EP0372939B1 - Trennungsverfahren für n-Olefine und n-Paraffine aus Kohlenwasserstoffgemischen - Google Patents

Trennungsverfahren für n-Olefine und n-Paraffine aus Kohlenwasserstoffgemischen Download PDF

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EP0372939B1
EP0372939B1 EP19890312735 EP89312735A EP0372939B1 EP 0372939 B1 EP0372939 B1 EP 0372939B1 EP 19890312735 EP19890312735 EP 19890312735 EP 89312735 A EP89312735 A EP 89312735A EP 0372939 B1 EP0372939 B1 EP 0372939B1
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olefins
adsorption
mixture
olefin
zeolite
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EP0372939A1 (de
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Alexis Alexander Oswald
David William Savage
Edward Kantner
Ramon Luis Espino
Di-Yi Ou
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • 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 for n-olefins and n-paraffins from hydrocarbon mixtures.
  • the early sieve adsorbents were crystalline aluminosilicates commonly known as zeolites. However, during the last ten years similar crystalline 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.
  • the early 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 C 4 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 C 4 hydrocarbons from the zeolite.”
  • Neuzil et al. aimed their process for the separation of isobutylene from C 4 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 C 6 olefins from cyclic and branched C 6 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 C 5 to C 1 9, preferably Cs to C 1 9, mixtures of n-olefins and n-paraffins from a feed mixture comprising aliphatic and aromatic hydrocarbons, and for the conversion of the separated n-olefins to isoparaffins, which process comprises:
  • the process of the present invention can be operated using a mixture comprising open chain and cyclic aliphatic hydrocarbons and aromatic hydrocarbons, for example 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 C 6 to C 8 carbon range were found to be absorbed 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 Cs to C 19 range containing mostly aromatic, bulky sulfur compounds such as benzothiophene, are preferred.
  • 1-n-olefins were found to be absorbed with an increased selectivity as compared to other products in the feed stream.
  • An attractive feature of the present separation process is that it can utilize 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. a-) 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 neutral molecular sieve preferably a metal zeolite such as sodium ZSM-5, has a minimum silica to alumina ratio of 20. It is more preferably a silicalite, most preferably a silicalite substantially free from alumina, which has been preferably pretreated by an acid and then a base.
  • the selective absorption is from the liquid phase under pressure sufficient to maintain liquid phase, and in the temperature range of 10 ° C to 250 ° C more preferably 20 ° C to 150 ° C, most preferably 100 ° C to 140 ° C.
  • the desorption step is conducted by contacting the resulting zeolite containing the n-olefin and n-paraffin enriched extract with a more volatile desorbent gas and/or liquid, preferably liquid, under pressure sufficient to maintain liquid phase; preferably an n-olefin and/or n-paraffin, more preferably an n-olefin or n-paraffin; under conditions sufficient to effect displacement from the sieve of said extract, preferably under the conditions employed in the adsorption step.
  • a more volatile desorbent gas and/or liquid preferably liquid, under pressure sufficient to maintain liquid phase
  • an n-olefin and/or n-paraffin more preferably an n-olefin or n-paraffin
  • the olefin components of the separated mixture may be oligomerized in the presence of an acid catalyst, preferably a boron trifluoride complex, more preferably a boron trifluoride alcohol complex, to selectively produce an oligomer containing 2 to 6 monomer units. Thereafter the olefinic double bonds of said oligomer are hydrogenated to produce isoparaffins, for example an isoparaffin lubricant.
  • the unreacted n-paraffin components are separated from the isoparaffin-containing reaction mixture, preferably by distillation.
  • 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 preferably 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 C 1 to C 3 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 C 1 to C 3 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 majority of olefins are Type I and Type II olefins as indicated by the following tabulation showing approximate concentration ranges determined by proton magnetic resonance spectrometry (NMR),
  • 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 2 to C 1 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 C 5 to C 7 carbon range there are major amounts of thiols present.
  • the C 8 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 C 8 to C 11 range. Benzothiophenes are mostly present in the C 12 to C 15 range. In the higher boiling fractions, dibenzothiophenes are major sulfur compound components.
  • the zeolite adsorbents employed in 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 zeolite adsorbents employed in 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 Cs 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.
  • the neutral zeolites for use in the invention can be prepared by the neutralization of protonated zeolites by the appropriate metal base or salt, such as aqueous sodium hydroxide or sodium chloride.
  • 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/AI 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 A1 2 0 3 . 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 C 5 to C19 s 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 Cs to C 15 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 C 8 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, C 5 to C 8 distillate, feeds can be carried out at low temperatures, in the 10 to 100 ° C regime. The adsorption of Cs to C19 fractions at optimum diffusion rates requires increasing temperatures, ranging from 100 to 200 °C. However, 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.
  • 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 C 6 feed, 1-hexene for a C 7 to C 9 feed, 1-n-octene for a Cs to C 13 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 C 8 to C 15
  • the low boiling part of the extract e.g. a mixture of C 8 , Cs 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.
  • 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 BF 3 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.
  • oligomers containing an average of 3 to 4 monomer units, trimers and tetramers are produced by reacting a mixture rich in Cs to C 13 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 C 13 to C 17 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 oligomerization of n-olefins produces polyolefins in the C 16 to C50 range. These may subsequently be used to alkylate benzene to produce C 16 to Cso alkylbenzene intermediates for the synthesis of oil soluble calcium and magnesium alkylbenzene sulfonate detergents.
  • oligomerizations preferably C 5 to C S n-olefins are employed.
  • the unconverted paraffin components of the n-olefin oligomer product mixture are removed preferably by distillation.
  • 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 400 ° 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, C 5 and C 6 , 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.
  • 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 1 g 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 1 g 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.
  • silicalite S115 from Union Carbide Corporation
  • the liquid-solid suspension was allowed to settle overnight to separate into two phases.
  • the supernatant liquid phase which had become discolored, was decanted and 1 liter of fresh 18% HCI was added to the solid with stirring and again allowed to settle overnight.
  • This acid washing procedure was repeated a third time, after which the liquid phase remained colorless.
  • the silicalite was collected and washed repeatedly with deionized water until the wash water gave a neutral reaction to litmus.
  • 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 C 7 and C 8 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 C 8 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.
  • the data show a highly selective adsorption of both 1-n-decene and n-decane.
  • a minor isomerization of 1-n-decene is indicated by the readily distinguished GC peaks of 4-decene and trans-2-decene.
  • the approximate capacity of the silicalite for these compounds together is 10.1 %.
  • 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 inbetween-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 C 9 to C 13 model feed mixture contained about equal amounts (9 wt.%) of C 9 to C 12 1-n-olefins. Also, similar amounts (5,7 wt.%) of C 9 to C 12 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 C 9 to C 13 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 C 14 n-aliphatic hydrocarbons were adsorbed by the silicalite. However, the n-tetradecenes were more selectively removed than n-tetradecane.
  • a mixture of Cs to C 13 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 C 9 to C 13 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.
  • polyolefin lubricant products Due to the presence of significant amounts of linear internal olefins and minor amounts of monomethyl branched olefins in the feed the polyolefin lubricant products are distinct over products of the prior art. The presence of comparable amounts of even and uneven carbon number olefin reactants in the feed also distinguishes the products over the prior art poly-a-olefin lubricants derived from ethylene via even numbered 1-n-olefins.

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  • 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)

Claims (13)

1. Verfahren zur Abtrennung von Cs- bis Cig-Mischungen von n-Olefinen und n-Paraffinen aus einer Einsatzmaterialmischung, die aliphatische und aromatische Kohlenwasserstoffe umfaßt, und zur Umwandlung der abgetrennten n-Olefine zu Isoparaffinen, bei dem
die Einsatzmaterialmischung mit einem neutralen Zeolithadsorbens, das eine Porengröße von 3,5 bis 7,0 x 10-10 m (3,5 bis 7,0 Å) und ein Siliciumdioxid-zu-Aluminiumoxidverhältnis von mindestens 20 aufweist, unter Bedingungen kontaktiert wird, die ausreichend sind, um eine selektive Adsorption von n-Olefinen und n-Paraffinen bewirken;
die adsorbierte, an n-Olefin und n-Paraffin angereicherte Mischung von dem Zeolith desorbiert wird; die n-olefinische Komponente der angereicherten Mischung oligomerisiert wird und die olefinische Ungesättigtheit der resultierenden Oligomere hydriert wird, um Isoparaffine herzustellen, und
die nicht umgesetzte n-Paraffinkomponente aus der Isoparaffin enthaltenden Mischung entfernt wird.
2. Verfahren nach Anspruch 1, bei dem der Zeolith ein Silikalit ist.
3. Verfahren nach Anspruch 1, bei dem der Zeolith Natrium-ZSM-5 ist.
4. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der Zeolith zuvor mit Säure und Base behandelt worden ist.
5. Verfahren nach einem der vorhergehenden Ansprüche, bei dem sowohl Adsorption als auch Desorption im Temperaturbereich von 10 bis 250 ° C durchgeführt werden.
6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Desorbens ein n-Olefin und/oder ein n-Paraffin ist.
7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Kohlenwasserstoffeinsatzmaterialmischung organische Schwefelverbindungen in einer Konzentration entsprechend 0,05 bis 3 % Schwefel enthält.
8. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Kohlenwasserstoffeinsatzmaterialmischung ein Destillat ist, das durch thermisches Cracken bei hoher Temperatur aus Erdölrückständen hergestellt worden ist.
9. Verfahren nach Anspruch 8, bei dem das Destillat 1-n-Olefine als den überwiegenden Typ von Olefinkomponente enthält.
10. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die olefinische Komponente der angereicherten Mischung in Gegenwart eines sauren Katalysators oligomerisiert wird.
11. Verfahren nach Anspruch 10, bei dem der Katalysator ein Bortrifluorid-Alkoholkomplex ist.
12. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die olefinische Komponente der angereicherten Mischung oligomerisiert wird, so daß Oligomere mit 2 bis 6 Monomereinheiten hergestellt werden.
EP19890312735 1988-12-07 1989-12-06 Trennungsverfahren für n-Olefine und n-Paraffine aus Kohlenwasserstoffgemischen Expired - Lifetime EP0372939B1 (de)

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US5132486A (en) * 1990-10-09 1992-07-21 Wylie Engineering & Construction, Inc. Adsorption-desorption separation process for the separation of low and high octane components in virgin naphthas
WO1993002154A1 (en) * 1991-07-25 1993-02-04 Exxon Chemical Patents, Inc. Adsorption process for liquid separation
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
US5262144A (en) * 1991-12-26 1993-11-16 Uop Siliceous molecular sieves having low acid activity and process for preparing same
US5698943A (en) * 1996-03-22 1997-12-16 Osram Sylvania Inc. Starting flag for use in mercury discharge lamp and lamp employing same
EP1027312B1 (de) * 1997-08-08 2005-01-12 The Procter & Gamble Company Verfahren zur herstellung von oberflächaktiven verbindungen mittels adsorptiven trennung
KR101985784B1 (ko) * 2017-09-13 2019-06-04 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
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

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US4309281A (en) * 1979-12-19 1982-01-05 Mobil Oil Corporation Selective sorption by zeolites

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