in turn can be a basis for the production of plasticizers or surfactants.
  • Another technical application for the process according to the invention of fluorine or chlorine-containing compounds largely freed technical C4 hydrocarbon streams, especially those with high 1-butene content, is the preparation of pentanols and / or pentanals by oxo synthesis (hydroformylation). mylierung).
  • pentanals such as n-valeraldehyde can subsequently be converted by Aldolkondensation and subsequent hydrogenation to 2-propylheptanol, which in turn can be a basis for the production of plasticizers or surfactants.
  • the said polymerization of the isobutene by means of a fluorine- or chlorine-containing catalyst, in particular a boron trifluoride-containing catalyst, is carried out by methods known to the person skilled in the art.
  • the polyisobutene produced usually has a number average molecular weight of 400 to 50,000 and a content of vinylidene groups of more than 50 mol%.
  • vinylene group content refers to the percentage of polyisobutene molecules having a vinylidene group based on the number of all olefinically unsaturated polyisobutene molecules in a sample. It can be determined by 1 H-NMR and / or 13 C-NMR spectroscopy, as is known in the art.
  • the content of methylidene groups is more than 50 mol%, preferably at least 60 mol%, particularly preferably at least 75 mol%.
  • the polyisobutene thus obtained has a number-average molecular weight M n of from 400 to 50,000, preferably from 500 to 5,000, in particular from 700 to 2,500.
  • the dispersity (D Mw / Mn) is typically less than 2.5, preferably less than 2.0, and more preferably less than 1.8.
  • moderators In the polymerization of isobutene with fluorine-containing catalysts such as boron trifluoride hydrogen cyanide, cyanides or nitriles can be included, which control the reactivity of the boron trifluoride catalyst and therefore can be referred to as "moderators". In contrast to other measures for controlling the catalyst activity, such. As lowering the temperature, these moderators allow high isobutene sales, whereby the formation of undesired Isobutenoligomerer and fluorinated compounds is pushed back.
  • fluorine-containing catalysts such as boron trifluoride hydrogen cyanide
  • moderators In contrast to other measures for controlling the catalyst activity, such. As lowering the temperature, these moderators allow high isobutene sales, whereby the formation of undesired Isobutenoligomerer and fluorinated compounds is pushed back.
  • Suitable moderators in the polymerization of the isobutene are hydrogen cyanide (hydrocyanic acid) or organic nitriles of the general formula R-CN, where R is alkyl, alkenyl, alkynyl, alkaryl or aralkyl having preferably up to 12 carbon atoms.
  • the moderator is selected from acetonitrile, propionitrile, acrylonitrile and benzonitrile.
  • inorganic cyanides in particular alkali metal and / or alkaline earth metal cyanides, such as sodium cyanide or potassium cyanide are also suitable.
  • the cyanides may conveniently be applied to inert insoluble carriers which are suspended in the reaction mixture.
  • the hydrocarbons other than isobutene can play the role of an inert diluent.
  • Isobutene itself can also be used as diluent if the polymerization is operated only to a partial conversion.
  • the diluents are freed prior to their use of impurities such as water, carboxylic acids or mineral acids, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
  • boron trifluoride complex catalysts are preferred. This is understood to mean catalysts of boron trifluoride and at least one cocatalyst. Suitable cocatalysts are usually oxygen-containing compounds.
  • the catalyst preferably has the composition:
  • L 1 is water, a halogenated hydrocarbon, a primary C 1 to C 8 alkanol, a C 3 to C 8 secondary alkanol, a phenol and / or a tertiary butyl ether,
  • L 2 represents at least one aldehyde and / or one ketone
  • the ratio b: a lies in the range from 0.9 to 3.0, preferably 1, 1 to 2.5,
  • the ratio d: a is in the range from 0 to 1.0, preferably 0.1 to 1, in particular 0.1 to 0.6.
  • the solubilizers L 3 have a solubilizing effect and increase the solubility of the catalyst complex in the feedstock.
  • ethers which are other than tert-butyl ethers and have at least 5 carbon atoms or long-chain and / or sterically hindered alcohols which provide shielding against the access of isobutene molecules. It is preferable to use dialkyl ethers having 5 to 20 carbon atoms, a secondary alkanol having 6 to 20 carbon atoms, a primary alkanol having 6 to 20 carbon atoms, and / or a tertiary C 4 to C 20 alkanol.
  • the BF3 concentration in the reactor is generally in the range of 0.005 to 1 wt .-%, based on the liquid reaction phase, in particular in the range of 0.01 to 0.7 wt .-% and especially in the range of 0.02 to 0.5% by weight.
  • the polymerization is generally carried out at a temperature in the range of -60 ° C to + 40 ° C, preferably less than 0 ° C, more preferably in the range of -5 ° C to -40 ° C and especially in the range of -10 ° C to -30 ° C.
  • the heat of polymerization is dissipated by means of a cooling device accordingly. This can be operated, for example, with liquid ammonia as a coolant. Another way to dissipate the heat of polymerization is the boiling-cooling. In this case, the heat released is removed by evaporation of the isobutene and / or other volatile constituents of the isobutene feedstock or the optionally volatile solvent.
  • the polymerization of the isobutene is carried out in at least two successive reactors, of which at least the first reactor is remixed in some areas, wherein one doses at least in the second and / or further reactor one or more of the above moderators.
  • a first subset of the moderator (s) is metered into the first reactor and at least one further subset is metered into the second or further reactor.
  • the proportion of the metered in the first reactor subset of the total amount of moderators is preferably 40 to 90%.
  • the isobutene supplied is generally polymerized to a partial conversion of up to 95%, preferably 50 to 90%, particularly preferably 70 to 90%, based on the isobutene introduced into the first reactor.
  • the discharge from the first reactor is preferably passed without further work-up into the second reactor or from a preceding to the subsequent reactor.
  • the further polymerization takes place without the addition of fresh isobutene.
  • the residence time of the reaction mixture in the first reactor is usually 5 to 60 minutes when adjusting an isobutene conversion of 50 to 90%, but may be shorter or longer, depending on whether a very active or less active catalyst is used.
  • a residence time of from 1 to 180, preferably from 2 to 120 minutes is generally set.
  • isobutene conversion is set in the last reactor so that the total conversion of the isobutene is 90 to 99.5%.
  • concentration of isobutene in the liquid reaction phase in the main reactor is generally in the range of 0.2 to 50 wt .-%, preferably in the range of 0.5 to 20 wt .-% and in particular in the range of 1 to 10 wt. -%, based on the liquid reaction phase.
  • polyisobutenes with number-average molecular weights M n in the range from 500 to 5000 it is preferable to work at an isobutene concentration in the range from 1 to 20% by weight and in particular in the range from 1 to 5% by weight.
  • an isobutene concentration in the range from 4 to 50% by weight preference is given to working at an isobutene concentration in the range from 4 to 50% by weight.
  • an isobutene concentration of 3% by weight does not fall below.
  • the temperature of the liquid reaction mixture in the polymerization reactor has a steady state value and does not change or only slightly during operation of the reactor.
  • the polymerization in the second reactor may be at a lower polymerization temperature than in the first reactor; it then usually requires further activation by addition of, for example, fresh boron trifluoride or a regulator, such as an aldehyde or ketone, z. Acetone.
  • the discharged from the polymerization reaction mixture still contains active catalyst.
  • the polyisobutene formed in the polymerization reactor may be adversely affected in terms of molecular weight, molecular weight distribution and end group content. Therefore, in order to prevent further reaction, the polymerization is usually stopped by deactivating the catalyst.
  • the deactivation can be effected, for example, by adding water, alcohols, acetonitrile, ammonia or aqueous solutions of mineral bases or by introducing the discharge into one of the abovementioned media.
  • the deactivation with water which is preferably carried out at temperatures in the range of 1 to 60 ° C (water temperature).
  • the deactivated discharge can be suitably used for pre-cooling of the inlet, z. B. in a countercurrent heat exchanger.
  • the boron trifluoride complex catalysts can also be largely separated from the effluent and recycled to the polymerization reaction.
  • the separation and recycling of the catalyst from the discharge of the polymerization reaction is known from WO 99/31 151, to which reference is made in its entirety.
  • To separate the catalyst from the discharge is preferably used sparingly soluble boron trifluoride complex catalysts and / or the reaction mixture to temperatures of, for example, 5 to 30 Kelvin below reactor temperature, preferably 10 to 20 Kelvin below reactor temperature, from.
  • the isobutene concentration in the discharge to values below 2 wt .-%, preferably 1 wt .-% and in particular below 0.5 wt .-%, based on the discharge, lower.
  • the catalyst precipitates in the form of finely divided droplets which, as a rule, rapidly change into a coherent phase.
  • the complex droplets or the coherent phase have a significantly higher density than the polymer solution.
  • they can therefore be separated from the polymer-rich, catalyst-poor product phase with the aid of separators, separators or other collecting containers.
  • the thereby separated polymer-rich product phase is generally homogeneous and contains only small amounts of soluble catalyst components. These are deactivated in the manner described above, preferably with water.
  • reaction mixture may, prior to adsorbent treatment, be subjected to various other treatments, e.g. B. a laundry for catalyst deactivation / removal and / or removal of volatile components.
  • This inorganic adsorbent generally comprises oxides and salts such as halogenides, in particular chlorides, sulfates, phosphates, carbonates or nitrates of silicon, aluminum, zirconium, calcium and / or titanium, which can have various dopings.
  • oxides and salts such as halogenides, in particular chlorides, sulfates, phosphates, carbonates or nitrates of silicon, aluminum, zirconium, calcium and / or titanium, which can have various dopings.
  • alumina, zeolites and combinations thereof The alumina used can in particular with a base, for. Example, an alkali or alkaline earth metal hydroxide or an alkali or alkaline earth metal cyanide, be doped.
  • the inorganic adsorbent may have an acidic, a neutral or a basic character.
  • Particularly well-suited inorganic adsorbents are those which have on their surface in addition to acidic or weakly acidic regions also basic or weakly basic ranges; The latter are able to covalently bind split-off hydrogen fluoride or hydrogen chloride. Efficient removal of the hydrogen fluoride or hydrogen chloride in particular prevents the undesired acid-catalyzed structural isomerization of 1-butene to 2-butene.
  • the inorganic adsorbent comprises an aluminum oxide.
  • Aluminum oxides are known as adsorbents for gases, liquids and solids, especially in chromatographic processes and methods.
  • Acid, neutral or basic aluminum oxides can be used for the process according to the invention for the removal of fluorine- or chlorine-containing compounds, in particular basic aluminas are suitable for this purpose.
  • Acidic aluminas usually have a pH of from 3 to 6, typically about 4.
  • Neutral aluminum oxides usually have a pH of 6 to 8, typically of about 7, on.
  • Basic aluminum oxides usually have a pH of 8 to 1 1, typically of about 9.5, on.
  • the aluminum oxides mentioned generally have pore volumes of 0.5 to 1.5 ml / g, typically of about 0.9 ml / g, usually inner surfaces of 70 to 250 m 2 / g, typically of about 150 m 2 / g, and usually particle sizes in the range of 30 to 300 microns, typically from 60 to 150 microns.
  • the inorganic adsorbent comprises a zeolite having mean pore sizes of at least 3 ⁇ , in particular from 5 to 15 ⁇ .
  • the mean pore size is determined by the crystal structure of the zeolite and z. B. are determined from X-ray structure data.
  • the fluorine-containing compounds to be removed can diffuse poorly and are therefore inadequately adsorbed or split.
  • the zeolites used are substantially free of acid.
  • Preferred zeolites are selected from zeolite A, zeolite L, zeolite X and zeolite Y.
  • zeolite 10 A which already shows a high absorptive cleavage performance at comparatively low temperatures.
  • the fluorine- or chlorine-containing compounds to be removed are presumably cleaved and the fluorine- or chlorine-containing cleavage products, such as hydrogen fluoride or hydrogen chloride, are adsorbed on the zeolite or chemically bound by the cations contained therein.
  • the hydrogen fluoride or hydrogen chloride by addition of an acid scavenger, z. B: an amine or a nitrile, to bind.
  • the inorganic adsorbent is conveniently activated prior to use by heating it usually under reduced pressure to a temperature of at least 150 ° C.
  • the technical C 4 -hydrocarbon stream is dried to a residual water content of 5 ppm by weight, in particular 3 ppm by weight, before it is brought into contact with the inorganic adsorbent.
  • the gas stream is preferably brought into contact with a zeolite having an average pore size of 4 ⁇ or less, usually at a temperature of less than 40 ° C., eg. At 5 to 35 ° C.
  • the contacting of the C4 hydrocarbon streams with the inorganic adsorbent can be carried out by any conceivable discontinuous or continuous process.
  • the usually gaseous technical C 4 hydrocarbon streams are usually passed over the inorganic absorption medium in the form of a solid, the absorbent being essentially fixed in its position in the apparatus or installation.
  • the adsorbent is in a fixed bed or in a loose bed disposed in an adsorption column through which the gas stream is passed.
  • the adsorption column is preferably arranged vertically and is flowed through by the gas flow in the direction of gravity or preferably against the force of gravity. It is also possible to use a plurality of adsorption columns connected in series.
  • the contacting of the technical C4 hydrocarbon streams with the inorganic adsorbent to remove the fluorine- or chlorine-containing compounds is generally carried out at temperatures of 5 to 240 ° C, preferably 30 to 200 ° C, especially 40 to 150 ° C.
  • the technical C4 hydrocarbon streams are usually adjusted in this contact to a pressure of 1 to 100 bar, in particular 1, 1 to 50 bar, especially 2 to 30 bar.
  • the usually present in gaseous technical C4 hydrocarbon streams may also be liquefied in exceptional cases.
  • the residence time ie the time during which the gas stream is in contact with the adsorbent, is typically 10 to 100 minutes.

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Abstract

Procédé d'élimination de composés fluorés ou chlorés de flux d'hydrocarbures C4 techniques contenant normalement en tant que constituants essentiels du 1-butène, du 2-butène, de l'isobutène et du butane, par exemple des flux de raffinat 1, de raffinat 1P ou de raffinat 2, qui consiste à mettre en contact le flux d'hydrocarbure C4 technique avec des agents d'adsorption inorganiques, habituellement des oxydes d'aluminium, des halogénures d'aluminium, des oxydes de zirconium, des oxydes de titane, des oxydes de calcium, des silicates ou des zéolithes.
PCT/EP2007/050029 2006-01-13 2007-01-03 Procédé d'élimination de composés fluorés ou chlorés de flux d'hydrocarbures c4 techniques WO2007082785A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4391677A (en) * 1979-03-21 1983-07-05 Davy Mckee (Oil & Chemicals) Limited Process for producing substantially sulphur-free butene-1
WO1991015444A1 (fr) * 1990-04-06 1991-10-17 Exxon Chemical Patents Inc. Enlevement d'organochlorures
US5371313A (en) * 1993-11-24 1994-12-06 Polysar Rubber Corporation Purification of hydrocarbon streams
US5792897A (en) * 1994-09-23 1998-08-11 Uop Llc Hydrocardon recovery from corrosive effluent stream
EP0889015A1 (fr) * 1997-07-04 1999-01-07 Haldor Topsoe A/S Procédé de séparation de composés acides d'un courant d'hydrocarbures
US5952541A (en) * 1992-07-30 1999-09-14 Exxon Chemical Patents, Inc. Method of loading hydrogen halide onto an adsorbent to enable removal of lead impurities from liquid hydrocarbons
EP1081165A1 (fr) * 1999-02-23 2001-03-07 Nippon Petrochemicals Company, Limited Procede pour deshalogener des hydrocarbures contenant une double liaison carbone-carbone
DE10361638A1 (de) * 2003-12-30 2005-08-04 Basf Ag Herstellung hochreaktiver Polyisobutene mit niedrigem Fluorgehalt unter Verwendung eines Moderators

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4391677A (en) * 1979-03-21 1983-07-05 Davy Mckee (Oil & Chemicals) Limited Process for producing substantially sulphur-free butene-1
WO1991015444A1 (fr) * 1990-04-06 1991-10-17 Exxon Chemical Patents Inc. Enlevement d'organochlorures
US5952541A (en) * 1992-07-30 1999-09-14 Exxon Chemical Patents, Inc. Method of loading hydrogen halide onto an adsorbent to enable removal of lead impurities from liquid hydrocarbons
US5371313A (en) * 1993-11-24 1994-12-06 Polysar Rubber Corporation Purification of hydrocarbon streams
US5792897A (en) * 1994-09-23 1998-08-11 Uop Llc Hydrocardon recovery from corrosive effluent stream
EP0889015A1 (fr) * 1997-07-04 1999-01-07 Haldor Topsoe A/S Procédé de séparation de composés acides d'un courant d'hydrocarbures
EP1081165A1 (fr) * 1999-02-23 2001-03-07 Nippon Petrochemicals Company, Limited Procede pour deshalogener des hydrocarbures contenant une double liaison carbone-carbone
DE10361638A1 (de) * 2003-12-30 2005-08-04 Basf Ag Herstellung hochreaktiver Polyisobutene mit niedrigem Fluorgehalt unter Verwendung eines Moderators

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