CA2004430A1 - Zeolite separation process for olefin-paraffin mixtures useful in synlube production - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

This invention relates to a separation process for the adsorption-desorption of n-olefin n-paraffin mixtures in zeolites, particularly acid free silicalite molecular sieves. Preferred hydrocarbon feeds for the present separation process are C9 to C19 distillates derived via the thermal cracking of petroleum residua. Such distillates, e.g. light FLEXICOKER and Fluid-coker gas oils contain 1-n-olefins and n-paraffins as the main types of components and minor components of branched olefins and paraffins as well as aromatic hydrocarbons and sulfur compounds. Mixtures mostly consisting of 1-n-olefins and n-paraffins can be separated from such coker distillates containing relatively high concentrations of sulfur compounds via the present process.

The olefin components of n-olefin and n-paraffin mixture products of the present molecular sieve separation can be utilized as reactants in polymerization, alkylation and carbonylation reactions, wherein the unconverted paraffin components are subsequently separated by distillation. Such a three step sieving, conversion, distillation process is particularly attractive as a low cost approach for the preparation of polyolefin based synthetic lubricants.

Description

FIELD OF THE INVENTION

The separation process of the present invention is 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.

One aspect of the instant invention is the description of the selective adsorption of various types of hydrocarbons and organic sulfur compounds particularly olefins, from hydrocarbon mixtures containing olefins, paraffins, aromatic hydrocarbons and sulfur compounds. High selectivities were particularly found for Cg to C3s n-olefins and n-paraffins.

Another aspect of the instant invention is the selective adsorption of mixtures of ~-olefins (l-n-olefins) and n-paraffins from distillates produced by thermal cracking operations, especially FLEXICOKER and FLUID-COKER distillates.

A further aspect of the disclosure is the conversion of the olefin components of the n-olefin and n-paraffin mixtures which have been separated via molecular sieves. Tbese conversions include polymerizations, alkylations and carbonylations and are followed by a distillation proces~ to remove the unconverted paraffins from the converted product.

~. ~

2Qo~o The conv~rsion of thQ Cg-C13 ~-olefin components separated ~rom below~fuel-value FLEXICOKER distil-la~es to poly-~-olefin type synthetic lubricants is particularly discussed.

PRIOR ~RT VERSUS T~E PR~SENT INVENTION

Selective adsorption o~ hydrocarbons in molecular sieve~ has been known for more than 25 years. The selectiv~ ad~orption of n-paraffins by molacular sieves is a widely employed com~ercial m~thod of separation.

Tha early ~ievQ adsorbent~ wer~ crystal-line aluminosilicates co~monly known as zeolites.
Ho~e~er, during the last ten years si~ilar crystal-lin~ sieve compound3 o~ difPerent chemical composi-tion~ were synthesized. The e include alumino phosphatec and variou~ microporous crystalline ~ilica, including silicalite, which may contain small amounts of alumina. In tha present invention all the~ ~hapQ ~lectl~ ad~orbent compounds are broadly t~rm2d a~ zeolite~.

The ~arly aluminosilicate zeolites were mo~tly activ~ a~ catalysts, due to their polar, acldic charact~r. They l~d to olefin i30meriza~ion, oligo~erizatlon, alkylation, polymerization and cracking rQaGtion~. N~erth~le~s, they were often dlsclo~d a~ ~d80rb~nt~ ~or ~paration~ applicable in ro~inery proces~s wh~r~ s~lectivitie~ and the ab~ence o~ sid~ r~actions w~ro 1~YS critica~. ~ost o~ the prior pat~nts w~r~ ai~ed at tho separation of n-para~fin~. -L3~

~ berly and Webb described in U.S. Patent 3,485,748 th~ s~paration of normal and branched chain paraffins and ole~in3 from aromatic hydrocar-bons, using an acid tr~ated mordenite having an SiO2/A12O3 molar ratio above 25.

A number o~ patent-~ assigned to Mobil Oil Corporation di3close the uRe o~ ZS~-5 and related zeolites ~or the separation of normal paraffins.
Gorring and Shipman de~cribed in U.S. Patents 3,894,938 and 3,980,550 the catalytic hydrodewaxing of gas oil using multivalent transition metal derivatives of ZSM-5 and the li~Q. Thiæ process for tha production of lubricatin~ oil~ of reduced pour point was improved by Garwood and ~aesar. They disclose in U.S. Patent 4,149,960 that the addition of water to the gas oil feed reduces coke formation.
U.S. Patent 4,517,402 by Dessau disclosed a procsss for the ~12ctivQ separation of llnear aliphatic compounds with ZS~-ll. Dessau shows the separation of n-paraf~ins ~rom ~ranch~d paraf~in~ and aromatics and the separation n-olQfinc ~ro~ branched olefins.
However, he n~ith~r show~ nor suggests the s~para-tion of an n-paraffin and n-olefin mixture from a ~ed containing both allphatic and aromatic hy~ro-caxbonR.

U.S. Pat~nt ~,619,758 by Pratt, Sayles, Bow~rs and Scott disclo~ tha s~leGtiv~ adsorption o~ n-para~ins by zeolit~s such a~ ZSM-5, from hydrocarbon mixtur~Q ~or exampl~ vacuum gas oil, followed by cracking o~ sa$d n para~ins in the zeol$t~.

' U.S. Patent 3,969,223 by Rosback and Neuzil disclos~3 the s~paration of olefins from ole~in - paraffin mixtures, such as crac~ed wax by an X z201ite with an amorphous binder previously treated by aqueous sodium hydroxide to increase its sodiu~ cation concentration. The trea~ment resulted in less olefin dimerization durlng the separation.
However, thi~ large pore dia~eter zeolite could not be used to separate straight chain and branched chain compounds.

N~uzil and Xulprathipanja were the first to disclose, in U.S. Patent4,455,445, column 1, lines 25 to 32, "that silicalite i8 abl~ to ~f~ect the separation of normal C4 hydrocarbons from isobutyl2ne with substantially complete elimination of the aforemention~d und~ired ~ide effects of olefin di~erization and poly~rization, particularly when pentene-l i3 used to displace the normal C4 hydrocarbon3 fro~ the zeolite." Neuzil et al. aimed th~ir process for th~ separation of isobutylene from C4 hydrocarbons, ~inc~ isobutylene is userul e.g. as a ga~oline blending agent and as a monomer ~or the production o~ polyi~obutylen~. They naither dis-clo~d nor ~ugg~st~d this s~paration for the pro-duction ~r u~eful mixtures of higher n-olefins and n-paraf~in~.

Kulprathip~n~a and Neuzil al50 disclosed in U . S . Patant 4, 48~, S18 th~ adsorption of norMaI C6 ol~fins fro~ cycIic and branchad C6 ole~in8 u~ing a ilicalite wi~h alu~ina ~ a bind~r. l-P~ntene or l-bu~ene WerQ U~Qd Por d~orption. l-Octene could nev~r co~pletaly displace l-hexen~. In U.S. patent 2gl~43QI

4,433,195, ~ulprathipanja disclosed the separation o~ a trans-olefin ~rom a cis-olefin via selective adsorption by a silicalite. A~ an example he described the adsorption o~ trans-2-butene from a mixture o~ Ci8- and trans-2-butenes ~ollowed by desorption with l-pentene.

U.S. patent 4,455,444 by Kulprathipanja and Neuzil di~closed the selectiva adsorption of n-paraffins in silicalite and their desorption by n ole~in3, particularly l-hexene. However, this patent empha~ized that thQ ~eed~ are li~i~ed to hydrocarbons containing little or no ol~fins. The disclosure~ of th~ parent patsnt by Xulprathipanja and NQuzil, i.e. U.S. patent 4,367,364, were also limited to selective n-paraffin adsorption in ~ilicalites in the pre~enca o~ lit~le or no olefins.
Additionally, the proce~s of thi~ patent and the proces~ of th~ above di~cu~sed subse~uent patents by the sa~e inventor~ were limited to hydrocarbon feeds containing cyclia hydrocarbon~ having more than six carbons. This exclude~ benz¢ne which can enter the pores of the ~ilicalit~

Overall the disclosure3 of the Xulprathipan~ and NQuzil patent~ suggest that all th~ work wa~ carri~d out with silicalit~ plus alu~in~ binder co~po~ition~. The r~ ults were probably a~rected by the pre~nce Or th~ acidic alu~ina even though th~ Si/~l ra~io~ were above 12 ~8 st~ted in U.S. pa~ent 4,~86,618.

Some o th~ fundamen~al in~ormation di~closed in th~ Kulprathlpan~a and NQuzil patents Z~ 3~) wa3 previously publl5hed in an article announcing the discovery of silicalite: A research group of the Union Carbide Corporation and J.V. Smith of ~he University of Chicago r~ported, in volume 271, p~ges 512 to 516 of Nature, the synthesis, structure and generic adsorption propertie~ of silicalite in 1978.
Silicalite was patented in 1977 as a novel composi-tion of matter in U.S. Paten~ ~,061,724 by R.W.
Grose and E.M. Flanigen, a~3igned to Union C~rbide.
A more recent publication of thi composition by Y.H. ~a and Y.S. Lin appe red a3 paper No. 68h-21 in the pr2prints o~ the 1984 Annual ~eetin~ in San Francisco of the American In~titute o~ Ch~mical Engineer It wa~ found that th~ equilibrium adsorption capacity of silicalite ~or th~ investi-gated hydrocarbon in n-hexene ~olution d~crea~es in the following order~ 1-heptene ~ cyclohexene >
benzene > cyclohexane > n-octan~ and the pre3ence of alumina binder aff~cted the ad~orption in most cases.

The prior art di.closures generally contrast with those of the present invention. The process~s disclo~d in the prior art were directed e~ther to the s~paration of ole~in-~ or to the ~para~ion o~ para~in~. Ther~ were no processe~
di~closed or ~ugge~ted ~or the ~paration of Cs to Clg n-ol~Pin an~ n paraf~in ~ixtur~s fro~ branched ol~$n~, branch~d para~lns, aromatic hydrocarbons and ~ul~ur con~aining compounds by th~ use of zeolites.

In ~act, the prior art teaches away from the ~epara~lon of Cg and higher n-ole~ins. It 2~ 30 ~ 7 -generally emphasiZeS that the hydrocarbon feeds for zeolite separation should contain little or no ole~ins.

The prior art implie~ that hydrocarbon f~eds containing high concentration~ o~ aromatic hydrocarbons other than benzene, nitrogen and sulfur co~pounds are to be avoided because ~uch compounds would deactivatQ the molecular sieves by blocking off the salective pore passageways. (See U.S.
pat~nt 4,455,445, lines 45 to 56 and U.S. patent 4,433,195, lines 7 to 14).

In con~rast to the prior art, the present invention i5 directed toward the ~eparation o~ Cs to Clg n-olefin and para~fin mixture~ fro~ branched olefins, branched para~fin~, aromatics hydrocarbons and sulfur containing compounds by th~ use of zeolites. In spite o~ th~ negativa teaching~ of the prior art, it wa~ Pound that the pre~ent process could be apera~ed using a ~ix~ure compri~ing open chain and cyclic al~phatic hydrocarbons and benzene.

It wa~ ~urpri~ingly found that the present proces~ i~ applicabla to hydrocarbon ~trea~s con-~aining relativsly large a~ounts of aromatic sulfur co~pounds. Thioph~ne, a~thylthiophenes and dimethy-lthioph~n~ which boll in the C6 to Cg carbon range wor~ ~ound to b~ ad~arb~d in the zQolite. Higher boiling, bulklGr aro~a~ ul~ur compound~ such a~
b~nzo~hiophQna w~re rejected.

Unexp~ctadly, th~ proc~ og the present invention i~ applicable to sulfur containing 43~
- B -ol~finic di~tilla~es derived by the high temperature thermal cracking of petroleum re~idua. Distillates in the Cg to c1g range, containing mo~tly aromatic, bulky sulfur compounds such as benzothiophene, are ~ preferred. In this high carbon range, l-n-olefins were found to be adsorbed with an increased selecti-vity as compared to other pr~ducts in the feed stream~

In th~ present invention acid-base treat~d silicalite~ and sodium ZSM-5 wer~ found to be particularly suitable adsorb2nt~ ~or the separation of mixtures and 1-n-ole8in~ and n-paraf~ins, because of their red~ced olefin iso~erization activity.

The co~bined separation - olefin convar-sion process o~ the present invention is additional-ly distingui hed over the pricr art. The combined proces~ conv~rt~ the ole~in co~ponents of the ~eparated ole~in-paraf~in ~ixtures to hiyher boiling products and re~ove~ the unconverted paraffins thereafter by ~la~h of~. Thi~ uniquQ combination of proces~ 5tep3 ha~ never been contemplated prior to the instant inv~n~ion.

F~ C~ Io~_oF T~ ~ S

Figure 1 illuRtrat~ th~ capillary gas chro~atcgra~ o~ a harp Clo F~EXICOKER distillate ~raction, which was mo~t Prequently us~d a~ a feed for z~olit~ ceparations.

Figure 2 illu~trat~ the da~orp~ion, by n-hexanQ in a pulse te~t, of arom~tic ra~finate Z~43~3 g component~ and a l-n-decene plu~ n-decane extract.
This figure is discu~sed in detail in Example 12, Figure 3 illustrate~ the capillary gas chromatogram o~ a n-decenes plu8 n-decane extract of the Clo FLEXICOXER distillate fraction, said ex~ract having been obt~ined in the p~l a test.

Figure 4 and 5 show the capillary gas chromatograms of a feed mixtura of Cg to Cl2 model compound~ and the raffinate derived ~rom it by sodium ZSM-5 adsorption. The datails are discussed in Exa~pl~ 16.

Figur~s 6 and 7 show the gas chro~atograms of a Cg to C13 FLEXICOKER di~tillat~ feed and its raffinate product. Tho details o~ the selective adsorption involvad are di~cus ed in Example 17.

SYM~ARY OF ~ VENTI~N

Thi~ inv~ntion provid~ a new sepaxation approach ~or obtaining nor~al olefin, particularly ~-ole~in reactant~, suitable as chemical inter-~ediates. Known chemical mQthods for the pr~para-tion of ~uch olefin~ are ethylene oligomerization, par2ffin crac~ing and dehydrogenation and alkyl ~hlorida d~hydrog~nztion ~nd alkyl chloride dehydro-chlorination. Pa~t s~par~tions were direc~ed to the separation o~ ol~in~. In contrast, the presen~
in~ention provid~s a proce~ which s~parates a ~ixture o~ n-olefins and n-par~fin~ by a neutral ~olecular sieve o~ pr~ferably high ~ilica alumina ratio. Tha olefin componen~ o~ thi~ mix~ure are then ~electively converted to desired higher mole-cular weight~prodUCtS in a separate step. Finally, the unreacted paraffins are removed from the reac~
tion mixture by distillation.

The key process step of the present invention i~ a molecular sieve separation. Past sieve separation proces~es were usually aim2d at the separation of single types of compounds. Distinct processeR wer~ developed ~or th~ separation of olefins and noxmal paraffins. In contrast the present proces~ separate~ a mixture o~ n-ole~ins and n-paraffins.

A k~y attractive f~ature o~ the present separation pro~ess is that it utilizes low C08t ol~$nic hydrocarbon feed~ which contain not only aliphatic hydrocarbonc but aro~atic hydrocarbon and sulfur compound~ a~ well. Such ole~inic hydrocarbon feed~ are produced by the high temperature thermal cracking of p~roleu~ re~idua, particularly vacuum re3id~. The~ ds contain hig~ concentrations of linear terminal (i.e. 3-) olefins of Type I and lin~ar int~rnal olefin~ of Typ~ II.

~ noth~r i~portan~ r~atur~ of th~ present ~æparation is th3 U5Q 0~ a neutral mol~cular sieve.
T~ ini~ize~ ole~in ~id~ reactions and allows ~he s~paration o~ l-n-ole~ln - n-paraX~in mixtures withou~ any major ter~inal, e.q. olafin to internal ola~in iso~erization. In the present process, pr~f~rably low alu~ina z~olites having le~s than 5000 pp~ alumina ar~ used for ~lective ad~orption.

Z0~ 3iD

From the viewpoint of process economics, it is most important that the present process can use feeds containing substantial amounts of aromatic components. 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 ~acuum residua by Fluid-coking or FLEXICOKING. These distillates contain 1-n-olefins as the major type of olefin components and organic sulfur.

DESCRIPTION_OF THE PREFERRED EMBODIMENTS

The present invention relates to a process for the separation of Cs to Clg preferably Cg to C1g 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 Clg 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, mors 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 temp~rature range of 10C to 250C, more Z(~ 3(~

preferably 20C to 150C, most preferably 100C to 140C, and contacting the resulting sieve 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 conditions of the adsorptian step.

Nore specifically the invention provides a process for the separation of Cg to C1g mixtures of n olefins and n-paraffins from aliphatic and aromatic hydrocarbons and, optionally, sulfur containing compounds, preferably l-n-olefins and n-paraffins, comprising containing a mixture of Cg to C19, preferably Cg 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 80C and 200C preferably lOO~C
to 150C 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.

Advantageously, the present invention provides a process for the separation of Cs to C19, preferably Cg to ClS, more preferably Cg to C13 mixture of 1-n-olefins and n-paraffins from 2~ L30 aliphatic and aromatic hydrocarbons and, optionally, sulfur containing compounds comprising contacting a corresponding ole~inic 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 10C and 200OC for a sufficient time to effect adsorption and desorbing the resulting l-n-olefin - n-paraffin enriched mixture from the sieve with a more volatile n-olefin and/or n-paraffin, preferably n-olefin, under adsorption conditions.

Most advantageously the present invention represents a process for the separation of Cg to Clg, preferably Cg to C1s, mixtures of l-n-olefins and n-paraffins comprising contacting a Cg to Clg 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 Z~0~30 temperature range of 80C and 200~ for a su~ficient 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 conditions.

The present invention also encompasses a separation - conversion process comprising contacting an olefinic Cs to C1g, preferably Cg to C1g 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 250C for a time sufficient to effect a selective adsorption of the l-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 preferably oligomerization to products having two to six monomer units, alkylation of benzene to alkyl-henzenes and carbonylation to aldehydes wherein the aldehyde products are preferably further converted to alcohols or carboxylic acid~, and removing the unconverted paraffin component from the olefin derived product preferably by distillation.

20~3~43() More specifically, this invention covers a selective separation - conversion process comprising contacti.ng a Cg to C13 olefinic cracked petroleum distillate feed, produced from vacuum residua by high temperature thermal cracXing in a Fluid coker or FLEXICO~ER 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, prefsrably in the liquid phase, in the temperature range of 100C to 250OC, preferably 100 to 150C for a sufficient time to effect selective adsorption of the l-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-olefin, converting the olefin components of the thus separated mixture 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, hydrogenating the olefinic double bonds o~ said oligomer to produce an isoparaffin lubricant, and removing the unreac~ed n-paraffin components from the isoparaffin containing reaction mixture 7 preferably by distillation.

SPECIFIC DETAILS OF THE EMBODIMENT

The specific details of the embodiments of the present invention will be discussed in terms of ~C)0~43~

the hydrocarbon feeds of the present separation process and the zeolite adsorbents employed.
Thereafter, the conditions of the selective adsorption of n-olefin - n-paraffin mixtures will be described. The description of the separation process will conclude with that of the desorption step.

The combined separation - conversion proce~s 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.

Hydrocarhon Feeds The pre~erred 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. A detailed description of the most preferred feeds, i.e. distillate feeds, produced from petroleum residua by high temperature thermal cxacking processes such as Fluid-coking and FLEXICOKING, is found in U.S. patent 4,711,968.

The olefin compounds of the feed are preferably in concentrations exceeding 10 wt.%, more preferably 20 wt%, most preferably 30%. In preferred olefinic feeds, the normal, i.e. linear, 200~3~

olefins are the major olefin component. More preferably, the largest single type of olefin is Type I, of the formula RCH=CH2, representing 20% or more of the total olefins. The prevalent specific olefins ar0 l-n-olefins. Some preferred olefin feed components are l-pentene 3-hexene, 3-methyl-~-pentene, l-octene, trans-2~decene, tetradecene, 1-octadecene.

The 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-methylnonané, decalin, hexadecane.

The aromatic hydrocarbon components preferably represent from 1 to 60 wt.% of the feed more preferably 10 to Ç0 wt.%. The preferred aromatic hydrocarbons are either unsubstituted or substituted by short Cl to C3 alkyl groups such as benzene, p-xylene, l-methyl-4 ethyl-benzene, 1,2,3-trimethylbenzene, naphthalene, 2-methylnaphthalene, phenanthrene.

The sulfur compounds are usually present as impurities in the hydrocarbon *eed. 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 .

~:0~ 43~
' 1~ ~

ara preferred. These aro~atic ~ulfur compounds can ba sub~tituted by one or more short chain alkyl groups, preferably Cl to C3 alkyl, more preferably methyl.

The preferred oleinic distillate feeds of the prcsent invention are produced ~rom petroleum residua by high temperature thermal cracking. The percentage of the mo~t desired l-n-olefin cvmponents o~ such feed-~ generally increas~s with the t~mpera-ture o~ cracking. Theregore, the distillate pro-ducts oÇ high temperature thermal cr~cking process~s ~uch as Fluid-coking and FLEXICORING are preferred fesds for the pres~nt proce~s. Delayed coking which i normally operated at lowez temperature~ can also produce 3uita~1e feed~ for the pre ent process although the~e ~eed~ contain higher concentrations of n-paraffin~ than 1-n-olefin~. Othsr less pre-ferred, but sultabl~, g~nerally milder crackin~
processes to produc~ ~eed3 for the present invention are the ther~al cracking of ga~ oils and the vis-breaking o~ vacuum residu~

ThQ prQforred feed3 o~ Fluid-coking and FLEXICOKXNG àre highly ole~inic with olefin concen-tr~tion~ excQeding 20 wt.%, prefarably 30%. The aliphat~c hydrocarbons ar~ ~milin~ar in charac~er.
Th~ ~ain component~ ~re linear, i.e~ normal olefins and normal p~ra~ins. ThQ largo~t ~peci~ic type o~
compounds ar~ l~n-ol~in~3 ~ollowed by n-para~ins.
The ma~crity o 016i~in8 ar~ 3 I and Type II
ole~ins a~ indicat~d ~y th~ ~ollowing tabulation ~howing approxiDlate conc~n~ration rang~3 det~rmined by proton magn~t~ c: resonanc~ ~pectrometry (NMR), Z~)~4~3~

RCH=CH2 RCH=CHR R2C=CH2 R2C=CHR R2C=CR2 Type I Type II Type III Type IV Type V
-25-45% 15-25% 10-20% 10-20% Not indicated The R groups in the formulas of the various types of olefins can be straight chain or branched alkyl groups. However, the alkyl groups of the preferred coker olefins of Type I and Type II
are predominantly either straight chain or monomethyl branched. Additionally, the Type III and Type IV olefin components of these preferred feeds predominantly possess a methyl group as one of the alkyl grups 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 prePerred.

The 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 increaees with the carbon number of the distillate fractions.
Of course the percentages of olefins and paraffins ~00~3~

decrease accordingly. In the preferred Cg to C1g carbon range 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. The 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 Cls 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%. In the Cs 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 Cg to C11 range. Benzothiophenes are mostly present in the C12 to C1s range. In the higher boiling fractions, diben~othiophenes are major sulfur compound components.

Z~)ai4430 Zeolite Adsorbents 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 l'Molecular Sieves" in Kirk-Othmer's Encyclopedia of Chemical Technology, published by J. Wiley & Sons o~ New York. More detailed information is available in two monographs, entitled "Zeolite Molecular Sieves" and "Zeolites and Clay Minerals as Sorbents and Molecular Sieves"
by D. W. Breck and R. M. Barrer, respectively.
These monographs were published by the R. E. Krieger Publishing Co, Malabar, Florida, in 1984 and by Academic Press, New York, N.Y. in 1978.

Separations based on the molecular sieve effect generally employ dehydrated zeolites.
Zeolites can selectively adsorb molecules based upon dif~erences in molecular size, shape and other properties such as polarity.

The preferred zeolite adsorbents of the present in~ention possess pore diameters ranging from 3.5 to 7~A. Zeolites of this pore diameter range ~rom chabazite to ZSM-5 and silicalite.

, 2~0~L~3~) Such zeolites can adsorb n-paraffins and 1-n-olefins while rejecting bulky hydrocarbon molecules such as branched olefins, branched parafins and cg 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.
To produce a reduced polarity, i.e. increased hydrophobic character, 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 i5 incorporated herein by reference. Similar zeolites are ZSM-ll 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 5.4A. The MEL
framework oP ZSM-ll is similar. Both MFI and MEL
structures have pores with 10 ring windows.

A typical silica to alumina ratio ~or ZSM-5 and ZSM-ll is 30. Although pure silicalite is by definition has an alumina free framework, the silicalites used in the present invention also had a 2~

significant alumina ~ontent. For the purpose of the present invention sodium ZSM-5 i~ distinguish~d from the silicalites employed by it~ ~odium content which results in a lesser olefin isomerization activity than the silicalites have.

The ~ilica to alumina ratio o~ zeolites can be increased by acid treatment which remove some of the alumina. This reduce~ the acidity and the polarity of the thu~ treated 2eol ite. Acid treat-ment can also affect pore ~iZQ. These combined effect increa~e the adsorptive capacity and ~electi-vity o~ zeolite while reducing the ~xtent of undesired ~ide reactions.

While protonated aluminosilicat~ type zeolite~ o~ low acidity can ba employed as adsor-bents in the present invention it is preferred to e~ploy their sodium dQrivative~, more particularly sodium. Such derivatives can be prepared by the neutralization o~ protonated zeolite~ by the appro-priato m~tal ba~0 or sal~, such a~ aqusou~ sodium hydroxide or sodiu~ chloride. Such a base treatment can also a~fect advantageou~ly the pore diameter and shap~ o~ th~ zeolitQ. Change in the cations also r~ults in ~l~ctric fi~ld ~ffects, resulting dif-fsrent interaction~ with ad~oxbate ~olecules. For ~xample, thQ calciu~ exchanged ~orm o~ the synthetic zsolit~ A ha~ a por~ diam~ter o~ 4.2 ~A. Thi~ sieve i~ r2gerr~d to a~ 5A. ThQ natural zeolite, chabazi~e, i~ another alu~ino8ilicate wi~h a ~imilar pore diametsr. The pr~err~d ZS~-5 ~ a high Si/Al ratio ~odium alu~ino~ilicate having a pore diameter above 5'A. Sodiu~ ZSM-5 ca~ be prepared ~ro~ either 4~;~0 -the corresponding quaternary ammonium derivative via thermal d~compo~ition and neutralization or by direct synthesis.

The preferred zeolite adsorbents are silicalites which topologically resemble ZS~-5 and contain the same type of building unit. The two sets of intersecting channels o~ silicalite have pore sizes rangin~ from S.2 to 5.7-A. It i~ common-ly assumed that silicalites contain no exchangeable metal cations and a~ such they are highly no~ polar with high affinity for nonpolar hydrocarbon mole-cules.

Commercially available silicalite from Union Carbide Corporation contains significant amount~, about 0.5%, alu~inu~ as A1203. Signi~icant amount3 o~ thi~ i~purity can be removed by aoid treatment.. Th~ r~sulting low alumina (about 0.3~
Al) silicalit~ is then treated with a base to neutralizQ and re~ov2 acid impuritie~. The result-in~ aeid-ba3e tr~ated silicalite has improved selectivity and a uch ls a preferred adsorbent in the pr~sant proce~.

~ he crystallin~ zeolite ad~orbents are u~ually ~ormed lnto 3phsrQ~ or cylindrical pellets ~hich hav~ high mechani~al attrikion resistance.
Thi~ i~ achi~v~d u~ing bind~rs which do not serious-ly hind~r diffusion in the micropore~. A~ birlders silica, alumina and crosslinked organic polymars can be e~ployed.

9L3~

Adsorptio~

Adsorption by zeolit~ molecular sieves is performed using gaseous and liquid feeds. In the present process, zeolite~ are regenerated and used for many adsorption-desorption cycles. The present process is directed at the separation of two rather than one typ~s of molecules and as such does not follow th~ rules and predictions developed for processe~ separating a single type o~ compounds.
HOWQVer, process technique~, such a~ counter-current liquid phas~ ad orption, developed for single type hydrocarbons, axe applic~ble.

The present invention ~omprises the selectiv~ adsorption of both n-olefin~ and n-paraf-fins from a mixture of al$phatic and aromatic hydrocarbon co~pounds. The pre~erred feed mixtures ar~ in the C5 to Clg range. Preferably l-n-oleins and n-para~Pin~ are ~ainly ad~orbed from a feed richer in ter~inal l-n-ole~in~ than internal n-olefins. Such prQf~rred feed~ are the distillates produced ~ro~ p~trol~um re~idua by high temperature ther~al cracking. Thess feed~ addi~iona}ly contain ~ul~ur co~pounds.

Th~ absenc~ o~ c~talytic side reactions such a~ i~o~rization i~ particul~rly important ~or r~cov~ring a ~ix~ur~ o~ l-n-ol~fin5 and n-parar~ins.
l-n-Oletin~ ar~ part~cularly sub~ect to i~omeri-zation result~ng in int0rn~1 olafins. In gQneral, in~rnal ole~in~ ar~ d4s~ red than terminal olafins.

2~0~

~ orking with an acid-base treated sili-calite, it wa5 unexpectedly found in the present invention that the l-n-olefin components of the Cg to Cls f2eds are preferably adsorbed over the corresponding n-paraffins. The trans-isomers of the internal linear olaflns and l-olefins are adsorbed at comparative rates. Little adsorption of the very minor cis-i~o~ers occur~. In case of the minor conjugated linear diene components, such as trans-piperylene, a selective adsorption is also observed.

In addition to th~ selective adsorption of l-n-olefins and n-paraffin~, selective adsorpkion or rejection of aro~atic ~ulfur compounds was observed, using ZSM-5 and silicalite. It was ~ound that the thiophenic sulfur compound compsnents of Cs to C8 cracked distillate~ derived ~ro~ residua are selec-tively adsorbed in the pres~nt proces~. The adsorp-tion of 2,5-dimethylthiopheno i8 surprising in view o~ the rejection of toluene components o~ very minor concentration~. The adsorp~ion o~ the~e sulfur compound~ howav~r, doe~ ~ot interfere with the production of l-n-olefin plu3 n-paraffin rich extract~ desired the minor aromatic sulfur compounds ~an be removed fro~ the extracts, e.g. by che~ically modi~ied adsorbents, before any subse-guont ch~ical conv~rsion. ThQ benzothiophene type ~ulfuX com~ound~ present in the higher carbon di~tillat~ w~r~ not ad~orb~dq It was found that silicalite is a size s31~ctive ad~orb~n~ for cer~ain ~onom~thyl branched ol~in~. 3-Methyl-2-p~nten~ was selectively ad-sorbed, whil~ 2 methyl-2-penten~, 2-~thyl-l~pent~ne 43~

and 4-methyl-2-pentener were not. Some adsorption of C8 and highar carbon 2-methyl-l~alken2s and 2-methylalkanes wa~ observed. However, their presence in minor amount~ in the extracts of coker distillates does not interf~re with the use o~ such extracts in synlube preparation.

The adsorption occurs on contacting the hydroc~rbon feed and the zeolite at a temperature wherein th~ molecule~ to be adsorbed have a suffi-cient en~rgy to overco~e the repulsive interaction with the zeolite and pa~ through the aperture of the zeolite channels and r~v~r3ibly flll the ~icro-pores. To ach1av~ ~uffici~nt adsorbata dif~usion rates, increased temperature~ ar~ needed to ov~rcome th~ activation energy requirements of molecules of increasing size and/ar mol¢cular wei~ht.

Generally, pr~ferred adsorption tempera-tures are in ~h~ 10 to 250-C range. Adsorption of the low moleculax w~ight, Cs to C8 distillate, feeds can be carri~d out at low temperatures, in th~ 10 to 100 C regi~e. Th~ ad~orption of Cg to Clg frac-tions at opti~um di~fusion rate require~ increasing temperaturs~, ranging ~ro~ 100 to 200^C. ~owever, th~ opt~mu~ temp~rature~ o~ the present adsorption proces~ ar~ it~d by th~ need to avoid l-n-olafin i~o~riz~tlo~ and cracking. Th~ choice o~ adsorp-t~on t~perature al~o depend~ on the carbon rang~ of ~he hydrocarbon ~eed. Broad distilla~ ee~ cuts are procee~2d at t~mp~rature~ higher than warranted ~or their low bolling co~pon~nt~O

Ga~ pha5e adsorption is carried out pr~ferably at close to atmospheric pressurç in a temperature range wherein the ~eed is in the gaseous sta~e~ Similarly, liquid phas~ adsorption is per~ormed at temperatures wher~ the ~eed is liquid.
When processing a volatile feed, such as Cs, in the liquid phase, above atmospheric pressure may be used. In general, a liquid phase operation is preferred because it can be usually carried out at a lower temperatllre providing a higher extract yield.

Desorption Desorption, i.~. the removal of the n-olefin and n-paraffin rich extract from the zeolite adsorbents, can be carried out under varying condition as part o~ the adsorption-desorption cycle. A thermal swing cycle compri~e~ de~orption at a te~perature higher than that ~or th~ adsorp-tion. Similarly, a pressure 3wing cycl2 employs reduced pre~ure to effect de~orption. An isother-mal purg~ cycl~ e~ploy. a non-ad-Qorbed liquid to strip the adsorbate from the void~ and eventually ~rom the por~s o~ the zeolite. Finally, the di -placemQnt purge cycle e~ploys a desorbent which is equally or more ~ronqly ad~orbed th~n the ad-~orbats. ~hi~ dssorbent is then displaced by the ad~orbat~ in the adsorption cycle. For further inform~tion~ re~erenc~ i~ mad~ ~o an earlier quoted di~cus~ion Or ~ol~cular Si~e3 in Kirk-O~hm~r's Encyclopedia o~ Chemical Technology.

The pre~err~d de~orption i~ part o~ a di~placement purge cycle. This cycle i~ preferably X~0~3(~
-- 2g --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 34~h Annual Meating of the Society of Chemical Engineers at Tokyo, Japan on April 2, 1969 which ar~ incorporated hereby by reference.
Broughton particularly described a simulated moving bed countercurrent proce~s flow scheme preferred in the process of the present invention.

In general, a variety of compounds s~ch as C02, NH3, ~athane, butane, and butene can be used in the desorption Sep. However, ~or a prefsrred operation in the li~uid pha~e using the di~placement purge cycle, n-para~ins and~or n-olefins, particu-larly l-n-olefin~ are the choice desorb~nts. These preferred ~sorbents are liquids which are lower boiling than the feed~ In a pre~erred operation, the boiling point of th~ d~sorbent should be low enough for ea~y s~paration fro~ the feed by distil-lation but high enough so as to assure that the specific gravity and viscosity of tha ~eed are not drastically di~Qrsnt ~rom that of the feed. The latter ~acilitata~ ~ooth feed and extract displace-ment by liquid flow through th~ ad~oxbent bed.

Exa~plary desorbing agents include, n-p~ntan~ ~or a 4 ~aed~ 1-hex~ne ~or a C7 to Cg fQ~d~ l-n-oct~n~ for a Cg to C13 ~eed. In contrast ~o th~ prior ar~ n-oc~ene is a pre~arx~d desor-b~nt in the pr~s~nt proce~s. Ev~n though l-n-octenQ
may no~ be compl~tQly -~par~t~d ~rom th~ l-n-ol~fin n-paraf~in rich ~xtract, it~ pre~enc~ is not ZOOA4~0 objectionabl~ in the subsequent conversions of the 012in co~ponents.

In a preferred operation a broad feed fraction, such as C8 to C1s, is employed and the low boiling part of the extract, e.g. a mixture of Cg, Cg n-olefins and n-paraffin~, is used as a desor-bent. In such an operation, the low boiling com-ponents of the extract ara distilled and used as desorbents.

The broad temperature range of desorption is generally the same a~ th~t o~ the adsorption. In the isothermal or nearly isothermal process cycles, such as the preferred di~place~ent purge cycls and the stripping cycle, the preferred temperature ranges for d~sorpt~on and adsorption are similar by definitionO

With th~ exception o~ th~ pre~sure swing c~cle, th~ pr~33ure range~ o adsorption and de~orp-tion are gen~r~lly ~imilar. Close to atmospheric cycles are preferr~d. In ,a preferred liquid phase cycle, the u~e o~ a low boiling desorbent such as n-butane may r~quiro superatmospheric pressur~.

Adsorption-d~orption cycl~ o~ the pr~ent proce~ ar~ operated in a temperatura regime wh~re~ no ~ niPic~nt olQ~in ~ide r~action~ take placz. Nevertheleqs, the z~olite adsorberlt~ have flnite lifeti~a~ dus to ~lnor 3ide reaction~ result-ing in por~ plugging. R~gen~ration o~ the thu~
dcactiYated 2eol$te i~ g~nerally po~3ible by Z~ 9L3~

- 31 ~

calcination which resultg in the burning off of organic impurities.

Conversion The olefin component~ o~ n-olePin plus n-paraffin mixtures obtained in th~ present separa-tion proces~ ~re advantageouly converted to higher boiling derivatives -and then separated from the unreacted n-paraffins. Those conversions generally compris~ known chemical reactions and processes.
The preferred conver~ion~ ar~ oligomerization, alkylation of aromatics and carbonylation. A
preferred aspect of the present i~ven~ion i a unique combination of zeolite separation and selective conversion of n-olefin plus n-para~fin mixture~ followed by the ~paration af the n-para~-fin.

Th* pre~erred n-ole~in-n paraffin mixtuxes of ~he present invention contain 1-n-sle~ins as the main ola~inic co~pon~nt~. Thas~ l-n-ole~ins ar2 the pr~ferred reactant~ in nu~erous ~ype~ of conversions which are mora p~cifically polymerization, oli-gom~rizatlon, alkylation, carbonylation and various oth~r ol~rin conv~r~ion~. In ~ha following, mainly th~ conv~r~ions of these ol~fin~ will be discussed.
n~Ol~in~ g~nerally und~rgo ~ r conversions at a lower rat~.

Th~ acid catalyzod and ~re~ radical oligo~erization of l-n-ol0~in~ i~ widely known. In thQ presant proc~s~ acid catalys~d oligom~rization in the liquid phas~ 1~ pre~-rrod. The catalysts ar~

3~3 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 100C 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 most preferred oligomerizations produce polyolefin intermediates for synthetic lubricants. The preparation of synthetic lubricants via the polymerization of even numbered, pure 1-n-olefins was reviewed by J.A. Brennan in the journal, Ind. Eng. Chem., Prod. Res. Dev. Vol. 19, pages 2-6 in 1980 and the references of this article. Brennan concluded that isoparaffins, dèrived from 1 n-decene via trimerization catalyzed by boron trifluoride followed by hydrogenation, possess superior lubricant properties. Due to the position and legnth of their n-alkyl chains these trimers also exhibit superior stability. Their viscosity is relatively insensitive to temperature changes. Based on these and similar studies Cg, C1o and C12 ~-olefin based lubricants, having 30 to 40 atoms per isoparaf~in molecule, were developed.

2~ 3(~

More recently synthetic lubricants were also developed on an internal olefin basis. U.S.
patents 4,300,006 by Nelson and 4,319,064 by Heckelsberg et al. discuss the synthesis of such lubricants via khe BF3 catalyzed dimerization of linear internal olefins derived via ~-olefin metathesis. Heckelsberg also discloses in U.S.
Patent 4,317,948 the ~ynthesis of lubricants via the codimerization of linear internal and terminal, i.e.
~-olefins.

According to the present invention, the n-olefin components of a mixture of n-olefins and n-paraffins are conyerted into oligomers by reacting them in the presence of an acid or a free radical catalyst preferably an acid catalyst. In a preferred conversion step, oligomers containing an average of 3 to 4 monomer units, trimers and tetramers, are produced by reacting a mixture rich in Cg to C13 1-n-olefins and n-paraffins, in the presence of a boron trifluoride complex. In an alternative step, the l-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 o~ n-olefins, produces polyolefins in the C16 to Cso carbon range. These are subsequently used to alkylate benzene to produce C16 to cso alkylbenzene intermediate~ for the synthesis of oil soluble calcium and magnesium alkylbenzene .
-- -- ' .

2(~(~4~3~

sulfonate detergents. For these oligomerizations preferably Cs to C8 n-olefins are employed.

The unconverted para~fin components o~ 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.

Another preferred conversion of the n-olefin components of the n-olefin plus n-paraffin mixtures involves the acid catalyzed alkylation o~
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 100C.

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 150C.

2()0A430 After the alkylation of the aromatic compounds the unconverted olefins and other volatile components are removed by distillation.

A third preferred conversion is the carbonylation o~ the n-olefin components of the n-ole~in 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. In the case of the preferred l-n-olefin components the main reaction is the following:

RCH=CH2 ~ CO + HX > RCH2CH2COX
R = n-alkyl, x = H, OH, OR

The preferred carbonylation catalysts are cobalt and rhodium carbonyl complexes. The preferred carbonylation leading to aldehydes in hydroformylation.

co/H2 RCH=CH2 > RCH2CH2CHO + RCH(CH3)CO

The hydroformylation of the olefin components of whole FLEXICOKE~ distîllate 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. I contains mainly 1-n-olefins and n-paraffins separated from FLEXICOKER
distillates.

Th~ preferred n-olQfin - n-paraffin ~ixtures employed as carbonylation feeds are o~ a relatively narrow carbon range, containing com-ponents having 3 dif~erent adjacent carbon atoms or less. This allows the separation of the unconverted paraffin component~ and paraf~in by~products from the carbonyl compound products. In the case of hydroformylation the aldehyde product may be hydro-genated to tha corresponding alcohols prior to paraffin removal by hydrogenation.

For pslymerization~ and copolymerizations aimed at prod~cing high molecular weiyht poly~ers, l-n-olefin - n-para~f~n ~ixtures are preferred, wherein the l-n-olefin and n-paraf~in havQ the same particular number of carbon ato~s in the molecule.
For examplo, a ~ixture of l-n-hexen~ and n-hexane produced by the pr~sent proc2ss can be used to produce an ethyl~n~-hexene copoly~er. Similar l-n-olefin - n-paraffin~ wher~in the l-n-olefin and n-pararfin have thQ sa~e particular number of carbon atom~ in the moleculQ are pre~rably used in other ole~in convercio~s ~uch a~ hydroboration and epoxid-ation.

Za3~3(~

EXAMPLES

The ~ollowing example~ are provided to illustrate the presently cla~med process but are not intended to limit the scope o~ the invention. Most of the Examples describe the novel selective adsorp-tion in zeolites, particularly silicalites and sodium 7SM 5, of n-olefln - n-paraffin mixtures.
Adsorption studie~ o~ f~ed~ consisting o~ model compounds and l-n-olefin rich crac~ed distillates derived fro~ petroleum ra~idua will be pr~ented Si~Q by sid~. Th~ de~orption s~p of the present ad~orptive, molecular sieve procesC will be also illu3trated. Finally, an Qxample will be given for th~ converoion o~ th~ ole~in components o~ an n-olefin plu~ n-paraf~in rich produ¢~ o~ thQ present separation proce~s.

Prior to the speci~ic example~, the cracked d$~tillat~ fe~d ~mployed and thQ zeolits adsorbent~ used will ba described. The t~s~ methods and analytical tochnique3, i.~. the ~a~ an~ liquid phas~ standard static ad~orption tests, and raffi-nat~ analysis by`capillary ga~ chromatography, will ba di~cu~d.

~ h~ ~odel co~pound Q~xtures e~ployed as ~e~d~ in th2 adsorption te~t8 w~r~ made up ~ro~ pure laboratory chemical~ repr~ ~nting the ~ain t~pe~ of compound~ pre~nt in ~h~ fQ~d~ o~ present.
~paration proce~.

~OO~L430 Preferred feed fractions exami~ed in detail were 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 400OC overnight.
Thereafter, they were stored at 80c under nitrogen until usedO

ThP majority of the silicalites employed were supplied by Union Carbide Corporation. S115 was microcrystalline silicalite powder, R115 was silicalite pelletized with a silica binder Similarly P115 was pelletized silica with an alumina binder. A low alumina (less than 200 ppm) microcrystalline silicalite was also employed.

Some of the high alumina (5000 ppm) 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 ~ 39 -resulting from this acid base treatment was calcined a usual.

A laboratory preparation of ZSM-5 sodium aluminosilicate derivative derived ~rom the corres-ponding quaternary ammonium deriYative was also used. The microcrystalline powder wa~ also calcined and e~ployed in so.~.~ of the adsorption tests.
Sodium ZSM~5, mad~ via direct ~ynthe~is ~y Uetikon of Switzerland w~ al50 tested.

The ~odel compound ~ixtures and FLEXICOKER
di~tillate fractions Pmployed a~ feed~ in the adsorption tests and their re~pectlve raffinates, i.e. non-adsorbed product~ o~ these tests, were analyzed by capillary ga~ chromatography (GC). High reaolution GC analyses were carried out using a 50 m fused silica column coated with non-polar methyl-silicone~. Thu~ GC retention tim~s were approxi-mately proportiondl to the boiling points of the components.

In g~nQr~l, the adsorption tests were carried oUt with accurat~ly weighed amounts of z~olite ~nd hydrocarbon ~eed. A~ter contacting the z~olit~ and th~ f~ed, thç~ co~po~ition oS tha reject-~d hydrocarbon ra~finat~ was analyzed and compared with that o~ th~ feed.

Static ad~orption t~ts were carried out in both th~ gag and l:hel liquid phas~a, u~ing model co~pound mixture~ and Fr.EXICOKER ~ractions o~
varying car~on range~. In th~ ga~ pha~ teYt ahout 1 g zeolit~ and O . 2 g hydrocarbon ~ed wsare placed 3(1 into a small closed vial and kept there for four hours at 40 C. With the low, Cs and C6, fractions used in these tests, this was suf f icient to reach adsorption and ga~ liquid equilibria. Thereafter, the gas phase of tha test mixture representing the raffinate and th~ feed were both sampled for G.C.
analyses.

In the liquid pha e tests, the hydrocarbon feed wa~ diluted with a ~on ~dsorbing bulky com-pound, heptamethylnonane or decalin. In th~ ~ajor-ity of liquid phase test~ 2 g o~ a 10/90 mixture of hydrocarbon and diluent was usQd p~r g zeolite.
Thi~ proportion of th~ liquids to solids gave rise to a su~stantial supernatant liquid phas~ of the test ~ixturs which could b~ easily sample~. The test mixture wa~ heat~d for several hours with occasional shaking to reach equilibrium. The supernatant liquid was than an~lyzed by GC and its compo~ition was compared with that o~ the feed.

So~e o~ tha liquid pha~e tests were carried out with about lg of a 30/70 mixture of the feed plU~ diluent p~r g zeolite. These mixtures exhibitad no signi~icant ~upernatant liquld phase ~ter ~ttling. ~he sealed mixtur~s were heated to roa~h ~qull~bri~ a~ above. Due to the ab~nce of a ~parat~ liquid phas~, th~ equilibria were more rapidly a~tablish~d in th~ te~t~. Aftar equili-briation, the te~t mixture~ wer~ dilu~ed with a~out lg o~ isooctan~, 2,2,4-trimethylpantan~, ~r other suitable bulky co~pound and thoroughly mixed. After ssttl ing, tha cl~ar suparnatant ~ uid phase was analyzed by GC as usual.

L3~

It i~ noted that the absence of zeolite microcrystals from the liquid~ injected to the gas chromatograph is critical for correct compositional analyses of the raffinatesO These crystals, if present, are deposited in the high temperature (about 325~C) injection port of the chromatograph and act as cracking catalysts particularly ~or the l-n-olefi~ components.

The FLEXICOKER distillat2 feeds exhibited complex gas chromatogram~ with overlapping GC pea~s of some components, especially in case of the higher fractions~ As a consequence the nominal GC percen-tages of so~e small co~ponents were depend~nt on the GC sample ize.

Th~ s~lectivitie~ and capacities of zeolite adsorbents for the compon~nt~ o~ the test mixture~ w~ra e~timated by the ratio o~ their respective concentrations in the ra~inate. High ratios indicated selectiv~ adsorption while low ratio3 wer~ signs o~ re~ection by the zeolite.

Pr~paration o~ Acid Base ~ Qillçalite on~ liter of 18% by wt~ hydrochloric acid, at room te~peratur~, w~ added to 20g ~ilicalite (S115 from Union Carbid~ Corporation) with stirr-ing. The liquid-~olid æuspen~ion wa~ allowed to s~ttl~ overnight to s~parat~ into two phasa~. The supernatant liquid pha~e, which hzd b~come di~color-ed, was decanted and 1 liter o~ ~ra~h 18~ HCl was 3~

added to the solid with ~tirring and a~ain allowed to settle overnight. Thi3 acid washing proc2dure was repeated a third ti~e, aft~r which the liquid phase remained colorle~s. The silicalite was collected and washed repeatedly with deionized water until the wash wa~er gave a neutral reaction to litmus. The silicalite wa~ th~n washed in 1 liter o~ a mildly basic 301ution 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 go- - 95C and calcined at 400~C ~or a minimum of 4 hrs. at which ti~ it was ready fer u e.

Adsorption o~ n-Pentenes and n-Pentane From C~ FL~XI~OXER Naphtha A sealed mixture o~ about 0.2g C5 FK feed fraction and lg acid ba e treated Rilicalite was heated at 40C ~or four hour~ Subsequent gas phase analyse~ of th~ ~ed and the raffinate (Raf.) by GC
indicated th~ p~rcentage compo~ition listed in Table I. (ThQ ~ain compon~nt~ are listed in the order of th~ir retention time~.) ThQ data o~ Tab1Q I how that th~ concen-trations o~ l-n-p~nten~, cl~- and trans-pentenes and n pentane ar~ ~igni~icantly rQduced in the raf-finate, indicating th~ir s~l~ctive adsorption. In contra~t thQ conc~ntration~ o~ methyl branched butenes and isopentanQ (2~ hylbutane) ar~ increas-ing in the raPfinato, indicating their r~jection.

2~ 3~

Table X

Adsorption o~ Cs FLEXICOKER Fraction by Acid/Bas~ Treated Silicalite Component Ratio, Name of Conc... GC ~ Feed Compon~nt ~ç~ RaS. o Raf.
3-Methyl-l-butene 4.5 9.3 0.48 Isopentana 13.4 21.8 0.61 1-n-Pentene 38.1 22.6 1.69 2-Methyl-l-butene 18.4 24.2 0.76 n-Pentane 12.5 6.7 1.86 Isoprene 3.1 4.5 0.69 trans-2-Pentene 4.9 3.1 1.58 ci -2-Pen~ene 1.8 1.3 1.38 2-Methyl-2-butene 0.8 3.2 0.25 :~}

Adsorption o~ n-Hexene~ and n-Hexane ~

Rbout 0.2g of a ~ixtura o~ si~ilar amounts o~ n-h~x~nos, n-haxan~ and 2-m~thylpentane and lg acid/ba. 9 washed 3ilicalit~ w~r~ contacted a~ 40C
~or four hour~ and analyz~d by~the ga~ pha~e method u~ing GC. The compo ition~ o~ the re~ulting raf-~inate and th3 ~tarting ~¢ed are compared in Table II. :

Tha data o~ th~ tabl~ indicatQ that with th~ axception o~ cia-2-haxen~, ~ll the n-hexenes : . .

~4~3~

plu8 the n-hexane in the mixture were adsorbed.
Trans-2-Hexene was preferentially adsorbed over cis-2-hexene.

A rejection o~ 2-methyl branched l-pentene wa3 indicated.

Calculations have shown that the approxi-mate capacity of the silicalite ~or 2-hexenes and l-hexene wa~ about 4.7 wt.% an~ 1.9 wt.%, respec-tively.

Table II

Adsorption of Model Mixture of C6 ~ydrocarbons by Acid/8ase Treated 5ilicalite Component Name of CQnc.~ G ~Ratio, Feed Ccmponent F~e~ to ~af.
2-Methyl-1-pentene 18.5 33.00.56 l-n-Hexene 17.0 13.81.23 n-Nexane 18.0 12.61.43 trans-2-Hex~ne 22.7 14.71.55 ci~-2-H~xene 1~.8 17.0 1.1 Ex~m~le 4 Ad~orption of n-Hexenes and n-H~xane Fro~ C~ FL~XIÇO~ER Naphtha A ga~ pha~e adsorption test was carried out with a mixture o~ about O.2g broad C6 FLEXICOKER
feed fractlon and lg acid/bas~ trea~ed ~ilicalite for four hour~ at 40-C. Sub~equent GC analy~es of the f~ed and thQ raffinate obtained are ~hown in Table III.

The data of th~ tabl~ ~how that, a~ong the C5 components, cyclopentene and cyclop~ntane are not ad~vrbed. In contrast, ci~ and tr~ns-piperylene appear to g~t adsorbed a~ong the nu~erous C6 hydro-carbon~, the n-hexene~ ~xh~bited the positive ad~orption b~h~vior obs~rv~d in the r6 model ~ix-ture. The methyl branch~d pen~ene~ ~id not get appreciably ad~orbed 2xc~pt th~ 3-methyl branched 2 p2nten~. Among the C6 paraffins present, only n-hex~ne wa~ ~d~orbed.

Calculations ind~cated that the approxi-m~t~ cap~city o~ tA~ siIicalit~ for ~he main two co~pon~nts, l-n-hexene and: n-h~xane wa 3.5~ and 1.8%, r~pQctlvelyo Z0~4~3~

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ExamPl~ 5 Adsorption of l-n-Octen~ and n-Octane F~om a Mix~u~e o~ C~ ~od~l Compound5 About 2.4g of 10/90 mixture of Cg model compounds and h~pta~ethylnonane diluent were added to two lg acid/base wa~h~d sa~ple~ to pr~pare two test mixtures. The~ mixtur~ were then heated at 110-C for 2 hour~ ~nd at 150C for 4 hour~. The supernatant liquid~ of the~e compositions were then analyzed by GC. The GC ~ompositions o~ the two C8 raffinate compo3itions are compared to that of the ed in Tabl~ IV.

The data o~ th~ table indicate that l-n-octenQ and n-octane ar~ ~electively adsorbed from a mixture containing C7 and C8 aromatic hydro-carbons at both ta~t te~peratur~. There is only minor i~om~rization of l-oc~ene to in~ernal i.e. 2-, 3- and 4-octen~s~ Th~ aromatic sulfur compounds pre~nt, 2-methylthioph~ne and 2, S-dimethylthio-phenQ, ar~ highly ~lectiv~ly adsorbed. The selec-tivity a~ indic~t~d by th~ ratio of raffinate to ~Qd i~ particularly high ~or the les~; bulky methyl-thiophen~.

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Exa~ 5 Adsorption of l-n-Octena and n-Octane from Cg FLEX~ÇOR~R Naphtha A liquid phase adsorption te~t was carried out with about ~.2 ml of a 10/90 mixture of a Cg FLEXICOKER distillate and hepta~ethylnonane and 1 acid/~ase washed silicalite. The mixture was heated at llO-C for 2 hour The ~upernatant raffinate was analyzed by GC and its ~o~po~ition compared with that of the feed. Tha results a~e ~hown in Table V.

The data indicate l n-octene and n-octane are sele~tively adsorbed. It appear~ that some of thQ l-n-octene was iso~riz~d ko intarnal octenes.
4-~ethyl-1-heptene i~ appar~ntly not adsorbed appraciably bacause of tha branching in tha middle of the cAain. The ~ thyl branched aliphatic hydrocarbons ars co~pl~tely re~cted. Si~ilarly, the aromatlc hydrocarbons, toluene and ethylbenzene, appaar to be rQ~ectsd.

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2Qi~4~3~
- Sl -Example 7 Adsorption ;f 1-n-Nonene and n-Nonane Versus 2-Methylnonene and 2 Methylnonane from a Mixture of _CQ Mode~ Compounds About 1 g each of a 40/60 mixture of model compounds and decalin diluent were mixed with about 1 g each of acid/~ase wa~hed silicalite and sodium ZSM~5. The mixtures wer~ heated in closed vials at 1501C for on~ hour in a liquid phase adsorption test. Therea~ter, thay were diluted with about mole i-octane. The solid zeolite~ wers then allowed to settle and the ~upernatant raffinate liquids analyz~d by GC. The composition o~ the raffinates is compared with that of th~ starting mode mixture in Table VI.

The data of Table VI indicate that l-n-nonene and n-nonene are strongly 2nd about equally adsorbed on both thQ silicaIit~ and the sodium ZSM~5 adsorbent. 2-~ethyl-1-nonene and 2 methylnonane are only slightly ad~orb~d. In contrast, both of the trim~thylbenzen~ i~om~r~ are completely rejected.

In the pre~nc~ of the silicalite a slight i~omerization o~ l-n-nonene to cis-and trans-2-nonene~ occurred. Seemingly, a major isomerization o~ 2-~thyl l-non~ne probably to 2-m~thyl-2-nonene took placa in ths pre~nco o~ ~ilicalite. In the presenc~ o~ ~odiuo ZSM-5, ther~ was no indication of any i~omerization.~

The decr~a3ed concentrations of l-n-nonene and n-nonana in the ra~inate~ indicate that :the ' .
, 2~4~30 combined capacities ~or these two compounds of silicalite and sodium ZS~-5 are about 8.3 and 9.2%, respec~ively.

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.

43~

Adsorption of 1-n-Decene and n-Decane from _ Their Mixture Wit~ eth~lb~nzenes About 1.~ g of a 15% solution of l-n-decene, n-decane, 1,2,4- and 1,2,3-trimethylbenzenes in heptamethylnonane was added to l g acid/base washed silicalite. The mixture was heated at 150C
for 3 hours. A sub~equent GC analysi~ of the supernatant liquid raffina~ ~howed a major change in the composition of the model compo~nds as shown by Table VII.

The data show a highly selective adsorp-tion of both 1-n-decene and n-decane. A minor isomerization of 1-n-decene i~ indicated by the readily distingui~hed GC peak~ of 4-decene and trans-2-decane. Ba~ed on the decrea~ed concentra-ticns o~ 1-n-d~ne and n-decane, the approximate capacity o~ the silicalite ~or these compounds together is 10.1~.

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~oo~o ~xam~e 9 Adsorption of Isomeric n-Decenes from a_Mixtu~e of ~odel Compound~
About 2.7 g of a 1/1 mixture of Clo model compounds and heptamethylnonane was added to a 1 g acid/basa washed ~ilicalite. The resulting test mixture was then heated at 150-C for 2 hours. The supernatant raffinate liquid waY then analyz0d by GC
and its composition compared with that of the feed mixture. The result~ are shown by Table VIII.

The data show that all the n-decenes are adsorbed in contrast to the tri~ethylbeAzene com-ponents~ However, it i~ not possible to determine the relative electivities of their adsorption bQcause of thelr concurrent isomerization. At a concentration co~parabl~ to those of n-decenes, 2,5-dimethylthiophene i~ ad orbed to a lesser degree although it is clearly not rejected like the tri-methylbenzenes.

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2~1[)4~3~

~mple 10 Adsorption of l-n-D~cene and n Decane ~rom a Mixture o~ C1~_Model Co~pounds by Va iou~ Silicalites About 1 g of each of an about 10/90 mixture of Clo model compounds and heptamethylnonan~
was added to 1 g samples of variou~ silicalites.
The resulting mixtures were heated at 150-C for 2 hours and the raffinates analyz~d by GC. The data are shown by Table IX.

A co~pari~on o~ the ~eed composition with tho~e of the raP~inates indicat¢ that all the silicalite tested seloctively adsorb l-n-decene and n-decane. The untreated and acid/base washed ~ilicalites were e~pecially ePfectiva in adsorbing $-n-decene. It is indicated by the low concentra-tion of cis-2-decene in the raf~inat~, that no significant i~omerization o~ 1-n-decene occurred.
The concentration o~ indene in the raffinate o~` the mixturQ with thQ untreated silicalite is sharply reduced. Thi~ i~ probably du~ to acid catalysed dimerization, oligo~rization. The reduced concen-tration~ of 2,5-dimethylthiophene indicate its selectiv~ ~d~orption by all the zeolites. It is not~d that a s~lective 2,5- dimethylthiophene adsorption was not observed in the previous example wh~ro larg~ a~ount~ of 2,5-dime~hylthiophene were employed. ~hQ bulk~er ~ul~ur compound, benzo-thiophen~, wa~ not ad~orbQd in ~th~r ~he present or the previou~ exa~pl~.

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, 36~

~ 60 -E~mpl8 11 Adsorption of 1-n-Decene and n-Decane from a Mixture Of Cl~ Model Compounds With _ SQdium ZS~ ~and Si~cal~te _ Adso~ption experiments were carried out at 120-C in the manner described in the previous example with sodium ZSM-5 and a silicalite pelleted with alumina binder. The result~ are shown in Table X.

The data ~how th~t ZSM~5 exhibi s a ~imilar adsorption behavior to that o~ the alumina bound silicalit~ o~ this example and the silicalites of the previou~ example. l-n-Decene and n-decane are selectively adsorb&d. 2,5-Di~ethylthiophene is adsorbqd while b~nzothioph~ne i9 re~ected. All the aromatic hydrocarbon~ ars re~e~ted.

A timQ study o~ tha adsorption with the sili,calite showed that the proce~ was assentially complet~ in 30 ~inute~ or 1~~.

2~443~

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Z~ 3~

Example 12 Adsorption of l-n-Decene and n~Decane from Clo FLExIcOKE~ Naphtha by Acid/~e Washed Silicalite About 1.9 g o~ a 10/90 mixture of a sharp Clo FLEXICOKER naphtha fraction, of bp. 155 to 171C, was added to 1 g acid/base washed silicalite.
The resulting test mixture was heated for 4 hours at 150~ he feed and the ~upernatant raf~inate liguid were then analyzed by GC. The gas chroma-togram o~ th~ f~ed is shown by Figura 1. The cQmpositions of the feed and the rafflnate arP
compared in Table XI.

The data of th~ table show that the concentration~ of the main l-n-decen~ and n-decane components are drastically reduced on treatment with silicalite. Thi~ is apparently due to th~ selec-tive adsorption o~ these component~. As a conse-qu~nce o~ the selQcti~e adso~ption of the linear aliphatic compound~ the concentration of the aro-matic co~ponant3 i~ generally increased.

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.
.

L3q~
- 64 ~

Adsorption-Desorption of n-Decenes and n-Decane fro~ Cl~ FLEXICOR~_Naphtha Era~tio~ in a Pulse Test About 4.51 g acid base washed silicalite, having a bed volume o~ 5 ml, was packed into a 1 ft.
stainless steel colu~n of a dia~eter of 1/4 in. The r~sulting adsorbent bed wa8 pre-wetted with n-hexane desorbent at a liquid hourly space velocity [LHSV]
of 1. 3, i . e. 6 . 5 ml p~r hour. A~ter the desired operating condi~ions, i.e. 140-C and 270 psi, were lined out, a 0.25 ~1 Clo FLEXICOKER ~eed pu}se, of the composition ~hown in the previouS example, was injected into th~ column. After the injection, the ~low of n-hexane desorbent was resu~ed and the feed components were elutsd . Ef ~luent samples were collected periodically and analyzed by GC. Their composition was plotted against the volume o~ the eluted de~orbsnt a~ ~hown by Figure 2.

Figur~ 2 indiGa~e~ ~hat the aro~atic (and branched aliphatic) hydrocarbon components of the ~eed w~r~ elutsd at first, due to their simple di~pIac~m~nt by :th~ dasorbant ~rom the voids of the 9ilic~ colu~n. This early fraction is the r~lnat~. ~lutior; of th~ n-d~c:ane and l-n-decen componerlt rich extract occurr~d distinctly la~er.
se co3llponent~ o~ the extract clearly coeluted, dua their concurrent di~placeln~nt ~ro~ the channels o~ th~a silicalit~ by th~ d~sorb~nt. The l-n-d~cene wa3 sllghtly mor~ di~ficul~ to displace than the n-dec:ane. A~ lt i~ shown by tha Figure an in-.

' Z~ 3~

between-cut of the elu~nt wa3 taken ~etween the ra~inate and the extract.

Both the raffinate and the extract were analyzed by GC in som~ detail. T~e analysis o~ the raffinate showed that essentially all the aromatic components of the f~ed were recovered. The results of the GC analy~i~ o~ the extract are illu~trated~by Figure 3.

Figure 3 ~hows that b~ides n-decane and 1-n-decene, significant amount3 of internal linear decenes (5-,4-and 2 decenas) were recovered in the ~xtract. The latter co~pound~ were in part already present in the ~eed. Additional amounts were ~orm~d via l-n-decene i~omerization during the adsorption desorption proce#s.

The chromatogra~ of th~ figure also indicate~ the presence in th~ extract o~ small amount~, about 0.5%, of 2-methyl-1-nQnene. Some adsorption by the 3ilicalit~ of thi3 compound and the related 2-~ethylnonane was indicated by the model c~pound experiment de~cribed in Example 7.

Exa~

Adsorption of 1-n-Decene and n-Decane from Cg About 0.8 g ~ach o~ an approxima~ely 20/80 mixture o~ tho sharp Clo F~EXICOKER distillate fraction o~ tha pr~viou~ ~x~pl~ wa~ added ~o about 1 g of an appropriate molecular siev~. The result-ing test mixture3 wer~ heated ht 120C for l hour 4a~3~3 and the raffinates analyzed. The re~ults are shown in Table XII.

Th~ data of the table indicate the concen-trations o~ l-n-decene, n-decane, trans-2-decene and the ~ajor, identi~ied aromatic hydrocarbon com-ponent~. Compared to the oomposition of the feed, the percentage~ of l-n-decene and n-decane decreased in all th~ raffinates~ indicating their ~elective adsorption. The concentrations oP most aromatic hydrocarbon~ increased in the raffinate, du~ to their rejection. Tha various silicalites and sodium zeolite exhibited a ~i~ilar adsorption behavior.

Si~ilar tests with different te~t periods showed that the adsorption i e~entially complete in one hour.

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Adsorption of l-n-Dodecene and n-Dodecane from a Mi~tu~e of Model C~m~ound~
About 2.5 g of a 10/90 mixture of model compounds and heptamethylnonane solvent wa~ added to 1 g acid/base washed silicalite to obtain a test mixture. Thi~ wa~ then heated for 150C for 2 hourc. Thereafter, the ~upernatant ra~finate liquid and the starting feed were analyzed by GC. Their compo~itions are compared in T~ble XIII.

The data of the table indicate that l-n-dodecene and n-dodecane were adsorb~d by the silicalite while the aromat~c hydrocarbon~ and benzothiophene of their boiling range were rejected.

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E~am 1~_16 Adsorption of l-n-Dodecene and n-Dodecane F~om ~2 FL~XICORER ~1sti~ e About 1.4 g o~ a 10/90 mixture of a sharp C12 distillate fraction of light FLEXICOKER gas oil (of bp. 212-C) and heptamethylnonane were added to 1 g of acid/base washed silicalit~. The resulting mixtur~ wa~ then heated at 150 C for two hours.
5amples o~ the ~upernatant ra~finat~ liquid and the starting ~eed were then analyzed by GC. The per-centages o~ so~e of the main component~ are shown in Table XIV~

The data of the table show decreased concentration~ o~ 1-n-dod~cene and n-dodecane and corre~ondingIy incr~ased conc~ntration~ of 1,2,3,5-tetramethylbenzen~ and naphthalene in thQ ra~inate.
Thi~, o~ course, indicate3 the selective adsorption o~ the two main lin~ar alipha~ic hydrocarbon com-ponents. Si~ilar result~ were obtained when the t~st ~ixtur~ was h~ated at 195-C instead of 150C.

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Ex~mple 17 Adsorption of l-n-Olefins and n-Paraffins from a Mixt~re of cg to C13 Model Compou~ds by Sodi~LZ~M-5 About 1 g of a 15/85 ~ixture of Cg to C13 model csmpounds and heptamethylnonane was added to sodium ZSM-50 The resulting test mixture wa~ heated at 120-C for 2 hours. SamplQs taken after 1 and 2 hours were analyzed by GC and their compositions were compared with that of the feed. The capillary gas chromatogra~s of the l'~ed and the l hour raf-finate are shown by Figur~s 4 and 5 to illu~trate the result~. The quantitativ~ GC compositions of the feed and the r~fPinates ar0 shown by Table XV.

~ he data of thQ table show that the Cg to C13 model feed mixture contained about equal amounts (9 wt.%) of Cg to C12 l-n-olefins. Al~o, similar amounts (5,7 wt.%) of Cg to C12 n-paraf~ins were present in th~ ~eed. The concentrations o~ the rest of the hydrocarbon componsnt~ werQ about 3.5% by weight. Due to ~h~ di~ren~ ~actor o~ GC detec-tion, th~ p~rc~n~ag~s d~t~r~ined by GC wer~ somewhat differ~nt but ~imilar.

A co~pari~on o~ Fi~ure~ 1 and 2 indicate th~t tha conc~ntration~ of all the l~n-ole~in~ and n-p~ra~in~ were dscr~a3~d in thQ raffinate du~ to ~Ql~ctiv~ co~dsorption. Surpri~ingly, th~ d~crease Or th~ir concentration3 incr~as~d with thoir in-cr~asing ¢arbon num~r. The GC concen~ration of l-n-nonen~ decreased fro~ 9.7 to g.4% whil~ that of l-n-dodecene d~crea~ed from 9.1 to 1.1% in two ' .

43~

hour3. A similar trend wa~ observed in the case of the n-paraffin components a~ indicated by a compari-son of Figure~ 4 and 5 and the data o~ the table.

Based on the changes in their respective concentration~, the slightly branched C1o aliphatic hydrocarbons, 2-methylnonan~ and 2-methyl-1-nsnene, ware found to be adsorbed so~what but to a much lesser degree than the linear C1o aliphatics, n-decane and l-n-decene.

The concentrations o~ ths aromatic hydro-carbon components were greatly increased in the raffinate, indicating their rojection from the ad~orbate. Ths two arom~tic ~ul~ur components, 2,5-dimethylthiophene and benzothiophene, showed a size dependent behavior. The ~maller 2,5-dimethyl-thiophene wa~ ad~orbed so~ewhat while the larger b~nzothioph~n~ molecule wa~ not.

. A comparison of the compositions of the and 2 hour raffinat~ sample~ indicated that most of the adsorption occurs during the first hour.
Similar bu~ slow~r adsorp~ion waR found ~o take plac~ at 80-C. ~periment3 with a C6 to C13 mixture o~ ~od~l co~pound~ ~how~d a ~i~ilar affQct of the ~ol~cular woight on the coadsorption of l-n-olefins and n-paraf~ins. The abova exp~rimenk~ suggest that thn pre~ent ~apara~ion proce~ appllcable to broad carbon range re~inery ~tream~ such a~ heavy FLEXICOKER naphth~ and light cok~r ga~ oil.

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Ad~orp~ion o~ l-n-Olefins and n-ParafPins fro~
a ca to ~3 F~XIC0~ R ~ist~a5e bY Sodium ZSM-5 A Cg to C13 mixturs of FLEXICOKER distil-lates wa~ prepared by co~bining fractions in the 139 ~o 234 C boiling rang~ in proportion~ providing l-n-ol~fin concentratlon~ ln th~ 2.1 to 3.1% range.
This ~eed was then diluted with hepta~ethylnonane to obtain a 21~5% te~t solution. The molQcular sieve employed for adsorption wa3 a sodium ZS~-5 zeolite prepared by Uetikon of Switz~rland via direct synthesi~. Abou~ 1.2 g ~G~ solution wa~ added to 1 g zeolite and thQ mixtura was heated at 120-C for hour. The supernatant raf~inate liquid waR then analyzed by GC and its compo~ition was compared with that o~ the ~ed. The capillary gas chro~atogram of the fQed and tha raf~tnate ar~ shown by Figure 6 and 7, respectively.

A fir~t look at the chro~atogra~s indicat-ed that th~ 1 n-ol~in and n-para~fin components were selactiv~ly ad~orbed. Their GC peaks were hardly o~rv~bl~ in th~ raPfinate. Quantitative data, ~howing th~ conc~ntration~ oP theso componants and 80~0 id~n~ d aro~a~ic compound~ in the feed and th~ r~finata, ara ohown by Tabla XVI. Th~ data o~ th~ tabl~ ~how thzt a~ th~ concentr~ion~ of l-n-ol~in~ and n-par~rins d~crea~d in the raf-~inate, the co~centra~ion~ o~ aro~atic~ incr~ased.
Th~ d~creas~, in th~ conc~n~ration o~ line~r al~phatic co~pound~:due to ad~orption, appaar~d to b~ gre ter in ~hQ Cg to Cll th~rl ln ~he C12, C13 2~ 3C~

range, probably due to greater aromatic GC peaX
ovexlaps in the high carbon range.

Thus the present s~lective adsorption-desorption process appears applicable to broad as well as narrow carbon range Peed~.

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L3~31 - ~8 -~xa~ 1~9 Adsorption o~ I~o~ric n-Tetradecenes fro~ a Mixtura o~Q~l Co~ounds A mixture of model co~pounds was made up ~rom 5 wt% o~ each, l-n-tetradecene, 7~tetradecene, n-tetradaca~e, 1% benzothiophen~ and 84% of decalin.
About 2.7 g o~ thi~ mixtur~ wa~ mix~d with 1 g of acid/base wa~had silicallt~ and heated at 150~C for 2 hours. A subsequent analy~i~ of the supernatant raffinate indicated that all th~ C~4 n-aliphatic hydrocarbon~ were ad orbed by the silicalite.
However, the n-tetradec~ne~ wer~ ~ore 831~ctively removed than n-tetradecan~.

Adsorption o~ 1-n-Tetradec~ne and n-Tetradecane ~q~ C14 F~EXICOK~R ~i~tillate About 1.5 q o~ ~ 10/90 ~ixture of a sharp C14 distillatQ fraction oP light FLEXICO ÆR gas oil o~ (bp. 248-2B0-C) and dec~lin w~re added to 1 g of acid/bas~ wa~hed ~ilicalite. ~he ~est ~ixture was then haated at 200-C for 1 hour. Subsequent GC
~naly~ o~ the ~sed and thQ ~up~rnatant ra~inate indicat~d th~t, a3 a re~ult o~ adsorption by ~he ~ilic~lit~, th~ conc~ntration o~ l-n-tetradecane in tho Cl~ F~XICORE~ fraction d~crea~ed Prom 15.6 to 0.4% (39 ~old decr~a). Tho ¢onc~ntration of n-tetrad~can~ wa. ~i~ilaæly dropp~d lg.0 to 0.7~ t27 ~old dRcreas~ i9 not~d ~hough th~t ~he~e valu~s w~re ~lquantitativ~ dus to ~he el~vat~d GC
baselin~. In ~his h~gh s~rbon range of co~er 2~ 3(~

. ,9 di~tilla~e feQd~ and raffinates, an exack determin-ation o~ 3ingle co~pound~ i~ usually impossible on a boiling point type GC column.

Isomerization o~ l-n-decene by Silicalite in the P~esence_~n~L~bsence o~ ~n~_th~ophene The iso~erization of excesR l-n-decene by silicalite without acid/basQ treatm2nt at 120-C in 1 hour wa~ deter~insd in the ab~ence and the presence o~ about 5% banzothioph~n~. In th~ ab~ence o~ the sul~ur co~pound, 30% o~ intQrnal nodecQnes were found by GC a~ a coneeguence o~ i~o~rization via double bond ~igration. In the pre~ence o~ sulfur, only 10% o~ the feed wa~ isomerized.

E~2.

Preparation o~ Synthetic Polyalkene Lubricant from A ~iXtUrQ 0~ Cg to C13 n-ole~ins and n-paraf ~in8 i~ s~para~d ~ro~ ~a corresponding broad FLæXICORE~ di3tillat~ via a molQcular adsorp-tion o~ th~ typ~ de~cri~d in Exa~ple 12. This ~ixtur~, containing Cg to C13 l-n-ola~ins as the m~in re~c~iv~ co~ponen~s, i~ th~n oligom~rized using a boron tri*luorid~ co~pl~x o~ an alcohol, i.e.
n~op~ntyl alcohol. The oligo~rization i~ carried out in th~ liquid pha~ at te~p~rature~ and pres-sur~ suP~ici~n~ to conv~rt not only th~ terminal l-n-ole~in co~pon~t~ but mo~t o~ th~ internal L3~

n-olafins a~ w~ll to polyolefin oli~omers containing olefin trimer~ a~ the main components.

The re ulting polyole~in - n-paraffin mixture i3 then hydrogenated in the presence of a sul~ur insen~itiv~ transition ~etal sul~ide cata-lyst. Thi~ provides an i~oparafrin plus n-paraffin ~ixturQ which i~ then separated by distillation.
The n-paraffins and the isoparaf~in dimers are distilled. The residual isopara~fin product com-prising mainly trimers and t~tram2rs i8 a desirable synthetic lubricant. The n-paraffin distillate is converted via known chlorination - dehydrochlori-nation reactions to linear olefin intermQdiates of biodegradable alkylb~nz2ne sul~onate manu~acture.
Th~ isoparaffin di~ar are u~ul a~ olvents o~ low volatility.

Dua to ths presence of significant amounts of line~r internal ole~in~ and minor amounts o~
monomethyl branch~d ol~ins in the ~e~d, the poly-ol~in lubric~nt pEoduct3 ara dis~inct over products of th~ prior art. Tha pr~sence o~ comparable amount~ o~ ov~n and un~v~n carbon number olefin roactant3 in th~ ~eed al~o distingNishe3 th~ pro-ducta ovor ~h~ prior art poly-~-olefin lubricants dorivod ~ro~ athyleno vi~ ~von nu~bered 1-n-ole~ins.

Claims (23)

1. A process for the separation of C5 to C19 mixtures of n-olefins and n-paraffins from mixtures of aliphatic and aromatic hydrocarbons comprising 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.

2. The process of claim 1 wherein both adsorption and desorption are carried out in the temperature range of 10°C and 250°C.

3. The process of claim 1 wherein said adsorption and desorption occurs in the liquid phase.

4. The process of claim 1 wherein the molecular sieve adsorbent is a silicalite.

5. The process of claim 4 wherein the silicalite adsorbent has been previously acid and base treated.

6. The process of claim 1 wherein the desorbent is a n-olefin and/or n-paraffin.

7. The process of claim 1 wherein the process is selective for the separation of a mixture of 1-n-olefins and n-paraffins.

8. The process of claim 1 wherein the hydrocarbon feed contains organic sulfur compounds in concentrations equivalent to from 0.05% to 3%
sulfur.

9. The process of claim 1 wherein the hydrocarbon feed is a distillate produced from petroleum residua by high temperature thermal cracking.

10. A process for the separation of C9 to C19 mixtures of n-olefins and n-paraffins comprising contacting a mixture of said aliphatic and aromatic hydrocarbons with a neutral molecular sieve in the liquid phase in the temperature range of 80°C and 200°C for a sufficient time to effect adsorption of said mixture of said n-olefin and said paraffins, and desorbing the resulting n-paraffin and n-olefin enriched mixture from the sieve with a more volatile n-olefin.

11. The process of claim 10 wherein the molecular sieve adsorbent is a silicalite.

12. The process of claim 10 wherein the process is selective for the separation of a mixture of 1-n-olefins and n-paraffins.

13. A process for the separation of C5 to C19 mixtures of 1-n-olefins and n-paraffins from a mixture of aliphatic and aromtic hydrocarbons comprising contacting a C5 to C19 olefinic cracked petroleum distillate feed produced from petroleum residua by high temperature thermal cracking and containing 1-n-olefins as the major type of olefin components and organic sulfur compounds in concen-trations exceeding 0.05% sulfur with a neutral molecular sieve in the liquid phase in the tempera-ture range of about 10°C and about 250°C for a sufficient time to effect adsorption of said n-olefins and said n-paraffins and desorbing the resulting 1-n-olefin - n-paraffin enriched mixture from the sieve with a more volatile n-olefin or n-paraffin under adsorption conditions.

14. The process of Claim 13 wherein the molecular sieve adsorbent is a silicalite.

15. A prosess for the separation of C9 to C19 mixture of 1-n-olefins and n-paraffins from a mixture of aliphatic and aromatic hydrocarbons comprising contacting a C9 to C19 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% olefins and more than 30% of said olefins being of Type I and additionally contains organic sulfur compounds in concentrations exceeding 0.3%
phase in the temperature range of about 80°C and about 200°C for sufficient time to effect adsorp-tion of said n-olefins and said n-paraffins and desording the resulting 1-n-olefin - n-paraffin enriched mixture from the sieve with a more volatile n-olefin and/or n-paraffin.

16. The process of Claim 15 wherein the molecular sieve adsorbent is a silicalite.

17. The process of Claim 15 wherein the molecular sieve adsorbent is sodium ZSM-5.

18. A selective separation- conversion process comprising contacting a C5 to C19 mixture of aliphatic and aromatic hydrocarbons with a neutral molecular sieve in the gas or liquid phase in the temperature range of about 10°C to about 200°C for a sufficient time to effect a selective adsorption of the 1-n-olefin and n-paraffin components and desorb-ing the resulting 1-n-olefin and n-paraffin enriched mixture with a more volatile n-olefin or n-paraffin converting the olefin components of the mixture to less volatile products via reactions selected from the group consisting of oligomerization, alkylation and carbonylation and removing the unconverted paraffin components from the olefin derived product by distillation.

19. The process of Claims 18 wherein the adsorbent sieve is a silicalite.

20. The process of Claim 18 wherein the olefin is converted to an alkylbenzene by an alkylation process.

21. The process of Claim 18 wherein the olefin is converted to an alcohol via carbonylation.

22. A selective separation-oligomeriza-tion 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% olefins and 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 moleculr sieve adsorbent in the liquid or gas phase in the tempera-ture range of about 100-C to about 250°C for a sufficient time to effect selective adsorption of the 1-n-olefin and n-paraffin components, and desorbing the resulting 1-n-olefin -n-paraffin enriched mixture from the sieve with a more volatile n-olefin or n-paraffin, and reacting the olefin components of the thus separated mixture in the presence of an acid catalyst to selectively produce an oligomer containing 2 to 6 monomer unit, hydrogenating the olefinic unsaturation of said oligomer to produce an isoparaffin lubricant, and removing the unreacted n-paraffin components from the isoparaffin containing reaction mixture by distillation.

23. The process of Claim 19 wherein oligomerization of the olefin components is carried out in the presence of a boron trifluoride alcohol complex.