EP0372939A1 - Procédé de séparation de n-oléfines et n-paraffines à partir de mélanges d'hydrocarbures - Google Patents

Procédé de séparation de n-oléfines et n-paraffines à partir de mélanges d'hydrocarbures Download PDF

Info

Publication number
EP0372939A1
EP0372939A1 EP89312735A EP89312735A EP0372939A1 EP 0372939 A1 EP0372939 A1 EP 0372939A1 EP 89312735 A EP89312735 A EP 89312735A EP 89312735 A EP89312735 A EP 89312735A EP 0372939 A1 EP0372939 A1 EP 0372939A1
Authority
EP
European Patent Office
Prior art keywords
olefin
olefins
adsorption
mixture
feed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89312735A
Other languages
German (de)
English (en)
Other versions
EP0372939B1 (fr
Inventor
Alexis Alexander Oswald
David William Savage
Edward Kantner
Ramon Luis Espino
Di-Yi Ou
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0372939A1 publication Critical patent/EP0372939A1/fr
Application granted granted Critical
Publication of EP0372939B1 publication Critical patent/EP0372939B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only

Definitions

  • This invention relates to a separation process based on the selective adsorption-desorption of n-olefins and n-paraffins in neutral molecular sieves, particularly MFI-framework zeolites such as silicalite, ZSM-5 and compositional variances thereof.
  • the early sieve adsorbents were crystalline aluminosilicates commonly known as zeolites. However, during the last ten years similar cystalline sieve compounds of different chemical compositions were synthesized. These include aluminophosphates and various microporous crystalline silica, including silicalite, which may contain small amounts of alumina. In the present invention all these shape selective adsorbent compounds are broadly termed as zeolites.
  • aluminosilicate zeolites were mostly active as catalysts, due to their polar, acidic character. They led to olefin isomerization, oligomer­ization, alkylation, polymerization and cracking reactions. Nevertheless, they were often disclosed as adsorbents for separations applicable in refinery processes where selectivities and the absence of side reactions were less critical. Most of the prior patents were aimed at the separation of n-paraffins.
  • Dessau shows the separation of n-paraffins from branched paraffins and aromatics and the separation n-olefins from branched olefins. However, he neither shows nor suggests the separa­tion of an n-paraffin and n-olefin mixture from a feed containing both aliphatic and aromatic hydro­carbons.
  • U.S. Patent 4,619,758 by Pratt, Sayles, Bowers and Scott discloses the selective adsorption of n-paraffins by zeolites such as ZSM-5, from hydrocarbon mixtures for example vacuum gas oil, followed by cracking of said n-paraffins in the zeolite.
  • U.S. Patent 3,969,223 by Rosback and Neuzil discloses the separation of olefins from olefin - paraffin mixtures, such as cracked wax by an X zeolite with an amorphous binder previously treated by aqueous sodium hydroxide to increase its sodium cation concentration. The treatment resulted in less olefin dimerization during the separation. However, this large pore diameter zeolite could not be used to separate straight chain and branched chain compounds.
  • Neuzil and Kulprathipanja were the first to disclose, in U.S. Patent4,455,445, column 1, lines 25 to 32, "that silicalite is able to effect the separation of normal C4 hydrocarbons from isobutylene with substantially complete elimination of the aforementioned undesired side effects of olefin dimerization and polymerization, particularly when pentene-1 is used to displace the normal C4 hydrocarbons from the zeolite.”
  • Neuzil et al. aimed their process for the separation of isobutylene from C4 hydrocarbons, since isobutylene is useful e.g. as a gasoline blending agent and as a monomer for the production of polyisobutylene. They neither dis­closed nor suggested this separation for the pro­duction of useful mixtures of higher n-olefins and n-paraffins.
  • Kulprathipanja and Neuzil also disclosed in U.S. Patent 4,486,618 the adsorption of normal C6 olefins from cyclic and branched C6 olefins using a silicalite with alumina as a binder.
  • 1-Pentene or 1-butene were used for desorption.
  • 1-Octene could never completely displace 1-hexene.
  • Kulprathipanja disclosed the separation of a trans-olefin from a cis-olefin via selective adsorption by a silicalite.
  • trans-2-butene from a mixture of cis- and trans-2-butenes followed by desorption with 1-pentene.
  • U.S. patent 4,455,444 by Kulprathipanja and Neuzil disclosed the selective adsorption of n-paraffins in silicalite and their desorption by n-olefins, particularly 1-hexene.
  • this patent emphasized that the feeds are limited to hydrocarbons containing little or no olefins.
  • the disclosures of the parent patent by Kulprathipanja and Neuzil, i.e. U.S. patent 4,367,364 were also limited to selective n-paraffin adsorption in silicalites in the presence of little or no olefins.
  • the process of this patent and the process of the above discussed subsequent patents by the same inventors were limited to hydrocarbon feeds containing cyclic hydrocarbons having more than six carbons. This excludes benzene which can enter the pores of the silicalite.
  • the present invention provides a process for the separation of C5 to C19 mixtures of n-olefins and n-paraffins from a feed mixture compris­ing aliphatic and aromatic hydrocarbons which process comprises contacting said mixture of C5 to C19 alipha­tic and aromatic hydrocarbons with a neutral molecular sieve adsorbent under conditions sufficient to effect selective adsorption of n-olefins and n-paraffins, and contacting the resulting sieve containing the adsorbed n-olefin and n-paraffin enriched extract with a more volatile desorbent under conditions sufficient to effect displacement from the sieve of said extract.
  • This invention provides a new separation approach for obtaining normal olefin, particularly ⁇ -olefin reactants, suitable as chemical intermediates.
  • Known chemical methods for the preparation of such olefins are ethylene oligomerization, paraffin cracking and dehydrogenation and alkyl chloride dehydrogenation and alkyl chloride dehydrochlorination.
  • Past separations were directed to the separation of olefins.
  • the present invention provides a process which separates a mixture of n-olefins and n-paraffins by a neutral molecular sieve of preferably high silica alumina ratio. The olefin components of this mixture may then be selectively converted to desired higher molecular weight products in a separate step. Finally, the unreacted paraffins may be removed from the reaction mixture by distillation.
  • the present invention is directed toward the separation of C5 to C19 n-olefin and paraffin mixtures from branched olefins, branched paraffins, aromatics hydrocarbons and sulfur containing compounds by the use of zeolites.
  • the present process could be operated using a mixture comprising open chain and cyclic aliphatic hydrocarbons and benzene.
  • the present process is applicable to hydrocarbon streams containing relatively large amounts of aromatic sulfur compounds.
  • thiophene, methylthiophenes and dimethylthiophenes which boil in the C6 to C8 carbon range were found to be adsorbed in the zeolite.
  • the process of the present invention is applicable to sulfur containing olefinic distillates derived by the high temperature thermal cracking of petroleum residua.
  • Distillates in the C9 to C19 range containing mostly aromatic, bulky sulfur compounds such as benzothiophene, are preferred.
  • 1-n-olefins were found to be adsorbed with an increased selectivity as compared to other products in the feed stream.
  • a key process step of the present invention is a molecular sieve separation.
  • Past sieve separation processes were usually aimed at the separation of single types of compounds. Distinct processes were developed for the separation of olefins and normal paraffins. In contrast the present process separates a mixture of n-olefins and n-paraffins.
  • An attractive feature of the present separa­tion process is that it utilizes low cost olefinic hydrocarbon feeds which contain not only aliphatic hydrocarbons but aromatic hydrocarbon and sulfur compounds as well.
  • Such olefinic hydrocarbon feeds are produced by the high temperature thermal cracking of petroleum residua, particularly vacuum resids. These feeds contain high concentrations of linear thermal (i.e. ⁇ -) olefins of Type I and linear internal olefins of Type II.
  • Another important feature of the present separation is the use of a neutral molecular sieve. This minimizes olefin side reactions and allows the separation of 1-n-olefin - n-paraffin mixtures without any major terminal, e.g. olefin to internal olefin isomerization.
  • a neutral molecular sieve preferably low alumina zeolites having less than 5000 ppm alumina are used for selective adsorption.
  • acid-base treated silicalites and sodium ZSM-5 were found to be particularly suitable adsorbents for the separation of mixtures and 1-n-olefins and n-paraffins, because of their reduced olefin isomerization activity.
  • the preferred feeds of the present separation process are olefinic distillates produced from petroleum residua by high temperature thermal cracking. Such cracked distillates are preferably produced from vacuum residua by Fluid-coking or FLEXICOKING. These distillates contain 1-n-olefins as the major type of olefin components and organic sulfur.
  • the present invention also provides a process for converting the olefins obtained from the separation process to less volatile products.
  • the combined process converts the olefin components of the separated olefin-paraffin mixtures to higher boiling products and removes the unconverted paraffins thereafter by flash off. This unique combination of process steps has never been contemplated prior to the instant invention.
  • the present invention relates to a process for the separation of C5 to C19, preferably C g to C19, mixtures of n-olefins and n-paraffins, preferably 1-n-­ olefins and n-paraffins, from a mixture of aliphatic and aromatic hydrocarbons and, optionally, sulfur containing compounds comprising a mixture of C5 to C19 aliphatic and aromatic hydrocarbons, preferably a mixture also containing organic sulfur compounds, specifically in concentrations equivalent to from 0.05% to 3% sulfur with a neutral molecular sieve, preferably a metal zeolite such as sodium ZSM-5 having a minimum silica to alumina ratio of 20, more preferably a silicalite, most preferably a silicalite substantially free from alumina, which has been preferably pretreated by an acid and then a base, under conditions sufficient to effect selective adsorption from the liquid and/or the gas phase, preferably from the liquid phase under pressure sufficient to maintain liquid phase, and in
  • the invention provides a process for the separation of C9 to C19 mixtures of n-olefins and n-paraffins from aliphatic and aromatic hydrocarbons and, optionally, sulfur containing compounds, preferably 1-n-olefins and n-paraffins, comprising containing a mixture of C9 to C19, preferably C9 to C13, aliphatic and aromatic hydrocarbons, which preferably also contains sulfur compounds, with a neutral molecular sieve, preferably a zeolite having a minimum silica alumina ratio of 20, sodium ZSM-5 or more preferably a silicalite, in the liquid phase and in the temperature range of 80°C and 200°C preferably 100°C to 150°C for a sufficient time to effect adsorption, and desorbing the resulting n-paraffin and n-olefin enriched extract from the sieve with a more volatile olefin or paraffin as described above.
  • a neutral molecular sieve preferably zeo
  • the present invention provides a process for the separation of C5 to C19, preferably C9 to C15, more preferably C9 to C13 mixture of 1-n-olefins and n-paraffins from aliphatic and aromatic hydrocarbons and, optionally, sulfur containing compounds comprising contacting a corresponding olefinic cracked distillate feed produced from petroleum residua by high temperature thermal cracking, preferably Fluid-coking or FLEXI-COKING, and containing 1-n-olefins as the major type of olefin components, the percentage of Type I olefins preferably exceeding 30 wt% of the total olefins, and organic sulfur compounds, preferably in concentration exceeding 0.05%, more preferably in the concentration range of 0.3% to 3% with a neutral molecular sieve, preferably an above described high Si/Al ratio zeolite, more preferably sodium ZSM-5 or a silica molecular sieve in the liquid phase in the temperature range of 10°C
  • the present invention represents a process for the separation of C g to C19, preferably C9 to C15, mixtures of 1-n-olefins and n-paraffins comprising contacting a C9 to C19 olefinic cracked distillate feed produced from vacuum residua by high temperature thermal cracking in a Fluid-coker or FLEXICOKER unit which contains more than 20% olefins, more than 30% of said olefins being of Type I, and additionally contains organic sulfur compounds in concentrations exceeding 0.3% sulfur, with a neutral molecular sieve, preferably an earlier defined high Si/Al ratio zeolite, more preferably a silicalite in the liquid phase in the temperature range of 80°C and 200°C for a sufficient time to effect adsorption, and desorbing the resulting 1-n-olefin - n-paraffin enriched extract from the sieve with a more volatile n-olefin and/or n-paraffin under adsorption
  • the present invention also encompasses a separation - conversion process comprising contacting an olefinic C5 to C19, preferably C9 to C19 mixture of aliphatic and aromatic hydrocarbon feed, the more preferred feeds being those defined above, with a neutral molecular sieve, preferably a zeolite with a high Si/Al ratio, preferably as defined above, more preferably a silicalite, in the liquid and or gas phase preferably in the liquid phase in the temperature range of 100° to 250°C for a time sufficient to effect a selective adsorption of the 1-n-olefin and n-paraffin components, desorbing the resulting 1-n-olefin and n-paraffin enriched extract with a more volatile n-olefin and/or paraffin, preferably n-olefin, and converting the olefin components of the extract to less volatile products via reactions preferably selected from the group consisting of oligomerization, aromatics alkylation and carbonylation, more
  • this invention covers a selective separation - conversion process comprising contacting a C9 to C13 olefinic cracked petroleum distillate feed, produced from vacuum residua by high temperature thermal cracking in a Fluid-coker or FLEXICOKER unit, which contains more than 20%, preferably more than 30%, olefins and more than 30% said olefins being of Type I and additionally contains organic sulfur compounds in concentrations exceeding 0.3% sulfur, with a neutral molecular sieve, preferably a silicalite or sodium ZSM-5 in the liquid or gas phase, preferably in the liquid phase, in the temperature range of 100°C to 250°C, preferably 100 to 150°C for a sufficient time to effect selective adsorption of the 1-n-olefin and n-paraffin components, desorbing the resulting 1-n-olefin - n-paraffin rich extract from the sieve with a more volatile n-olefin or/and n-paraffin, preferably n-olef
  • the combined separation - conversion process of the present invention will be detailed regarding the conversion encompassed within the inventive concept.
  • the conversion of the olefin components of the n-olefin - n-paraffin extract to synthetic lubricants will be particularly described.
  • the preferred hydrocarbon feeds of the present invention contain major amounts of olefins, paraffins and aromatic compounds. More preferably the feeds also contain significant amounts of sulfur compounds.
  • the olefin compounds of the feed are preferably in concentrations exceeding 10 wt.%, more preferably 20 wt%, most preferably 30%.
  • the prevalent specific olefins are 1-n-olefins.
  • Some preferred olefin feed components are 1-pentene 3-hexene, 3-methyl-2-pentene, 1-octene, trans-2-decene, tetradecene, 1-octadecene.
  • paraffin components are preerably in concentrations similar or lower concentrations than those of the olefins or lower, the normal paraffins being the major paraffin component.
  • exemplary paraffins are n-pentane, cyclohexane, n-octane, n-decane, 2-methylnonane, decalin, hexadecane.
  • the aromatic hydrocarbon components preferably represent from 1 to 60 wt.% of the feed more preferably 10 to 60 wt.%.
  • the preferred aromatic hydrocarbons are either unsubstituted or substituted by short C1 to C3 alkyl groups such as benzene, p-xylene, 1-methyl-4-ethyl-benzene, 1,2,3-trimethylbenzene, naphthalene, 2-methylnaphthalene, phenanthrene.
  • the sulfur compounds are usually present as impurities in the hydrocarbon feed.
  • the present process is preferred for feeds of relatively high sulfur content, 0.05 wt.% or above and can handle feeds having sulfur concentrations ranging from 0.3 to 3% sulfur.
  • the sulfur compounds are usually present as thiol and/or aromatic sulfur compounds.
  • Aromatic sulfur compounds such as thiophenes, benzothiophenes and dibenzothiophenes are preferred. These aromatic sulfur compounds can be substituted by one or more short chain alkyl groups, preferably C1 to C3 alkyl, more preferably methyl.
  • the preferred olefinic distillate feeds of the present invention are produced from petroleum residua by high temperature thermal cracking.
  • the percentage of the most desired 1-n-olefin components of such feeds generally increases with the tempera­ture of cracking. Therefore, the distillate pro­ducts of high temperature thermal cracking processes such as Fluid-coking and FLEXICOKING are preferred feeds for the present process. Delayed coking which is normally operated at lower temperatures can also produce suitable feeds for the present process although these feeds contain higher concentrations of n-paraffins than 1-n-olefins.
  • Other less pre­ferred, but suitable, generally milder cracking processes to produce feeds for the present invention are the thermal cracking of gas oils and the vis-­breaking of vacuum residues.
  • the preferred feeds of Fluid-coking and FLEXICOKING are highly olefinic with olefin concen­trations exceeding 20 wt.%, preferably 30%.
  • the aliphatic hydrocarbons are semilinear in character.
  • the main components are linear, i.e. normal olefins and normal paraffins.
  • the largest specific type of compounds are 1-n-olefins followed by n-paraffins.
  • the R groups in the formulas of the various types of olefins can be straight chain or branched alkyl groups.
  • the alkyl groups of the preferred coker olefins of Type I and Type II are predominantly either straight chain or monomethyl branched.
  • the Type III and Type IV olefin components of these preferred feeds predominantly possess a methyl group as one of the alkyl s on the completely substituted vinylic carbon.
  • NMR also indicated the presence of minor amounts of conjugated dienes ranging from about 2 to about 10% concentration.
  • the concentration of the various olefins generally decreases with their molecular weight, i.e. carbon number. Therefore, coker distillates having more than 19 carbons per molecule are less preferred.
  • paraffin components of the preferred coker distillate feeds are present in concentrations similar to but smaller than the olefin componentsl
  • the n-paraffins are the major single types of paraffins present.
  • the branched paraffins are largely methyl branched. Monomethyl branched paraffins are prevalent.
  • the aromatic hydrocarbons of the present feeds have a concentration range from 6% to 50%.
  • the percentage of the aromatic components increases with the carbon number of the distillate fractions. Of course the percentages of olefins and paraffins decrease accordingly.
  • the concentration of aromatics is between 10 and 50%.
  • the aromatic hydrocarbon components of these feeds are predominantly unsubstituted parent compounds such as benzene or substituted with methyl groups such as toluene.
  • concentration of ethyl substituted compounds is much smaller.
  • Propyl substituted aromatics are present in insignificant amounts.
  • Up to 12 carbon atoms, the aromatics are benzenoid hydrocarbons. From C12 to C15 most aromatics are of the naphthalene type. Among the higher carbon number hydrocarbons most aromatics are three membered fused ring compounds such as anthracenes and phenanthrenes.
  • the concentration and type of sulfur compounds in the preferred coker distillates depend on their carbon number.
  • the sulfur concentrations range from 0.1% to 3%. In general, sulfur concentrations increase with the carbon number to 3%.
  • the C5 to C7 carbon range there are major amounts of thiols present.
  • the C8 and higher fractions contain mostly aromatic sulfur compounds, mostly of the thiophene type.
  • the structure of aromatic thiol components is similar to those of the aromatic hydrocarbons. Methyl and ethyl substituted thiophenes are present in decreasing amounts.
  • Alkylthiophenes are the major sulfur compounds in the C8 to C11 range. Benzothiophenes are mostly present in the C12 to C15 range. In the higher boiling fractions, dibenzothiophenes are major sulfur compound components.
  • the zeolite adsorbents of the present process are molecular sieves which include not only crystalline alumino-silicates but aluminophosphtates, silicalites and similar crystalline materials. Zeolites either possess an internal pore system comprised of interconnected cagelike voids or a system of one, two or three dimensional channels. The zeolite minerals mordenite and chabazite are examples of these two types. Zeolites are mainly used as catalysts for chemical conversions and adsorbents for separations. They are described as "Molecular Sieves" in Kirk-Othmer's Encyclopedia of Chemical Technology, published by J. Wiley & Sons of New York.
  • Separations based on the molecular sieve effect generally employ dehydrated zeolites. Zeolites can selectively adsorb molecules based upon differences in molecular size, shape and other properties such as polarity.
  • the preferred zeolite adsorbents of the present invention possess pore diameters ranging from 3.5 to 7°A. Zeolites of this pore diameter range from chabazite to ZSM-5 and silicalite.
  • Such zeolites can adsorb n-paraffins and 1-n-olefins while rejecting bulky hydrocarbon molecules such as branched olefins, branched paraffins and C9 and higher aromatic hydrocarbons.
  • the other important characteristics of the preferred zeolites is their reduced polarity which increases their affinity toward aliphatic rather than aromatic hydrocarbons.
  • the silica to alumina ratio of the present zeolites is preferably above 12, more preferably above 30 such as ZSM-5.
  • U.S. Patent 3,702,886 describes ZSM-5 and is incorporated herein by reference. Similar zeolites are ZSM-11 described in U.S. Patent 3,709,979 and ZSM-12 described in U.S. Patent 3,832,449.
  • the zeolite frameworks were also classified by the pore structure as described by W. M. Meier and D. H. Olson in a monograph, entitled "Atlas of Zeolite Structure Types" which was published by Polycrystal Book Service in Pittsburgh, Pennsylvania in 1978. According to the nomenclature of Meier and Olson ZSM-5 and silicalite both possess a synthetically occurring MFI framework having two orthogonal interconnected channel systems with minimum diameter of 5.1 and 5.4°A. The MEL framework of ZSM-11 is similar. Both MFI and MEL structures have pores with 10 ring windows.
  • a typical silica to alumina ratio for ZSM-5 and ZSM-11 is 30.
  • pure silicalite is by definition has an alumina free framework
  • the silicalites used in the present invention also had a significant alumina content.
  • sodium ZSM-5 is distinguished from the silicalites employed by its sodium content which results in a lesser olefin isomerization activity than the silicalites have.
  • the silica to alumina ratio of zeolites can be increased by acid treatment which remove some of the alumina. This reduces the acidity and the polarity of the thus treated zeolite. Acid treat­ment can also affect pore size. These combined effect increase the adsorptive capacity and selecti­vity of zeolites while reducing the extent of undesired side reactions.
  • protonated aluminosilicate type zeolites of low acidity can be employed as adsor­bents in the present invention it is preferred to employ their sodium derivatives, more particularly sodium.
  • Such derivatives can be prepared by the neutralization of protonated zeolites by the appro­priate metal base or salt, such as aqueous sodium hydroxide or sodium chloride.
  • Such a base treatment can also affect advantageously the pore diameter and shape of the zeolite. Change in the cations also results in electric field effects, resulting dif­ferent interactions with adsorbate molecules.
  • the calcium exchanged form of the synthetic zeolite A has a pore diameter of 4.2 °A. This sieve is referred to as 5A.
  • the natural zeolite, chabazite, is another aluminosilicate with a similar pore diameter.
  • the preferred ZSM-5 is a high Si/Al ratio sodium aluminosilicate having a pore diameter above 5°A.
  • Sodium ZSM-5 can be prepared from either the corresponding quaternary ammonium derivative via thermal decomposition and neutralization or by direct synthesis.
  • the preferred zeolite adsorbents are silicalites which topologically resemble ZSM-5 and contain the same type of building unit.
  • the two sets of intersecting channels of silicalite have pore sizes ranging from 5.2 to 5.7°A. It is common­ly assumed that silicalites contain no exchangeable metal cations and as such they are highly non polar with high affinity for nonpolar hydrocarbon mole­cules.
  • silicalite from Union Carbide Corporation contains significant amounts, about 0.5%, aluminum as Al2O3. Significant amounts of this impurity can be removed by acid treatment. The resulting low alumina (about 0.3% Al) silicalite is then treated with a base to neutralize and remove acid impurities. The result­ing acid-base treated silicalite has improved selectivity and as such is a preferred adsorbent in the present process.
  • the crystalline zeolite adsorbents are usually formed into spheres or cylindrical pellets which have high mechanical attrition resistance. This is achieved using binders which do not serious­ly hinder diffusion in the micropores. As binders silica, alumina and crosslinked organic polymers can be employed.
  • Adsorption by zeolite molecular sieves is performed using gaseous and liquid feeds.
  • zeolites are regenerated and used for many adsorption-desorption cycles.
  • the present process is directed at the separation of two rather than one types of molecules and as such does not follow the rules and predictions developed for processes separating a single type of compounds.
  • process techniques such as counter-­current liquid phase adsorption, developed for single type hydrocarbons, are applicable.
  • the present invention comprises the selective adsorption of both n-olefins and n-paraf­fins from a mixture of aliphatic and aromatic hydrocarbon compounds.
  • the preferred feed mixtures are in the C5 to C19 range.
  • 1-n-olefins and n-paraffins are mainly adsorbed from a feed richer in terminal 1-n-olefins than internal n-­olefins.
  • Such preferred feeds are the distillates produced from petroleum residua by high temperature thermal cracking. These feeds additionally contain sulfur compounds.
  • 1-n-Olefins are particularly subject to isomeri­zation resulting in internal olefins. In general, internal olefins are less desired than terminal olefins.
  • the 1-n-olefin components of the C9 to C15 feeds are preferably adsorbed over the corresponding n-paraffins.
  • the trans-isomers of the internal linear olefins and 1-olefins are adsorbed at comparative rates. Little adsorption of the very minor cis-isomers occurs. In case of the minor conjugated linear diene components, such as trans­piperylene, a selective adsorption is also observed.
  • silicalite is a size selective adsorbent for certain monomethyl branched olefins. 3-Methyl-2-pentene was selectively ad­sorbed, while 2-methyl-2-pentene, 2-methyl-1-pentene and 4-methyl-2-pentene, were not. Some adsorption of C8 and higher carbon 2-methyl-1-alkenes and 2-methylalkanes was observed. However, their presence in minor amounts in the extracts of coker distillates does not interfere with the use of such extracts in synlube preparation.
  • the adsorption occurs on contacting the hydrocarbon feed and the zeolite at a temperature wherein the molecules to be adsorbed have a suffi­cient energy to overcome the repulsive interaction with the zeolite and pass through the aperture of the zeolite channels and reversibly fill the micro­pores.
  • increased temperatures are needed to overcome the activation energy requirements of molecules of increasing size and/or molecular weight.
  • preferred adsorption tempera­tures are in the 10 to 250°C range.
  • Adsorption of the low molecular weight, C5 to C8 distillate, feeds can be carried out at low temperatures, in the 10 to 100 °C regime.
  • the adsorption of C9 to C19 frac­tions at optimum diffusion rates requires increasing temperatures, ranging from 100 to 200°C.
  • the optimum temperatures of the present adsorption process are limited by the need to avoid 1-n-olefin isomerization and cracking.
  • the choice of adsorp­tion temperature also depends on the carbon range of the hydrocarbon feed. Broad distillate feed cuts are processed at temperatures higher than warranted for their low boiling components.
  • Gas phase adsorption is carried out preferably at close to atmospheric pressure in a temperature range wherein the feed is in the gaseous state.
  • liquid phase adsorption is performed at temperatures where the feed is liquid.
  • a volatile feed such as C5
  • above atmospheric pressure may be used.
  • a liquid phase operation is preferred because it can be usually carried out at a lower temperature providing a higher extract yield.
  • Desorption i.e. the removal of the n-olefin and n-paraffin rich extract from the zeolite adsorbents
  • a thermal swing cycle comprises desorption at a temperature higher than that for the adsorp­tion.
  • a pressure swing cycle employs reduced pressure to effect desorption.
  • An isother­mal purge cycle employs a non-adsorbed liquid to strip the adsorbate from the voids and eventually from the pores of the zeolite.
  • the dis­placement purge cycle employs a desorbent which is equally or more strongly adsorbed than the ad­sorbate. This desorbent is then displaced by the adsorbate in the adsorption cycle.
  • the preferred desorption is part of a displacement purge cycle.
  • This cycle is preferably practiced as outlined by D.B. Broughton in U.S. patent 2,985,589 and a paper entitled “Continuous Adsorptive Processing-A New Separation Technique", presented at the 34th Annual Meeting of the Society of Chemical Engineers at Tokyo, Japan on April 2, 1969 which are incorporated hereby by reference. Broughton particularly described a simulated moving bed countercurrent process flow scheme preferred in the process of the present invention.
  • n-paraffins and/or n-olefins are the choice desorbents.
  • These preferred desorbents are liquids which are lower boiling than the feed.
  • the boiling point of the desorbent should be low enough for easy separation from the feed by distil­lation but high enough so as to assure that the specific gravity and viscosity of the feed are not drastically different from that of the feed. The latter facilitates smooth feed and extract displace­ment by liquid flow through the adsorbent bed.
  • Exemplary desorbing agents include, n-pentane for a C6 feed, 1-hexene for a C7 to C9 feed, 1-n-octene for a C9 to C13 feed.
  • 1-n-octene is a preferred desor­bent in the present process. Even though 1-n-octene may not be completely separated from the 1-n-olefin n-paraffin rich extract, its presence is not objectionable in the subsequent conversions of the olefin components.
  • a broad feed fraction such as C8 to C15
  • the low boiling part of the extract e.g. a mixture of C8, C9 n-olefins and n-paraffins, is used as a desor­bent.
  • the low boiling com­ponents of the extract are distilled and used as desorbents.
  • the broad temperature range of desorption is generally the same as that of the adsorption.
  • the preferred temperature ranges for desorption and adsorption are similar by definition.
  • the pressure ranges of adsorption and desorp­tion are generally similar. Close to atmospheric cycles are preferred. In a preferred liquid phase cycle, the use of a low boiling desorbent such as n-butane may require superatmospheric pressure.
  • Adsorption-desorption cycles of the present process are operated in a temperature regime where no significant olefin side reactions take place. Nevertheless, the zeolite adsorbents have finite lifetimes due to minor side reactions result­ing in pore plugging. Regeneration of the thus deactivated zeolite is generally possible by calcination which results in the burning off of organic impurities.
  • n-olefin plus n-paraffin mixtures obtained in the present separa­tion process are advantageously converted to higher boiling derivatives and then separated from the unreacted n-paraffins.
  • These conversions generally comprise known chemical reactions and processes.
  • the preferred conversions are oligomerization, alkylation of aromatics and carbonylation.
  • a preferred aspect of the present invention is a unique combination of zeolite separation and selective conversion of n-olefin plus n-paraffin mixtures followed by the separation of the n-paraf­fin.
  • the preferred n-olefin-n-paraffin mixtures of the present invention contain 1-n-olefins as the main olefinic components. These 1-n-olefins are the preferred reactants in numerous types of conversions which are more specifically polymerization, oli­gomerization, alkylation, carbonylation and various other olefin conversions. In the following, mainly the conversions of these olefins will be discussed. n-Olefins generally undergo similar conversions at a lower rate.
  • the acid catalyzed and free radical oligomerization of 1-n-olefins is widely known.
  • acid catalysed oligomerization in the liquid phase is preferred.
  • the catalysts are generally strong acids such phosphoric acid, sulfonic acid, aluminum chloride, alkylaluminum dichloride and boron trifluoride complexes.
  • Boron trifluoride complexes are preferably those of protic compounds such as water, alcohols, and protic acids. Using BF3 complexes, cracking side reactions are avoided.
  • the oligomerizations are generally carried out in the -100 to 100°C temperature range at atmospheric pressure. Superatmospheric pressure may be used to assure a liquid phase operation.
  • the number of monomer units in the oligomer products is 2 to 30, preferably 2 to 6.
  • the n-olefin components of a mixture of n-olefins and n-paraffins are converted into oligomers by reacting them in the presence of an acid or a free radical catalyst preferably an acid catalyst.
  • oligomers containing an average of 3 to 4 monomer units, trimers and tetramers are produced by reacting a mixture rich in C9 to C13 1-n-olefins and n-paraffins, in the presence of a boron trifluoride complex.
  • the 1-n-olefin and internal normal olefin components of a C13 to C17 mixture of n-olefins and n-paraffins are cooligomerized to produce oligomers containing an average of 2 to 3 monomer units.
  • Another preferred acid catalyzed oligomerizaiton of n-olefins produces polyolefins in the C16 to C50 carbon range. These are subsequently used to alkylate benzene to produce C16 to C50 alkylbenzene intermediates for the synthesis of oil soluble calcium and magnesium alkylbenzene sulfonate detergents. For these oligomerizations preferably C5 to C8 n-olefins are employed.
  • the unconverted paraffin components of the n-olefin oligomer product mixture are removed preferably by distillation.
  • the distillation is performed either right after the oligomerization or subsequent to the next conversion step comprising either hydrogenation to isoparaffins or benzene alkylation to alkylbenzenes.
  • n-olefin components of the n-olefin plus n-paraffin mixtures involves the acid catalyzed alkylation of aromatic compounds.
  • exemplary reactants are benzene, toluene, o-xylene, naphthalene and phenol.
  • Benzene alkylation by n-olefins is important in the preparation of the linear alkylbenzene intermediates of biodegradable aqueous alkylbenzene sulfonate detergents and oil soluble linear alkylbenzene sulfonates.
  • Benzene alkylation can be effected with AlCl3 as a catalyst by known methods at temperatures between 0 and 100°C.
  • Phenol alkylation by n-olefins leads to linear alkylphenol intermediates of ethoxylated surfactants.
  • Phenol is highly reactive and can be readily alkylated in the presence of a crosslinked sulfonated styrene-divinyl benzene resin, Amberlyst 15, at 80 to 150°C.
  • a third preferred conversion is the carbonylation of the n-olefin components of the n-olefin plus n-paraffin extracts.
  • Carbonylation is a reaction with carbon monoxide and an active hydrogen compound to provide a carbonyl derivative of said olefin reactant.
  • the preferred carbonylation catalysts are cobalt and rhodium carbonyl complexes.
  • the hydroformylation of the olefin components of whole FLEXICOKER distillate feeds is described in the earlier referenced Oswald et al. patent. Similar hydroformylation catalysts and conditions are applicable to the n-olefin plus n-paraffin extracts of the present invention.
  • the preferred feed of the present carbonylations is also FLEXICOKER based. It contains mainly 1-n-olefins and n-paraffins separated from FLEXICOKER distillates.
  • n-olefin - n-paraffin mixtures employed as carbonylation feeds are of a relatively narrow carbon range, containing components having 3 different adjacent carbon atoms or less. This allows the separation of the unconverted paraffin components and paraffin by-products from the carbonyl compound products.
  • the aldehyde product may be hydrogenated to the corresponding alcohols prior to paraffin removal by hydrogenation.
  • 1-n-olefin - n-paraffin mixtures are preferred, wherein the 1-n-olefin and n-paraffin have the same particular number of carbon atoms in the molecule.
  • a mixture of 1-n-hexene and n-hexane produced by the present process can be used to produce an ethylene­hexene copolymer.
  • Similar 1-n-olefin - n-paraffins wherein the 1-n-olefin and n-paraffin have the same particular number of carbon atoms in the molecule are preferably used in other olefin conversions such as hydroboration and expoxidation.
  • model compound mixtures employed as feeds in the adsorption tests were made up from pure laboratory chemicals representing the main types of compounds present in the feeds of the present separation process.
  • FLEXICOKER distillates produced by cracking vacuum residua of mixed crudes of South American and Mideastern origin. Fluid-coker distillates similarly derived from Northwest American crude had similar molecular compositions. Both distillates are described in detail int he earlier referred Oswald et al. patent.
  • the zeolite adsorbents were calcined before use by heating at 40°C overnight. Thereafter, they were stored at 80°C under nitrogen until used.
  • S115 was microcrystalline silicalite powder
  • R115 was silicalite pelletized with a silica binder.
  • P115 was pelletized silica with an alumina binder.
  • a low alumina (less than 200 ppm) microcrystalline silicalite was also employed.
  • silicalite powder from Union Carbide Corporation was treated at room temperature at first with an 18% aqueous hydrochloric acid solution overnight 3-4 times, until the supernatant liquid was no longer discolored. Thereafter, the silicalite was treated with a dilute aqueous sodium hydroxide solution of pH 9-10 overnight. These treatments resulted in a significant reduction of its alumina content and the neutralization of acidic impurities.
  • the silicalite resulting from this acid base treatment was calcined as usual.
  • ZSM-5 sodium aluminosilicate derivative derived from the corres­ponding quaternary ammonium derivative was also used.
  • the microcrystalline powder was also calcined and employed in some of the adsorption tests.
  • Sodium ZSM-5, made via direct synthesis by Uetikon of Switzerland was also tested.
  • model compound mixtures and FLEXICOKER distillate fractions employed as feeds in the adsorption tests and their respective raffinates, i.e. non-adsorbed products of these tests, were analyzed by capillary gas chromatography (GC).
  • GC capillary gas chromatography
  • High resolution GC analyses were carried out using a 50 m fused silica column coated with non-polar methyl­silicones. Thus GC retention times were approxi­mately proportional to the boiling points of the components.
  • the adsorption tests were carried out with accurately weighed amounts of zeolite and hydrocarbon feed. After contacting the zeolite and the feed, the composition of the reject­ed hydrocarbon raffinate was analyzed and compared with that of the feed.
  • Static adsorption tests were carried out in both the gas and the liquid phase, using model compound mixtures and FLEXICOKER fractions of varying carbon ranges.
  • gas phase test about 1 g zeolite and 0.2 g hydrocarbon feed were placed into a small closed vial and kept there for four hours at 40°C. With the low, C5 and C6, fractions used in these tests, this was sufficient to reach adsorption and gas liquid equilibria. Thereafter, the gas phase of the test mixture representing the raffinate and the feed were both sampled for G.C. analyses.
  • the hydrocarbon feed was diluted with a non adsorbing bulky com­pound, heptamethylnonane or decalin.
  • 2 g of a 10/90 mixture of hydrocarbon and diluent was used per g zeolite. This proportion of the liquids to solids gave rise to a substantial supernatant liquid phase of the test mixture which could be easily sampled.
  • the test mixture was heated for several hours with occasional shaking to reach equilibrium. The supernatant liquid was then analyzed by GC and its composition was compared with that of the feed.
  • liquid phase tests were carried out with about 1g of a 30/70 mixture of the feed plus diluent per g zeolite. These mixtures exhibited no significant supernatant liquid phase after settling.
  • the sealed mixtures were heated to reach equilibria as above. Due to the absence of a separate liquid phase, the equilibria were more rapidly established in these tests.
  • the test mixtures were diluted with about 1g of isooctane, 2,2,4-trimethylpentane, or other suitable bulky compound and thoroughly mixed. After settling, the clear supernatant liquid phase was analyzed by GC as usual.
  • zeolite microcrystals from the liquids injected to the gas chromatograph is critical for correct compositional analyses of the raffinates. These crystals, if present, are deposited in the high temperature (about 325°C) injection port of the chromatograph and act as cracking catalysts particularly for the 1-n-olefin components.
  • the FLEXICOKER distillate feeds exhibited complex gas chromatograms with overlapping GC peaks of some components, especially in case of the higher fractions. As a consequence the nominal GC percen­tages of some small components were dependent on the GC sample size.
  • the selectivities and capacities of zeolite adsorbents for the components of the test mixtures were estimated by the ratio of their respective concentrations in the raffinate. High ratios indicated selective adsorption while low ratios were signs of rejection by the zeolite.
  • the silicalite was then washed in 1 liter of a mildly basic solution which was prepared by adding 0.3g NaOH to 1 liter water, again allowed to settle, and finally rinsed once with deionized water.
  • the silicalite was dried in air overnight at 90° - 95°C and calcined at 400°C for a minimum of 4 hrs. at which time it was ready for use.
  • the data of the table indicate that 1-n-octene and n-octane are selectively adsorbed from a mixture containing C7 and C8 aromatic hydro­carbons at both test temperatures. There is only minor isomerization of 1-octene to internal i.e. 2-, 3- and 4-octenes.
  • the aromatic sulfur compounds present, 2-methylthiophene and 2,5-dimethylthio­phene, are highly selectively adsorbed.
  • the selec­tivity as indicated by the ratio of raffinate to feed is particularly high for the less bulky methyl­thiophene.
  • a liquid phase adsorption test was carried out with about 2.2 ml of a 10/90 mixture of a C8 FLEXICOKER distillate and heptamethylnonane and 1 g acid/base washed silicalite. The mixture was heated at 110°C for 2 hours. The supernatant raffinate was analyzed by GC and its composition compared with that of the feed. The results are shown in Table V.
  • a comparison of the feed composition with those of the raffinates indicate that all the silicalites tested selectively adsorb 1-n-decene and n-decane.
  • the untreated and acid/base washed silicalites were especially effective in adsorbing 1-n-decene. It is indicated by the low concentra­tion of cis-2-decene in the raffinate, that no significant isomerization of 1-n-decene occurred.
  • the concentration of indene in the raffinate of the mixture with the untreated silicalite is sharply reduced. This is probably due to acid catalyzed dimerization, oligomerization.
  • ZSM-5 exhibits a similar adsorption behavior to that of the alumina bound silicalite of this example and the silicalites of the previous example.
  • 1-n-Decene and n-decane are selectively adsorbed.
  • 2,5-Dimethylthiophene is adsorbed while benzothiophene is rejected. All the aromatic hydrocarbons are rejected.
  • Figure 2 indicates that the aromatic (and branched aliphatic) hydrocarbon components of the feed were eluted at first, due to their simple displacement by the desorbent from the voids of the silicalite column. This early fraction is the raffinate. Elution of the n-decane and 1-n-decene component rich extract occurred distinctly later. These components of the extract clearly coeluted, due their concurrent displacement from the channels of the silicalite by the desorbent. The 1-n-decene was slightly more difficult to displace than the n-decane. As it is shown by the Figure an in­ between-cut of the eluent was taken between the raffinate and the extract.
  • Figure 3 shows that besides n-decane and 1-n-decene, significant amounts of internal linear decenes (5-,4-and 2-decenes) were recovered in the extract. The latter compounds were in part already present in the feed. Additional amounts were formed via 1-n-decene isomerization during the adsorption desorption process.
  • the chromatogram of the figure also indicates the presence in the extract of small amounts, about 0.5%, of 2-methyl-1-nonene.
  • the data of the table indicate the concen­trations of 1-n-decene, n-decane, trans-2-decene and the major, identified aromatic hydrocarbon com­ponents.
  • the percentages of 1-n-decene and n-decane decreased in all the raffinates, indicating their selective adsorption.
  • the concentrations of most aromatic hydrocarbons increased in the raffinate, due to their rejection.
  • the various silicalites and sodium zeolite exhibited a similar adsorption behavior.
  • the data of the table show that the C9 to C13 model feed mixture contained about equal amounts (9 wt.%) of C9 to C12 1-n-olefins. Also, similar amounts (5,7 wt.%) of C9 to C12 n-paraffins were present in the feed. The concentrations of the rest of the hydrocarbon components were about 3.5% by weight. Due to the different factors of GC detec­tion, the percentages determined by GC were somewhat different but similar.
  • a C9 to C13 mixture of FLEXICOKER distil­lates was prepared by combining fractions in the 139 to 234°C boiling range in proportions providing 1-n-olefin concentrations in the 2.1 to 3.1% range. This feed was then diluted with heptamethylnonane to obtain a 21.5% test solution.
  • the molecular sieve employed for adsorption was a sodium ZSM-5 zeolite prepared by Uetikon of Switzerland via direct synthesis. About 1.2 g test solution was added to 1 g zeolite and the mixture was heated at 120°C for 1 hour. The supernatant raffinate liquid was then analyzed by GC and its composition was compared with that of the feed. The capillary gas chromatogram of the feed and the raffinate are shown by Figure 6 and 7, respectively.
  • a mixture of model compounds was made up from 5 wt% of each, 1-n-tetradecene, 7-tetradecene, n-tetradecane, 1% benzothiophene and 84% of decalin. About 2.7 g of this mixture was mixed with 1 g of acid/base washed silicalite and heated at 150°C for 2 hours. A subsequent analysis of the supernatant raffinate indicated that all the C14 n-aliphatic hydrocarbons were adsorbed by the silicalite. However, the n-tetradecenes were more selectively removed than n-tetradecane.
  • a mixture of C9 to C13 n-olefins and n-paraffins is separated from the corresponding broad FLEXICOKER distillate via a molecular adsorp­tion of the type described in Example 12.
  • This mixture containing C9 to C13 1-n-olefins as the main reactive components, is then oligomerized using a boron trifluoride complex of an alcohol, i.e. neopentyl alcohol.
  • the oligomerization is carried out in the liquid phase at temperatures and pres­sures sufficient to convert not only the terminal 1-n-olefin components but most of the internal n-olefins as well to polyolefin oligomers containing olefin trimers as the main components.
  • the resulting polyolefin - n-paraffin mixture is then hydrogenated in the presence of a sulfur insensitive transition metal sulfide cata­lyst.
  • This provides an isoparaffin plus n-paraffin mixture which is then separated by distillation.
  • the n-paraffins and the isoparaffin dimers are distilled.
  • the residual isoparaffin product com­prising mainly trimers and tetramers is a desirable synthetic lubricant.
  • the n-paraffin distillate is converted via known chlorination - dehydrochlori­nation reactions to linear olefin intermediates of biodegradable alkylbenzene sulfonate manufacture.
  • the isoparaffin dimers are useful as solvents of low volatility.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Lubricants (AREA)
EP19890312735 1988-12-07 1989-12-06 Procédé de séparation de n-oléfines et n-paraffines à partir de mélanges d'hydrocarbures Expired - Lifetime EP0372939B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28130788A 1988-12-07 1988-12-07
US281307 1988-12-07

Publications (2)

Publication Number Publication Date
EP0372939A1 true EP0372939A1 (fr) 1990-06-13
EP0372939B1 EP0372939B1 (fr) 1993-09-15

Family

ID=23076747

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890312735 Expired - Lifetime EP0372939B1 (fr) 1988-12-07 1989-12-06 Procédé de séparation de n-oléfines et n-paraffines à partir de mélanges d'hydrocarbures

Country Status (3)

Country Link
EP (1) EP0372939B1 (fr)
JP (1) JPH02212595A (fr)
CA (1) CA2004430A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993002154A1 (fr) * 1991-07-25 1993-02-04 Exxon Chemical Patents, Inc. Procede d'adsorption pour la separation des liquides
US5220102A (en) * 1991-12-23 1993-06-15 Uop Process for separating normal olefins from non-normal olefins
EP0569631A1 (fr) * 1990-10-09 1993-11-18 Wylie Inventions, Inc. Procédé de séparation par adsorption-désorption
US5276246A (en) * 1991-12-23 1994-01-04 Uop Process for separating normal olefins from non-normal olefins
EP0797239B1 (fr) * 1996-03-22 2002-10-16 Osram Sylvania Inc. Lampe à décharge au mercure avec plaquette d'amorçage
KR20190029898A (ko) * 2017-09-13 2019-03-21 연세대학교 산학협력단 이산화탄소를 이용한 올레핀과 파라핀의 분리 공정
US10400177B2 (en) * 2017-11-14 2019-09-03 Exxonmobil Research And Engineering Company Fluidized coking with increased production of liquids
CN114210174A (zh) * 2021-11-10 2022-03-22 生态环境部华南环境科学研究所 一种强化吸收/吸附耦合的恶臭及有机废气治理方法
EP4206169A4 (fr) * 2020-08-26 2024-09-18 China Petroleum & Chemical Corporation Adsorbant composite pour la séparation d'éthylbenzène par rectification par adsorption et utilisation correspondante

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5262144A (en) * 1991-12-26 1993-11-16 Uop Siliceous molecular sieves having low acid activity and process for preparing same
CA2298618C (fr) * 1997-08-08 2007-04-03 The Procter & Gamble Company Procedes ameliores de fabrication de tensio-actifs selon une technique de separation par adsorption et produits ainsi obtenus

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0031676A1 (fr) * 1979-12-19 1981-07-08 Mobil Oil Corporation Sorption sélective à l'aide de zéolites

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0031676A1 (fr) * 1979-12-19 1981-07-08 Mobil Oil Corporation Sorption sélective à l'aide de zéolites

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0569631A1 (fr) * 1990-10-09 1993-11-18 Wylie Inventions, Inc. Procédé de séparation par adsorption-désorption
WO1993002154A1 (fr) * 1991-07-25 1993-02-04 Exxon Chemical Patents, Inc. Procede d'adsorption pour la separation des liquides
US5220102A (en) * 1991-12-23 1993-06-15 Uop Process for separating normal olefins from non-normal olefins
US5276246A (en) * 1991-12-23 1994-01-04 Uop Process for separating normal olefins from non-normal olefins
EP0797239B1 (fr) * 1996-03-22 2002-10-16 Osram Sylvania Inc. Lampe à décharge au mercure avec plaquette d'amorçage
KR20190029898A (ko) * 2017-09-13 2019-03-21 연세대학교 산학협력단 이산화탄소를 이용한 올레핀과 파라핀의 분리 공정
US10400177B2 (en) * 2017-11-14 2019-09-03 Exxonmobil Research And Engineering Company Fluidized coking with increased production of liquids
EP4206169A4 (fr) * 2020-08-26 2024-09-18 China Petroleum & Chemical Corporation Adsorbant composite pour la séparation d'éthylbenzène par rectification par adsorption et utilisation correspondante
TWI887476B (zh) * 2020-08-26 2025-06-21 大陸商中國石油化工科技開發有限公司 吸附精餾分離乙苯的複合吸附劑及方法
US12441672B2 (en) 2020-08-26 2025-10-14 China Petroleum & Chemical Corporation Composite adsorbent for separation of ethylbenzene by adsorption distillation and application thereof
CN114210174A (zh) * 2021-11-10 2022-03-22 生态环境部华南环境科学研究所 一种强化吸收/吸附耦合的恶臭及有机废气治理方法
CN114210174B (zh) * 2021-11-10 2023-08-04 生态环境部华南环境科学研究所 一种强化吸收/吸附耦合的恶臭及有机废气治理方法

Also Published As

Publication number Publication date
EP0372939B1 (fr) 1993-09-15
JPH02212595A (ja) 1990-08-23
CA2004430A1 (fr) 1990-06-07

Similar Documents

Publication Publication Date Title
US5292990A (en) Zeolite composition for use in olefinic separations
CA1199036A (fr) Reactions d'olefines avec catalyse acide stereo- selective au moyen de zeolithes cristallisees
US4417088A (en) Oligomerization of liquid olefins
RU2294916C2 (ru) Способ конверсии углеводородной загрузки
FI120627B (fi) Menetelmä olefiinien oligomeroimiseksi
JP4767393B2 (ja) オレフィン類の製造
US4542251A (en) Oligomerization of liquid olefin over a nickel-containing silicaceous crystalline molecular sieve
US2906795A (en) Recovery and utilization of normally gaseous olefins
US4423269A (en) Oligomerization of gaseous olefins
JP2010138405A (ja) プロピレンの製造
EP0372939A1 (fr) Procédé de séparation de n-oléfines et n-paraffines à partir de mélanges d'hydrocarbures
KR20080069215A (ko) 올레핀 이합체화 공정
US5198597A (en) Bimetallic catalysts for dehydroisomerization of N-butane to isobutene
US5210333A (en) Benzene removal from hydrocarbon streams
US5498811A (en) Process for producing gasolines and jet fuel from n-butane
EP3237581B1 (fr) Procédé de production d'hydrocarbures c2 et c3
EP0372938B1 (fr) Composition zéolitique utilisable en séparations d'oléfines
EP2649161B1 (fr) Procédé de production de composés de distillat moyen à partir de composés d'essence par oligomérisation d'olefines
US4458097A (en) Conversion of certain hydrocarbons using divalent-copper-containing ZSM-5 type catalyst
US5227552A (en) Process for hydrogenating alkenes in the presence of alkanes and a heterogeneous catalyst
US4650917A (en) Method for upgrading olefinic lubes
KR102142606B1 (ko) 경질 파라핀을 이성질체화하기 위한 플랫포밍법의 사용
WO2017050454A1 (fr) Procédé de régénération d'un adsorbant pour composés contenant de l'azote présents dans une alimentation en hydrocarbure
EP0615782A1 (fr) Systèmes catalytiques à base de zéolithe
US4395578A (en) Oligomerization of olefins over boron trifluoride in the presence of a transition metal cation-containing promoter

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): FR GB IT

17P Request for examination filed

Effective date: 19901130

17Q First examination report despatched

Effective date: 19910619

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): FR GB IT

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19931117

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19931203

Year of fee payment: 5

ITF It: translation for a ep patent filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19941206

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19941206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051206