JPH02212595A - Method for separating olefin/paraffin mixture useful for manufacture of synthetic lubricating oil,by using zeolite - Google Patents

Abstract

PURPOSE: To separate a mixture of n-olefin and n-paraffin by bringing a mixture of aliphatic and aromatic hydrocarbons into contact with a neutral molecular sieve adsorbent to adsorb n-olefin and n-paraffin and subsequently bringing both of them into contact with a describing agent.

CONSTITUTION: A mixture of 5-19C aliphatic and aromatic hydrocarbons is brought into contact with a neutral molecular sieve adsorbent under a condition sufficient to selectively adsorb nolefin and n-paraffin. Subsequently, a sieve product containing an extract having n-olefin and n-paraffin adsorbed thereon to be concentrated is brought into contact with a desorbing agent higher in volatility under a condition sufficient to expel the extract from a sieve. By this constitution, a mixture of 5-19C n-olefin and n-paraffin is separated from the mixture of aliphatic and aromatic hydrocarbons.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The separation method of the present invention uses neutral molecular sieves, especially MFI-framed zeolites such as silicalite, ZSM-5 and compositional variations thereof;
It is based on the selective adsorption-desorption of n-olefins and n-paraffins.

One aspect of the present invention is the disclosure of selective adsorption of various hydrocarbons and organic sulfur compounds, particularly olefins, from hydrocarbon mixtures including olefins, paraffins, aromatic hydrocarbons, and sulfur compounds.

In particular, selectivity is high for n-olefins and n-paraffins of CI to CSS.

Another aspect of the invention is that the a-olefins (1-n-olefins) from distillates produced by pyrolysis operations, particularly FLEXICOKER and FLUID-COKER distillates, are n −
Selective adsorption of a mixture of paraffins.

Yet another aspect of the present disclosure is the conversion of olefin components in mixtures of n-olefins and n-paraffins separated by molecular sieves. These conversions include polymerization, alkyl hydroxide, and carbonylation, followed by a distillation step to remove unconverted paraffins from the conversion product. The conversion of the C, C53, σ-olefin components separated from the less than fuel-value FLEX IC0KER distillate to poly-C-olefin based synthetic lubricating oils is specifically described.

Comparison of the prior art and the present invention Selective adsorption of hydrocarbons in molecular sieves has been known for more than 25 years. Selective adsorption of n-paraffins using molecular sieves is widely used as an industrial separation method.

Early sieve adsorbents were crystalline aluminosilicates commonly known as zeolites.

However, in the last decade, similar crystalline sieve compounds of different chemical compositions have been synthesized. These include various microporous crystalline silicas, such as silicalites, containing aluminophosphates and small amounts of alumina. In the present invention, all these shape-selective adsorbent compounds are referred to as zeolites.

Early aluminosilicate zeolites were polar and acidic in nature and were therefore usually active as catalysts. They led to olefin isomerization, oligomerization, alkylation, polymerization and cracking reactions. And also 1
However, these are often disclosed as adsorbents for separation operations that can be applied to purification processes in which selectivity and absence of side reactions are not of great importance. Most prior patents were directed to the separation of n-paraffins.

Everly and Webb
C. In U.S. Pat. No. 19485.748, normal and branched chain paraffins and olefins are extracted from aromatic hydrocarbons at a molar ratio of SiO*/AMto3 of 2.
Disclosed is separation using acid-treated mordenite greater than 5.

Mobil Oil Corporation
A number of patents assigned to the Corporation disclose the use of ZSM-5 and related zeolites for the separation of normal paraffins. Gorring and Shipman
n) U.S. Patent No. 19894.938 and No. 3.9
No. 80.550 disclosed the catalytic hydrodewaxing of gas oils using polyvalent transition metal derivatives of ZSM-5 and its analogs.

The method for producing this low pour point lubricant is Garwood (GB)
rvood) and improved by Caesar. They disclosed in US Pat. No. 4,149,960 that adding water to a gas oil feed reduces coke formation. US Pat. No. 4,517,402 to Dassau disclosed a method for the selective separation of linear aliphatic compounds by ZSM-11. Dessau shows the separation of n-paraffins from branched paraffins and aromatics and the separation of n-olefins from branched olefins. However, he does not demonstrate the separation of n-paraffins and n-olefin mixtures from feeds containing both aliphatic and aromatic hydrocarbons, and
I didn't even suggest it.

Pratt, Sayles
, Bowers and Sc
U.S. Pat.
discloses selective adsorption of n-paraffins by zeolites such as zeolites and subsequent decomposition of the n-paraffins in the zeolites.

Rosback and Ne
U.S. Pat. No. 3,969,223 by Uzil)
disclose the separation of olefins from olefin-paraffin mixtures, such as cracking waxes, by X zeolite with an amorphous binder previously treated with aqueous sodium hydroxide to increase the sodium cation concentration. be. This treatment reduces dimerization of the olefin during separation. However, this large pore diameter zeolite cannot be used to separate linear and branched chain compounds.

New Jill and Kulprathipanja are U.S. Patent No. 4.4
No. 55,445, column 1, lines 25-32,
For the first time, silicalites are capable of performing the separation of normal C4 hydrocarbons from imbutylene virtually completely free of the aforementioned undesirable side effects such as olefin dimerization and polymerization, and in particular of pentene-1. This is possible when the normal C1 hydrocarbons are expelled from the zeolite using the following method.

Newzil et al. aimed to use their method for the separation of inbutylene from C4 hydrocarbons. This is because imbutylene is useful, for example, as a gasoline blending agent and as a filler for the production of polyisobutylene. They do not disclose or suggest this separation for the production of useful mixtures of higher carbon n-olefins and n-paraffins.

Talpratibanja and Newzil also disclosed the adsorption of normal C, olefins from cyclic compounds and branched 06 olefin mixtures using silicalite with alumina as a binder in US Pat. No. 4,486,618. l-Pentene or l-butene was used for desorption.

l-octene could not completely expel l-hexene. Kruprachipanja in U.S. Pat. No. 4,433,195 disclosed the separation of cis- and trans-olefins by selective adsorption with silicalite. As an example, he adsorbed trans-2-butene from a mixture of cis- and trans-2-butenes and
-Disclosed that pentene is used for desorption.

U.S. Pat.
The selective adsorption of fins and their desorption by n-olefins, especially l-hexene, was disclosed.

However, this patent emphasizes that the feed is limited to hydrocarbons with small amounts or no olefins. The disclosure of the parent patent, U.S. Pat. No. 4,367,364, by Talbrachibanja and Newzil, was also limited to selective n-paraffin adsorption by silicalite in the presence of small amounts or the absence of olefins.

Furthermore, the process of this patent and the subsequent patent by the same inventor were limited to hydrocarbon feeds containing cyclic hydrocarbons with more than 6 carbons. This excludes penzene which can enter the pores of the silicalite.

Full disclosure of the Kurubrachibanja and Newzil patents can be found at
It is shown that all studies were carried out using a composition of silicalite plus alumina binder. St
Even if the /Aa ratio was greater than 12 as described in US Pat. No. 4,486,618, the presence of acidic alumina would have affected the results.

Some of the basic information disclosed in the Tarbrachi Panja and 14 Nijir patents has already been published in the paper announcing the discovery of silicalite. Union
n1on Carb
tde Corporation research group and the University of Chicago, V. Smith, Nature
re) volume 27L pages 512 to 516,
reported the synthesis, structure and general adsorption properties of silicalite in 1978. Silicalite was invented in 1977 in U.S. Patent No. 4.06 by R.W. Gross and E.M. Flanigen.
No. 13724, a novel acid material, which was assigned to Union Carbide. Y,)1. M
a) and Y.

A more recent publication on this composition was published by the American Institute of Chemical Engineers.
Material No. 68h of the proceedings of the 1984 meeting in San Francisco of Chemical Eng tnaars)
It was distributed as -21. It has been revealed that the equilibrium adsorption performance of silicalite in n-hexene for the studied hydrocarbons decreases in the following order: 1-heptene>cyclohexene>benzene>cyclohexane>
The presence of n-octane and alumina binder affected the adsorption in most cases.

The disclosure of the prior art is generally different from the disclosure of the present invention. The methods disclosed in the prior art were aimed at either the separation of olefins or the separation of paraffins. Using zeolite, branched olefins, branched paraffins,
C, to C□ from aromatic hydrocarbons and sulfur-containing compounds
No method was disclosed or suggested for separating the n-olefin and n-paraffin mixtures of .

In fact, the prior art disclosures are limited to C9 and higher n-
Not involved in olefin separation. Prior art disclosures generally emphasize that the hydrocarbon feed of zeolite separation must contain little or no olefins.

According to prior art proposals, hydrocarbon feeds containing high concentrations of aromatic hydrocarbons other than benzene, nitrogen and sulfur compounds should be avoided.

This is because such compounds block selective pore passages and deactivate molecular sieves.

(U.S. Pat. No. 4,455,445, lines 45-56,
and U.S. Pat. No. 4,433.195, lines 7-14).

In contrast to the prior art, the present invention aims to separate mixtures of CS to C19 n-olefins and paraffins from branched olefins, branched paraffins, aromatic hydrocarbons and sulfur-containing compounds using zeolites. Despite the negative teachings of the prior art, the present process can be operated with mixtures containing open chain and cycloaliphatic hydrocarbons and benzene.

It has surprisingly been found that the present invention can be applied to hydrocarbon streams containing relatively large amounts of aromatic sulfur compounds. It has been shown that thiophene, methylthiophene and dimethylthiophene boiling in the C1 to C8 carbon range are adsorbed on zeolites. Higher boiling, larger aromatic sulfur compounds such as benzothiophene were not adsorbed.

It is unexpected that the process of the present invention can be applied to sulfur-containing olefinic distillates produced by high temperature pyrolysis of petroleum residues. Distillates in the C to C13 range are preferred, usually containing aromatic large sulfur compounds such as benzothiophene. Within this high carbon range,
1-n-olefins were adsorbed with greater selectivity over other products in the feed stream.

- In the present invention, acid-base treated silicalite and sodium ZSM-5 are particularly suitable adsorbents for the separation of mixtures of 1-n-olefins and n-paraffins due to their weak olefin isomerization activity. There was found.

The combined separation-olefin conversion method of the present invention is superior to the prior art. The merging process converts the olefin components in the separated olefin-paraffin mixture to higher boiling products and then removes unconverted paraffins by flash off. This unique combination of processing methods has not been thought of prior to the present invention.

SUMMARY OF THE INVENTION The present invention provides a new separation technique for obtaining normal olefins, particularly sigma-olefin reactants suitable as chemical intermediates. Known chemical processes for the production of such olefins are the oligomerization reaction of ethylene, the cracking and dehydrogenation of paraffins, and the dehydrogenation of alkyl chlorides and the dehydrochlorination of alkyl chlorides. Past separations were aimed at separating olefins. In contrast, the present invention provides a method for separating n-olefin and n-paraffin mixtures by means of a neutral molecular sieve, preferably with a high silica-alumina ratio. The olefinic component of this mixture is then selectively converted to the desired higher molecular weight products in a separate step.

Finally, unreacted paraffins are removed from the reaction mixture by distillation.

The key processing step of the present invention is molecular sieve separation. The goal of past sieve separation methods was usually the separation of a single type of compound. Separate methods have been developed for the separation of olefins and normal paraffins. In contrast, the present method separates a mixture of n-olefins and n-paraffins.

A very advantageous feature of the present separation process is that it can utilize inexpensive olefinic hydrocarbon feeds that contain not only aliphatic hydrocarbons but also aromatic hydrocarbons and sulfur compounds. Such olefinic hydrocarbon feeds are produced by high temperature pyrolysis of petroleum residues, particularly vacuum residues. These supplies are type! It contains high concentrations of linear terminal (i.e. -) olefins and linear internal olefins of type II.

Another important feature of the present separation method is the use of neutral molecular sieves. This makes the olefin side reactions very small and allows separation of 1-n-olefin-n-paraffin mixtures without significant isomerization of terminal olefins to internal olefins. In this method, it is preferred to use a low alumina zeolite containing less than 5000 ppm alumina for selective adsorption.

From the point of view of the economics of the process, it is very important that the process is able to use feeds containing significant amounts of aromatic components. The preferred feed for this separation process is an olefin distillate made from petroleum residues by high temperature pyrolysis. Such cracked distillate is used in fluid coking or FLEXICO
Preferably, it is made from vacuum residue by KING.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides C1 to C1
9, preferably C9 to CtS n-olefin n-
/<2 fins Preferably, it relates to a method for separating a mixture of 1-n-olefins and n-paraffins.

The process also uses mixtures of aliphatic and aromatic hydrocarbons, preferably organic sulfur compounds, of Cs to C□, in particular 0.
A neutral molecular sieve, preferably with a minimum ratio of silica to alumina of 20.
A metallic zeolite such as M-5, more preferably a silicalite, most preferably a silicalite substantially free of alumina, preferably pretreated with an acid and then a base, and a liquid and/or gas. phase, preferably under sufficient pressure to retain the liquid phase and under conditions sufficient to effect selective adsorption.
and a step of contacting the n-olefin with the n-olefin in a temperature range of 10°C to 250°C, more preferably 20°C to 150°C, most preferably 100°C to 140°C.
- the sieving product containing the concentrated extract of paraffins is treated with a more volatile desorbent gas and/or liquid, preferably a liquid, preferably n-olefin and/or n-varaffin; more preferably The conditions of the adsorption step are preferably under sufficient pressure to retain the n-olefins or n-paraffins in the liquid phase and under conditions sufficient to drive the extract from the sieve. including the step of contacting under

More specifically, the present invention provides a method for producing C1 to C1
9 n-olefins and n-paraffins, preferably 1-
A method for separating a mixture of n-olefins and n-paraffins is provided. The process comprises passing a mixture of C9 to C19, preferably C9 to C,S aliphatic and aromatic hydrocarbons, preferably also containing sulfur compounds, through a neutral molecular sieve, preferably having a minimum silica-alumina ratio. 20 zeolite, sodium ZSM-5 or more preferably silicalite in liquid phase and at 80°C to 2°C.
00°C, preferably in the temperature range of 100°C to 150°C, for a time sufficient to effect adsorption and sieving the resulting concentrated extract of n-paraffins and n-olefins. desorption using the above-mentioned more volatile olefin or paraffin.

Advantageously, the present invention provides cI to C19, preferably C
3 to CI ms More preferably, a method is provided for separating a mixture of C9 to C13 1-n-olefins and n-paraffins from aliphatic and aromatic hydrocarbons and optionally sulfur-containing compounds, the method comprising: , a feed of the corresponding olefins in a cracked distillate, prepared from petroleum residues by high temperature pyrolysis, preferably by fluid coking or flexi-coking, and containing l-n-olefins as the predominant type of olefinic component. and the percentage of Type I olefins is preferably greater than 30% by weight of the total olefins and the organic sulfur compounds are preferably present at a concentration greater than 0.05%, more preferably from 0.3% to 3%. containing within the concentration range of a neutral molecular sieve, preferably the above-mentioned high Si/
A2 ratio zeolite, more preferably sodium Z
With SM-5 or silica molecular sieve, in the liquid phase, 1
contacting at a temperature range of 0°C to /200°C for a time sufficient to effect adsorption, and removing the resulting concentrated mixture of 1-n-olefins-n-paraffins from a sieve to the more volatile With n-olefins and/or n-paraffins, preferably n-olefins,
It includes a step of desorption under adsorption conditions.

Very advantageously, the present invention provides a method for separating mixtures of C9 to C19, preferably C9 to C11, 1-n-olefins and n-baraffins, the method comprising: A C, to C11 olefinic cracked distillate feed made from vacuum residue by high temperature pyrolysis in a fluidized coking or flexi-coking unit and containing more than 20% of the olefins and containing more than 30% of the olefins. % of type I and further containing organic sulfur compounds at a concentration of more than 0.3% sulfur, a neutral molecular sieve, preferably with a high Si/Aα ratio already defined. zeolite,
More preferably, in the liquid phase, silicalite and 80
contacting at a temperature range of 200 DEG C. to 200 DEG C. for a time sufficient to effect adsorption, and sieving the resulting 1-n-olefin-n-paraffin concentrated extract to the more volatile n-olefins. and/or desorption under adsorption conditions using n-paraffin.

The present invention also includes a separation-conversion process, which process comprises converting olefinic C. A feed of a mixture of aliphatic and aromatic hydrocarbons from CI9 to C13, preferably from C9 to C13, more preferably as defined above, is passed through a neutral molecular sieve, preferably a high Si/Aa ratio. 1-n with a zeolite, preferably as defined above, more preferably a silicalite, in the liquid and/or gas phase, preferably in the liquid phase, within a temperature range of 100°C to 250°C.
- contacting the olefin with the n-paraffin component for a sufficient time to effect selective adsorption of the n-paraffin component, producing 1-n-
desorbing the concentrated extract of olefins and n-paraffins with more volatile n-olefins and/or paraffins, preferably n-olefins, and oligomerizing the olefin components in the extract, preferably
Alkylation and carbonylation of aromatics, more preferably oligomerization to products with 2 to 6 heptamer units, alkylation of benzene to alkylbenzenes and aldehydes to produce aldehydes, preferably aldehyde products. further converting the unconverted paraffin component from the olefin-derived product by a reaction selected from the group consisting of carbonylation to an alcohol or carboxylic acid, and preferably distillation of the unconverted paraffin component from the olefin-derived product. including the step of removing by.

More particularly, the present invention relates to a selective separation-conversion process which comprises converting a feed of CI to CI3 olefinically cracked petroleum distillate from a vacuum residue into fluid coking or made by high temperature pyrolysis in a flexi-coking unit, containing more than 20%, preferably more than 30%, of olefins, and more than 30% of the olefins being of type I;
and further containing an organic sulfur compound at a concentration of more than 0.3% by weight sulfur, with a neutral molecular sieve, preferably silicalite or sodium ZSM-5, in liquid or gas phase, preferably in liquid phase. 1. within a temperature range of 100°C to 250°C, preferably 100 to 150°C. -n
- contacting the olefin and n-paraffin components for a sufficient time to effect selective adsorption, producing! -n-
The olefin-n-paraffin concentrated extract is combined with more volatile n-olefins or/and n-paraffins,
A step of desorption from the sieve, preferably using an n-olefin, in which the olefin component in the mixture thus separated is subjected to an acid catalyst, preferably a boron trifluoride complex, more preferably a boron trifluoride alcohol complex. A step of selectively producing an oligomer containing 2 to 6 heptamer units by converting the original, a step of hydrogenating the olefinic double bonds of the oligomer to produce an isoparaffin lubricating oil, and an isoparaffin-containing reaction. It includes the step of removing unreacted n-paraffin components from the mixture, preferably by distillation.

DETAILS OF EMBODIMENTS Details of embodiments of the present invention will now be described with respect to the hydrocarbon feed of the separation process and the zeolite adsorbent used.

Thereafter, conditions for selective adsorption of the n-olefin-n-paraffin mixture will be explained.

The description of the separation method ends with a description of the desorption process.

The separation-conversion-combination method of the present invention will be described in detail with respect to the conversion included in the inventive concept. The conversion of the olefin components in the n-olefin-n-paraffin extract to synthetic lubricating oils is specifically described.

Hydrocarbon Feed The preferred hydrocarbon feed of the present invention contains large amounts of olefins, paraffins and aromatics.

More preferably, the feed also contains significant amounts of sulfur compounds. A detailed description of the most preferred feeds, distillate feeds, made from petroleum residues by high temperature pyrolysis processes such as fluid coking and 7-lexi coking can be found in U.S. Pat. No. 4,711.968. .

The olefin compound in the feed is preferably 10% by weight,
More preferably it is present at a concentration of greater than 20% by weight and most preferably greater than 30%. In preferred olefin feeds, normal or linear olefins are the predominant olefin component. More preferably, the maximum single type of olefin is Type I of the formula RCH-C,
It accounts for more than 20% of all olefins. The predominant olefin type is 1-n-olefin. Some of the preferred olefin feed components are 1-pentene, 3-hexene, 3-methyl-2-pentene, 1-octene, trans-2-decene, tetradecene, 1-octadecene, and the like.

The paraffin component is preferably as low as or lower than the olefin concentration, and normal paraffins are the predominant paraffin component. Typical paraffins are n-pentane, cyclohexane, n-octane, n-decane, 2
-Methylnonane, decalin, hexadeca>)1, etc.

The aromatic hydrocarbon component preferably represents from 1 to 60% by weight of the feed, more preferably from 10 to 60% by weight. Preferred aromatic hydrocarbons are unsubstituted or substituted with C3 to C3 short alkyl groups such as: benzene, p-xylene, l
-Methyl-4-ethyl-benzene, 1,2,3-trimethylbenzene, naphthalene, 2-methylnaphthalene, phenanthrene.

Sulfur compounds are typically present as impurities in hydrocarbon feeds. The process is advantageous for relatively high sulfur content feeds of 0.05% by weight or more, and
．． Feeds with sulfur concentrations ranging from 3 to 3% sulfur can be processed. Sulfur compounds are usually present as thiols and/or aromatic sulfur compounds. Aromatic sulfur compounds such as thiophene, benzothiophene and dibenzothiophene are preferred. These aromatic sulfur compounds contain one or more short chain alkyl groups, preferably C
It may be substituted with 1 to C1 alkyl, more preferably methyl.

The preferred olefin distillate feed of this invention is produced from petroleum residues by high temperature pyrolysis. The most desirable of such supplies! The percentage of the -n-olefin component generally increases with the decomposition temperature. Distillate products of high temperature pyrolysis processes such as fluid coking and flexi coking are therefore preferred feeds for the present process. Delayed coking, usually operated at lower temperatures, also produces a suitable feed for the process.

However, these feeds contain higher concentrations of n-paraffins than 1-n-olefins. Other methods of producing the feed of the invention, which are less preferred, but are suitable - by boat fishing and milder cracking methods, include pyrolysis of gas oils, and vacuum residue cracking methods. It's braking.

Preferred feeds from fluid coking and flexi coking are rich in olefins, with olefin concentrations greater than 20% by weight, preferably greater than 30%. Aliphatic hydrocarbons are semilinear in nature. The main components are linear, ie normal olefins and normal paraffins.

The type of compound that occupies the largest amount is 1-n-olefin, followed by n-paraffin. The majority of olefins are Type I and Type ■ as shown by the following table, which shows the approximate concentration range determined by proton magnetic resonance spectroscopy (NMR): RCHIICH* RC? CHRRx
C”01t RzC-CHRR*CpCRx Type 1
Type ■ Type ■ Type ■ Type V ~ 25-
45% 15-25% 10-20% 10-20%
Not shown.

The R groups in the formulas of various types of olefins are straight chain or branched alkyl groups. However, type I and type ■
The alkyl groups in the preferred coker olefins are predominantly straight chain or monomethyl branched. moreover,
The type 1 and type 2 olefin components of these preferred feeds are overwhelmingly 1. A fully substituted vinyl has a methyl group as one of the alkyl groups on the carbon. N.M.
R also indicates the presence of a small amount of conjugated diene, whose concentration ranges from about 2 to about lθ%. The concentration of various olefins generally decreases with their molecular weight, ie, carbon number. Therefore, coke oven distillates containing more than 19 carbons per molecule are less preferred.

The paraffin component of the preferred coke distillate feed is present at a similar, but lower concentration than the olefin component. N-paraffins are the major single type of paraffins that exist.

Branched paraffins are mostly methyl branched. Monomethyl branched paraffins are common.

The aromatic hydrocarbon concentration of the feed ranges from 6% to 50%. The percentage of aromatic components increases with the carbon number of the distillate fraction. Therefore, the percentage of olefins and paraffins is of course reduced.

In the preferred C9 to C13 carbon range, the aromatic concentration is 10 to 50%.

The aromatic hydrocarbon components of these feeds are overwhelmingly substituted 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 but in insignificant amounts. Up to 12 carbon atoms, aromatics are benzenoid hydrocarbons. From C12 to C13, most of the aromatics are of the naphthalene type. Among higher carbon number hydrocarbons, most aromatics are fused three-ring compounds such as anthracene and phenanthrene.

The concentration and type of sulfur compounds in the preferred coke distillate vary depending on the carbon number of the distillate.

The concentration range of sulfur is from 0.1% to 3%. - For boat fishing, sulfur concentration increases with carbon number up to 3%.

In the C, to C7 carbon range, thiols are present in major amounts. The C, and higher carbon fractions contain mostly aromatic sulfur compounds, most of which are thio7-entamps. The structure of aromatic thiol components is similar to that of aromatic hydrocarbons. The methyl and ethyl substituted thiophenes are present in decreasing amounts. Alkylthiophene is C, to CI+
It is the main sulfur compound in the range. C12 to Ca
Benzothiophene is usually present within the g range.

In higher boiling fractions, dibenzothiophene is the main sulfur compound component.

Zeolite Adsorbent The zeolite adsorbent of the present process is a molecular sieve and includes not only crystalline aluminosilicates, but also aluminophosphates, silicalites, and similar crystalline materials. The internal pore system of zeolites is an interconnected cage (cage 1).
ike) a system consisting of voids or 112, or a system consisting of three-dimensional passages. The zeolite minerals mordenite and davidite are examples of these two types.

Zeolites are mainly used as catalysts for chemical reactions and as adsorbents for separations. These are owned by J. Wiley and Sons of New York.
Kirk-Otzdomer (Ki s) published by
rk-OLha+er) encyclopedia (En
"Molecular Sheets"("Mo1ecular5") at cyclopedia of (Chemical Technology)
ieves″′) tail.

For more detailed information, please refer to "Zeolite Molecular Thieves"
ves') and "Zeolites and Clay Minerals as Solvents and Molecular Thieves"
als as 5orbents andMolacu
lar 5ieves”), respectively, W.
Breck and R,M, Barea
available in two monographs by (rar). These monographs were published in 1984 by R.E. and Krieger (K.
rieger) Publishing
g) Company R (Co,) by Malabar, Florida and Academic Press, 1978 (
Academic Press, New York.

Published by N.Y.

Separations based on molecular sieving effects generally use dehydrated zeolites. Molecules can be selectively adsorbed based on differences in their size, shape, and other properties such as polarity.

The preferred zeolite adsorbent of the present invention is 3.5 to 7"A
with a pore diameter of up to. Zeolites with this pore diameter range from 2-upite to ZSM-5 and silicalite. Such zeolites are capable of adsorbing n-paraffins and 1-n-olefins while rejecting branched olefins, branched paraffins and C9 and higher carbon aromatic hydrocarbons. Another important property of preferred zeolites is their reduced polarity, which gives them an increased affinity for aliphatics than for aromatic hydrocarbons. In order to reduce polarity, i.e. increase hydrophobicity, the ratio of silica to alumina of the zeolites of the invention is preferably greater than 12, more preferably 30 as in ZSM-5.
It's bigger. U.S. Patent No. 3.702.886 is ZS
M-5 is disclosed. This is incorporated into this book as a reference. Similar zeolites are ZSM-11, disclosed in U.S. Patent No. 3,709,979, and ZSM-12, disclosed in U.S. Patent No. 19832,449.

Zeolites are classified according to their pore structure.
te 5structure types'') by W. M. Meier and H. Olson.

This nomograph was published in 1978 by Polycrystal Book Service, Pittsburgh, Pennsylvania.
Published by Crystal Book Service. According to Mayer and Olson's terminology, Z
Both SM-5 and silicalite have an MFI framework generated during synthesis that has two orthogonal intersecting passage systems with minimum diameters of 5.1 and 5.4'A. ZSM
The MEL framework of -11 is also similar. MFI and ME
Both L structures have pores with 10 ring windows.

The silica to alumina ratio for ZSM-5 and ZSM-11 is typically 30. Pure silicalite, by definition, has an alumina-free framework, but the silicalite used in the present invention also contains significant alumina. For the purposes of this invention, sodium z
5-r-5 is distinguished from silicalite. It is used because it contains sodium which results in less olefin isomerization activity than silicalite.

The silica to alumina ratio of the zeolite can be increased by removing some of the alumina by acid treatment. This reduces the acidity and polarity of the acid-treated zeolite. Acid treatment also affects pore size. These effects combine to increase the adsorption performance and selectivity of the zeolite and reduce the extent of undesirable side reactions.

Although protonated aluminosilicate pear zeolites of low acidity are used as adsorbents in the present invention, it is preferred to use their sodium derivatives, more particularly sodium. Such derivatives are
It is made by neutralizing a protonated zeolite with a suitable metal base or salt, such as an aqueous solution of sodium hydroxide or sodium chloride. Such base treatment also favorably affects the pore diameter and shape of the zeolite.

Changes in the cations also lead to electric field effects, which result in different interactions with the adsorbed molecules. For example, the pore diameter of the calcium exchange type of synthetic zeolite A is 4
．． It is 26A. This sieve is called 5A. Natural zeolite glue 3977 is another aluminosilicate with similar pore diameter. Preferred ZSM-5 has high Si/
It is a sodium aluminosilicate with a ratio of A12 and its pore diameter is 5'AJ: larger. Sodium ZSM-5
is made from either the corresponding quaternary ammonium derivative via thermal decomposition and neutralization or by direct synthesis.

A preferred zeolite adsorbent is silicalite, which is topologically similar to ZSM-5 and has the same budding units. Silicalite 2I! The pore size of the cross passages is from 5.2 to 5.7
'A range. Silicalites do not contain convertible metal cations and are therefore believed to be highly non-polar and have a high affinity for non-polar hydrocarbon molecules.

The silicalite reprinted from Union Carbide Corporation contains a significant amount of aluminum, ie about 0.5%, as An,03.

A significant amount of this impurity can be removed by acid treatment.

The resulting low alumina (about 0.3% Aff) silicalite is then treated with base to neutralize and remove acid impurities. The resulting acid-base treated silicalite has excellent selectivity and is therefore the preferred adsorbent in the present process.

Crystalline zeolite adsorbents are typically formed into spherical or cylindrical pellets with high mechanical abrasion resistance. this is,
This is accomplished using a binder that does not significantly impede diffusion in the micropores. Silica, alumina, and crosslinked organic polymers can be used as binders.

Adsorption through zeolite molecular sieves is carried out using gaseous and liquid feeds. In this method, the zeolite is regenerated and used in a number of adsorption-adsorption cycles.The method aims at the separation of two molecules instead of one type. Therefore, it does not follow the rules and predictions that have been developed for methods of separating single types of compounds. However, processing techniques such as countercurrent liquid phase adsorption, which have been developed for single hydrocarbon types, are applicable.

The present invention involves selective adsorption of both n-olefins and n-paraffins from mixtures of aliphatic and aromatic hydrocarbon compounds. Preferred feed mixtures are within the C5 to C0 range. Preferred are 1-n-olefins and n
- Paraffins are more terminal 1-n than internal n-olefins
- to be adsorbed primarily from one olefin-rich feed.

A preferred such feed is a distillate made from petroleum residues by high temperature pyrolysis. Such feeds further contain sulfur compounds.

1. There is no side reaction due to catalysis such as isomerization.
- Of particular importance for recovering mixtures of n-olefins and n-paraffins. 1-n-olefins are easily isomerized into internal olefins. - For boat fishing, internal olefins and terminal olefins are not required.

During the study of acid-base treated silicalite in the present invention,
The following was unexpectedly discovered. That is, C1 to C
The 1-n-olefins are preferably adsorbed more than the corresponding n-paraffins. Trans-isomers of internal linear olefins and 1-olefins are adsorbed at similar rates. Adsorption of very small amounts of the cis-isomer hardly occurs.

For trace amounts of conjugated linear diene components, such as trans-piperylene, selective adsorption has also been observed.

In addition to selective adsorption of 1-n-olefins and n-paraffins, selective adsorption or rejection of aromatic sulfur compounds was observed using ZSM-5 and silicalite. The thiophene sulfur compound components in the C to C1 cracked distillate produced from the residue were selectively adsorbed in this method. The adsorption of 2,5-dimethylthiophene is surprising since very small concentrations of toluene components are not adsorbed.

However, the adsorption of these sulfur compounds does not prevent the production of 1-n-olefin and n-paraffin concentrated extracts.

If desired, traces of aromatic sulfur compounds can be removed before the next chemical conversion, for example by chemically modified adsorbents. Benzothiophene type sulfur compounds present in higher carbon distillates are not adsorbed.

Silicalite has been shown to be a size-selective adsorbent for some monomethyl branched olefins. 3-Methyl-2-pentene was selectively adsorbed, but 2
-Methyl-2-pentene, 2-methyl-1-pentene and 4-methyl-2-pentene were not adsorbed. C
Some adsorption of 6 and higher carbon 2-methyl-1-alkenes and 2-methylalkanes was observed. However, their presence in minute amounts in coke distillate extracts does not preclude the use of such extracts in synthetic lubricant production.

hydrocarbon feed at a temperature such that the molecules to be adsorbed have sufficient energy to overcome repulsive interactions with the zeolite, pass through the zeolite channel pores, and reversibly fill the micropores. When zeolite is brought into contact with
Adsorption occurs. To achieve sufficient diffusion rates of the adsorbent, as the size and/or weight of the molecule increases, higher temperatures are required to overcome the activation energy required for that molecule.

Generally, preferred adsorption temperatures are within the range of 10 to 250°C. Adsorption of low molecular weight, ci to C, distillate feeds can be carried out at low temperatures, ie in the range of 10 to 100°C. In order to adsorb the C8 to C11 fractions at optimal diffusion rates, it is necessary to increase the temperature to a range of 100 to 200°C. However, the optimum temperature of the present adsorption process is limited by the need to avoid isomerization and decomposition of the 1-n-olefin.

The choice of adsorption temperature also depends on the carbon range of the hydrocarbon feed. Broad distillate feeds are grown at higher temperatures than warranted for their lower boiling point components.

Gas phase adsorption is preferably carried out at near atmospheric pressure within a temperature range in which the feed is in the gaseous state.

Similarly, liquid phase adsorption takes place at temperatures where the feed is a liquid. When processing volatile feeds such as those in the liquid phase, pressures higher than atmospheric pressure are used. - Liquid phase operation is preferred for boat fishing. This is because the operation is usually carried out at low temperatures and the yield of extract is high.

DesorptionDesorption, ie, the removal of concentrated extracts of n-olefins and n-paraffins from zeolite adsorbents, is carried out under various conditions as part of an adsorption-desorption cycle. A thermal swing cycle involves desorption at a temperature higher than the temperature of adsorption. Similarly, pressure swing cycles use lower pressures to perform desorption. Isothermal purge cycles use a non-adsorbent liquid to strip adsorbates from the voids and ultimately the pores of the zeolite. Finally, a displacement purge cycle uses a desorbent that adsorbs as strongly or more strongly than the adsorbed material. This desorbent is then replaced by the adsorbent in the adsorption cycle.

For information on Zara-7, see the cited discussion of molecular sieves in Kirk-Odmer's Encyclopedia of Chemical Technology.

The preferred desorption is that of a displacement purge cycle. The preferred method of performing this cycle is D, B, Bruton (
Brough ton), U.S. Patent No. 2.98
5,589, and presented at the 34th annual meeting of the Society of Chemical Engineers, Tokyo, April 2, 1969, entitled ``Continuous Attributive Processing - A New Separate Recon Technique''. Continuous Adsorptive
eProcessing-A New 5eparat
Bruton specifically discloses a simulated process flow diagram for a preferred countercurrent moving bed in the process of the present invention. did.

- In boat fishing, various compounds such as COx, NHs, methane, butane and butenes are used in the desorption process. However, in the preferred operation of the liquid phase using displacement purge cycles, 1, n-paraffins and/or monoolefins, especially 1-n-olefins, are the desorbents of choice.

These preferred desorbents are liquids with lower boiling points than the feed. In preferred operations, the boiling point of the desorbent should be low enough to be easily separated from the feed by distillation, but so as to ensure that the specific gravity and viscosity of the desorbent are not drastically different from that of the feed. Must be high enough. The latter facilitates smooth feeding and displacement of the extract by liquid flow in the adsorbent bed.

Typical desorbents include 1% pentane relative to the C6 feed.
l-hexene, c for C7-C1 feed.

~C1! against the supply of! -n-octyne is included. In contrast to the prior art, 1-n-octene is the preferred desorbent in the present method. ! -n-octene! −
Although the n-olefins cannot be completely separated from the n-paraffin concentrated extract, their presence does not pose an obstacle in the subsequent conversion of the olefin component.

In a preferred operation, a broad feed fraction such as C6 to CPS is used, and the low boiling portion of the extract, such as C1 C1 n-olefins and n-paraffins, is used as a desorbent. In such operations, the low boiling components of the extract are distilled and used as desorbents.

The general temperature range for desorption is generally the same as that for adsorption. The preferred temperature ranges for desorption and adsorption in isothermal or near static processing cycles, such as the preferred displacement purge cycle and stripping cycle, are similar by definition.

With the exception of pressure swing cycles, the pressure ranges for adsorption and desorption are generally similar. Cycles near atmospheric pressure are preferred. In the preferred liquid phase cycle, the use of low boiling desorbents such as n-butane requires superatmospheric pressure.

The adsorption-desorption cycle of the present process is operated at temperature conditions where little side reaction of the olefin takes place.

Nevertheless, zeolite adsorbents have a limited useful life due to pore clogging due to slight side reactions. Such deactivated zeolite can generally be regenerated by calcination to burn off organic impurities.

Conversion The n-olefin and n-olefin obtained in this separation method
The olefinic component of the paraffin mixture is conveniently converted to higher boiling derivatives and then separated from unreacted n-paraffins. These conversions generally involve known chemical reactions and processing methods. Preferred conversions are oligomerization, aromatic alkylation, and carbonylation.

A preferred aspect of the present invention is the unique combination of zeolite separation and selective conversion of n-olefin and n-paraffin mixtures followed by n-, (rough-in) separation.

Preferred n-olefin-n-paraffin mixtures of the present invention contain 1-n-olefins as the main olefin component. These 1-n-olefins are the preferred reactants in many types of conversions, such as polymerization, oligomerization, alkylation, carbonylation, and other various olefin conversions. In the following, the conversion of these olefins will be mainly explained. N-olefins generally undergo similar conversions at lower rates.

The oligomerization of 1-n-olefins with acid catalysts and free radicals is widely known. In this method, acid-catalyzed oligomerization in the liquid phase is preferred. The catalyst is generally a strong acid, such as phosphoric acid, sulfonic acid, aluminum chloride, alkyl aluminum dichloride, and boron trifluoride complexes. 37) The boron complex is preferably a complex of protic compounds such as water, alcohol and protic acids; the use of BF3 complexes avoids separation side reactions.

Oligomerization is generally carried out at atmospheric pressure and within a temperature range of -100 to 100<0>C. Superatmospheric pressures may be used to ensure operation in the liquid phase.

The number of monomer units in the oligomeric product is between 2 and 3.
0, preferably 2' to 6.

The most preferred oligomerization produces polyolefin intermediates for synthetic lubricating oils. The production of synthetic lubricating oils via the polymerization of equal numbers of pure 1-n-olefins was described by J. A. Brennan in 1980 in the Journal
of Industrial Chemistry (Journa)
l, lnd, Eng, Chea+, ), Pro
d, Res, Dav.

Vol, 19. pages 2-6 and the references of this paper. Brennan concluded that isoparaffins derived from 1-n-decene by boron trifluoride-catalyzed trimerization followed by hydrogenation have excellent lubricant properties. Due to the position and length of these n-alkyl chains, these trimers also exhibit excellent stability. These viscosities are relatively insensitive to temperature changes.

Based on these and similar studies, C1, C3° and C1! A lubricating oil based on σ-ole2yne of
Isoparaffins with 30 to 40 atoms per molecule have been developed.

More recently, synthetic lubricating oils have also been developed based on internal olefins. No. 4,300.006 to Nelson and No. 4,31 to Heckelsberg et al.
No. 9,064 discusses the synthesis of such lubricating oils by BFI-catalyzed duplication of linear internal olefins derived by metathesis of σ-olefins.

Hetzkelsberg also published U.S. Patent No. 4.317.948.
discloses the synthesis of lubricating oils by simultaneous dimerization of linear internal and terminal, i.e., σ-olefins.

According to the invention, n-olefins and n-olefins in n-paraffins are converted into oligomers by reacting them under an acid or free radical catalyst, preferably an acid catalyst. In a preferred conversion step, an average of 3 to 4 heptanomeric units is produced by reacting a concentrated mixture of cI to C13 1-n-olefins and n-paraffins in the presence of a boron trifluoride complex. Containing oligomers, ie trimers and tetramers, are produced. In another step, C13 to C10
1-n in a mixture of n-olefin and n-paraffin
- Olefin and normal internal olefin components are co-oligomerized to produce oligomers containing on average 2 to 3 monomer units.

Another preferred acid-catalyzed oligomerization of n-olefins produces polyolefins in the carbon range C10 to C1.

These are then used to alkylate benzene to produce cis to C1° alkylbenzene intermediates for the synthesis of oil-soluble calcium and magnesium alkylbenzene sulfonates. It is preferable to use C, to C8 n-olefins for these oligomerizations.

Unconverted paraffin components in the n-olefin oligomer product mixture are preferably removed by distillation. Distillation is carried out immediately after oligomerization or following a subsequent conversion step such as hydrogenation to isoparaffins or alkylation of benzene to alkylbenzenes.

n-Olefin Plus Involves acid-catalyzed alkylation of n-paraffin mixture aromatics. Typical reactants are benzene, toluene, 0-xylene, naphthalene and phenol.

Alkylation of benzene with n-olefins is important in the production of linear alkylbenzene intermediates of biodegradable aqueous alkylbenzene sulfonate detergents and oil-soluble linear alkylbenzene sulfonate salts. The alkylation of benzene can be carried out at temperatures from 0 to 100° C. by known methods using A+2CI23 as a catalyst.

Alkylation of phenol with n-olefins results in linear alkylphenol intermediates of ethoxylated surfactants. Phenol is highly reactive and is readily alkylated in the presence of a crosslinked sulfonated styrene-divinylbenzene resin, Amberlyst 15, at 80-150°C.

After alkylation of aromatics, unconverted olefins and other volatile components are removed by distillation.

A third preferred conversion is the carbonylation of the n-olefin components in the n-olefin and n-paraffin extracts. Carbonylation is the reaction of carbon monoxide and an active hydrogen compound to produce a carbonyl derivative of the olefinic reactant. For the preferred 1-n-olefin component, the main reaction is: RCH-CHt+CO+HXRCH, CHsCOXRm
n-alkyl,

Co/Ht RCH= CH! ------→-RCHtCHtCHO
+RCH(CHs)C.

Hydroformylation of olefin components in a flexi-coker total distillate feed is disclosed in the previously referenced Oswald et al. patent. Similar hydroformylation catalysts and conditions are applicable to the n-olefin and n-paraffin extracts of the present invention. The preferred feed for this carbonylation is also from a 7 lexicoke machine. The feed primarily contains 1-n-olefins and n-paraffins separated from the flexi-coker distillate.

Preferred n-olefin-n-paraffin mixtures used as carbonylation feeds are relatively narrow in carbon range and include components that differ by the number of adjacent carbon atoms by 3 or less. This means that
It allows unconverted paraffin components and paraffin by-products to be separated from the carbonyl compound product. In the case of hydroformylation, the aldehyde product is hydrogenated to the corresponding alcohol before removal of paraffins by hydrogenation.

For polymerization and copolymerization aimed at producing high molecular weight polymers, 1-n-olefin-n-paraffin mixtures, where the 1-n-olefin and n-paraffin have the same specific number of carbon atoms in the molecule, are used. For example, the mixture of 1-n-hexene and n-hexane made by this method can be used to make ethylene-hegysene copolymer.

Similar 1-n-olefin-n in which 1-n-olefin and n-paraffin have the same specific number of carbon atoms in the molecule
- Paraffins are also preferably used for other olefin conversions such as hydroboration and epoxidation.

EXAMPLES The following examples are provided to illustrate the presently claimed method but are not intended to limit the scope of the invention. Most of the examples illustrate new selective adsorption of n-olefin-n-paraffin mixtures on zeolites, especially silicalites and sodium ZSM-5. model compounds and derived from petroleum residues, 1-
Adsorption studies on feeds such as concentrated cracked distillates of n-olefins are also discussed. The desorption process of the present adsorptive molecular sieve is also explained. Finally, examples are given regarding the conversion of olefin components in the n-olefin and n-paraffin enriched products of the present separation process.

Before going into the side examples, the cracked distillate feed and zeolite adsorbent used are described. Test and analytical methods are described: standard static adsorption tests in gas and liquid phases, and analysis of raffinates by capillary gas chromatography.

Feeds, Test Methods and Analyzes The mixture of model compounds used as feeds for adsorption studies is pure research chemicals and is representative of the main types of compounds present in the feed of this separation method. made from something.

The preferred feed fraction studied in detail was Fregisi coke distillate, which was produced by cracking the vacuum residue of mixed crude oils of South American and Middle Eastern origin. The molecular composition of fluid coker distillate similarly obtained from Northwestern American crude oil was similar. Both distillates are described in detail in the already referenced Oswald patent.

The zeolite adsorbent was calcined by heating at 400° C. overnight before use. (After that, the adsorbent was heated for 8 hours under nitrogen until use.)
Store at 0°C.

Most of the silicalite used was supplied by Union Carbide Corporation. 5115 was a microcrystalline silicalite powder, and RJ15 was a silicalite pelletized using a silica binder. Similarly, pH
5 was pelletized with an alumina binder; silica. A low alumina (less than 200 ppa+) microcrystalline silicalite was also used.

High alumina (
A portion of the silicalite powder (5000 ppm) was first treated at room temperature with an 18% aqueous hydrochloric acid solution for 3-4 nights until the color of the supernatant liquid became clear. Thereafter, this silicalite was studied overnight using a dilute aqueous sodium hydroxide solution having a pH of 9 to 10. These treatments significantly reduced its alumina content and neutralized acidic impurities.

The silicalite obtained by this acid-base treatment was calcined in the usual manner.

ZSM- made from the corresponding quaternary ammonium derivatives
A pentasodium a) reminor silicate derivative prepared in the laboratory was also used. A fine crystalline powder was also calcined and used in part of the adsorption tests.

Sodium ZSM-5, produced by direct synthesis by Jetikon of Switzerland, was also tested.

Capillary gas chromatography (GC) was used for the analysis of the model compound mixtures and seven Lexico distillate fractions used as feeds for the adsorption tests and their respective raffinates, i.e., the non-adsorbed products of these tests.
;) was used. Highly resolved G
C analysis was achieved. Therefore, the GC residence time is directly proportional to the boiling point of the component.

Generally, the zeolite and hydrocarbon feeds were accurately weighed and used to conduct the adsorption studies. After contacting the feed with the zeolite, the rejected hydrocarbon raffinate was analyzed and compared to the feed.

For both gas and liquid phases, using mixtures of motile compounds of various carbon ranges and 7 lexicon fractions,
A static adsorption test was conducted. In the gas phase test, approximately 1 g of zeolite and 0.2 g of hydrocarbon feed were placed in a small sealed glass bottle and kept there for 4 hours at 40°C. The low carbon N cs and C used in these tests
For the lower fractions, this was sufficient to achieve adsorption and gas-liquid equilibrium. Both the gas phase representative of the raffinate in the test mixture and the feed were then sampled for C, C, analysis.

In liquid phase tests, the hydrocarbon feed was diluted with the non-adsorbable, large compounds heptamethylnonane or decalin. In the majority of liquid phase tests, 1 of the zeolite
2 g of 10/90 mixture of hydrocarbon and diluent per g
was used. This ratio of liquid to solid produced a significant liquid phase in the test mixture, which was easy to sample. The test mixture was heated for several hours with occasional shaking to reach equilibrium. The supernatant was then analyzed by GC and its composition compared to that of the feed.

A portion of the liquid phase tests were conducted at approximately 1 g of a 30/70 mix of feed and diluent per gram of zeolite.

These mixtures showed almost no supernatant liquid phase after settling. The mixture is sealed and heated to reach equilibrium as described above. Equilibrium was quickly established in these tests because there was no separate liquid phase. After equilibration, approximately 1 g of the test mixture
of isooctane, 2.2.4-) lynchylpentane or other suitable bulk compound and mixed thoroughly. After settling, the clear upper groove liquid phase was routinely analyzed by GC.

It should be noted that the absence of zeolite microcrystals in the liquid injected into the gas chromatograph is extremely important for correct compositional analysis of the raffinate. These crystals, if present, adhere to the high temperature (approximately 325 DEG C.) injection section of the chromatograph and act as decomposition catalysts, especially for the 1-n-olefin component.

The flexi-coker distillate feed showed a complex gas chromatogram, with the GC peaks of several components overlapping, especially in the higher carbon fractions. As a result, the display of some minor components GC
The percentages varied depending on the sample size of the GC.

The selectivity and performance of the zeolite adsorbents for the components of the test mixture were evaluated by the ratio of their concentrations to their respective concentrations in the raffinate.

A large ratio indicates selective adsorption, a small ratio is a sign of rejection by the zeolite.

Washing was repeated with water until the washing water showed a neutral reaction to lidomas. The silicalite was then washed in 1 liter of a weakly basic solution prepared by adding 0.39 NaOH to 1 liter of water and resedimented. and one final rinse with deionized water. The silicalite was dried overnight in air at 90°-95°C. Then, the needle was baked at 400°C for more than 4 hours, and the needle was ready for use. .

One liter of 18% by weight hydrochloric acid was added to 20 g of Silicalite CSTTS (Union Carbide Corporation) with stirring at room temperature. The liquid-isomer suspension was allowed to settle overnight and separated into two phases.

The already discolored supernatant liquid phase was decanted and a new 18% CI2.1! was added to this solid with stirring and allowed to settle again overnight. This pickling procedure was repeated three times, after which the liquid phase remained colorless.

The silicalite was collected and a sealed mixture of approximately 0.29 deionized CgFK feed fraction and 1 g of acid-base treated silicalite was heated at 40° C. for 4 hours. Subsequent GC gas phase analysis of the feed and raffinate (Raf)
The percentage compositions listed in the table are shown. (The main components are listed in order of their residence times.) According to the data in Table 1, in the raffinate 1-n-pentene, cis-1 and trans-pentene and n-
The concentration of pentanes is significantly reduced, indicating their selective adsorption. On the contrary, methyl-branched butenes and impentane (2-methylbutane) increased in the raffinate, indicating that they were rejected.

Table 1 Tenisopentane 13.4 21.8
0.611-n-pentene 38.1 22.
6 1.692-Methyl-1-bu 18.4
24.2 0.76 ten-n-pentane 12.5 6.7
1.86 Isoprene 3.1 4
．． 5 0.69 Trans-2-Pen 4.9
3.1 1. ．． 58 tensis-2-pentene 1.8 1.3
1.382-methyl-2-bu 0.8 3.
2 0.25 Ten Example 3 Approximately 0.2 g of a mixture of similar amounts of n-hexene, n-hexane and 2-methylpentane and 19 acid/base washed silicalites were contacted at 40° C. for 4 hours. Then, it was analyzed by a gas phase method using GC. The compositions of the produced 1t raffinate and the starting feed are compared in Table 1.

According to the data in the table, all of the n-hexene and n-hexane in the mixture were adsorbed, except for cis-2-hexene. Trans-2-hexene was adsorbed preferentially over cis-2-hexene.

Rejection of the 2-methyl branch of 1-pentene was demonstrated.

According to calculations, 2-hexene and l-
Approximate performance against hexene is approximately 4.7% by weight each
and 1.9% by weight.

Ir butene 1-rl-hexene 17.0 13.8
1.23n-hexane 18.0
12.6 1.43 trans-2-hex 22
．． 7 14.7 1.55 censis-2-hexene 18.8 17.0
1.110 Pentene and cyclopentane are not adsorbed. In contrast, cis and trans-piperylene appeared to be adsorbed among the most C, hydrocarbons, and n-hexene showed the aggressive adsorption behavior seen in the C, model mixture. Methyl-branched pentenes were not adsorbed much other than 3-methyl-branched 2-pentenes. Among the C@paraffins present, only n-hexane was adsorbed.

According to calculations, the approximate performance of silicalite for the two main components, 1-n-hexene and n-hexane, is 3.
．． 5% and 1.8%.

A mixture of a wide Q of about 0.29, 7 Lexicoix feed fractions and 1 g of acid/base treated silicalite.

A gas phase adsorption test was conducted at 40° C. for 4 hours. The results of the subsequent GC analysis of the feed and the resulting raffinate are ■
Shown in the table.

According to the data in this table, among the CS components, cS3('tsu, to Eight - Interchange.

Part 8 1゛゛( Example 5 In the case of methylthiophene, which is small in size, expensive.

Approximately 2.4 g of a 10/90 mixture of the model compound of C. and heptamethylnonane diluent was added to two 1 g acid/base wash samples to prepare two test mixtures.

These mixtures were then heated at 110°C for 2 hours and 15 minutes.
Heated at 0°0 for 4 hours. The synovial fluid of these compositions was then analyzed by GC. The GC compositions of the two C, raffinate compositions are compared to the feed composition in Table 1.

According to the data in this table, at both test temperatures, 1
-n-octene and n-octane are selectively adsorbed from a mixture containing C7 and C aromatic hydrocarbons. 1-
Only slight isomerization of octenes to internal octenes, namely 2-3- and 4-octenes, occurs. Aromatic sulfur compounds present, 2-methylthiophene and 2.5
-Dimethylthio7one is adsorbed very selectively. Selected Examples Depicted by the Raffinate to Feed Ratio Using approximately 2.2 mff of a 10/90 mixture of 6 C,7 Lexicoke distillate and heptamethylnonane and 19% acid/base washed silicalite, the liquid phase An adsorption test was conducted.

The mixture was heated at 110°C for 2 hours. The supernatant raffinate was analyzed by GC and its composition compared to that of the feed. The results are shown in Table 7.

According to the data, 1-n-octene and n-octane were selectively adsorbed. It appears that some of the 1-n-octyne is isomerized to internal octenes. It is clear that 4-methyl-1-heptene is poorly adsorbed due to the central branching of the chain. Dimethyl branched aliphatic hydrocarbons are completely rejected. Similarly, the aromatic hydrocarbons, toluene, and ethylbenzene, appear to be rejected.

6 AS to “l” silkworm 2　　　　　　　　　　　　-＼　H!mW　7 40/60W of model compound and decalin diluent.

Approximately 1 gram each of the hardware was mixed with approximately 1 gram each of acid/base washed silicalite and sodium ZSM-5. In liquid phase adsorption tests, the mixture was heated at 150° C. for 1 hour in a sealed glass bottle. These were then diluted with approximately 1 mole of i-octane. The solid zeolite was then precipitated and the supernatant raffinate was analyzed by GC. The composition of the raffinate is compared with that of the starting model mixture and is shown in Table 1.

(2) According to the data in the table, 1-n-nonene and n-nonane are adsorbed to both silicalite and sodium ZSM-5 adsorbents to a similar degree, although strongly. 2-Methyl-1-nonene and 2-methylnonane are only slightly adsorbed, whereas both trimethylbenzene isomers are completely rejected.

In the presence of silicalite, slight isomerization of 1-n-nonene to cis- and trans-2-nonene occurred. In the presence of silicalite, 2-methyl-1-
It appears that a large isomerization of nonene, possibly to 2-methyl-2-nonene, took place. Sodium ZSM-5
There was no sign of isomerization in the presence of .

The reduction in the concentration of 1-n-nonene and n-nonane in the raffinate indicates that the combined performance of silicalite and sodium ZSM-5 for these two compounds is approximately 8.
3 and about 9.2%.

Example 8 Milk' L 1-n-decene, n-decane, 1.2.4- and 1.
2.3-trimethylbenzene in hebutamethylnonane 1
Approximately 1.69 g of the 5% solution was added to 1 g of acid/base washed silicalite. The mixture was heated at 150°C for 3 hours.

Subsequent GC analysis of the supernatant liquid finate showed significant changes in the model compound composition, as shown in .

The data show highly selective adsorption of both 1-n-decene and n-decane. Slight isomerization of l-n-decene is indicated by easily distinguishable GC peaks of 4-decene and trans-2-decene. Based on the reduced concentration of 1-n-decene and n-decane, the approximate performance of silicalite for both these compounds is 10.1%.

l-decene 22.1 0.9
24.54-decene 0,1n
-Decane 22.0 2.8
7.9 trans-2-de 0.1 sen compared to that. Conclusion! 'F ■ Shown in table.

According to the data, all n-decene is adsorbed in contrast to the trimethylbenzene component. However, determining the relative selectivity of these adsorptions is not possible due to their simultaneous isomerization.

2,5-dimethylthiophene is not rejected as clearly as trimethylbenzene at a concentration comparable to that of n-decene, but its degree of adsorption is small.

Absorption of n-decene isomers from mixtures of modeled metals Approximately 2.79 g of a mixture of C1° model compounds and heptamethylnonane was added to 1 g of acid/base washed silicalite. The resulting test mixture was then heated at 150° C. for 2 hours. Next, the supernatant raffinate liquid was analyzed by GC, and its composition was determined from Table 1 of the feed mixture. 2-Decene a a The two GC peaks are not completely separated.

-ma i.

Various Silica C from a mixture of Cl11 model compounds
l19 model compound and about 10 of heptamethylnonane
Approximately 1 g of the /90 mixture was added to each 1 g sample of each type of silicalite. The resulting mixture was heated to 150°C.
The raffinate was analyzed by GC. The data are shown in Table ■.

Comparison of the feed composition with the raffinate composition shows that all of the tested silicalites contain 1-n-decene and n
-Selective adsorption of decane. Untreated and acid/base washed silicalites were particularly effective in adsorbing l-0-decene.

1 due to the low concentration of cis-2-decene in the raffinate.
It is clear that not much isomerization of -n-decene occurs. In the case of untreated silicalite, the concentration of indene in the raffinate of the mixture is significantly reduced. This is probably due to acid-catalyzed dimerization and oligomerization. The decreasing concentration of 2,5-dimethylthiophene showed selective adsorption by all zeolites, and no selective adsorption of 2,5-dimethylthiophene was observed. The larger sulfur compound, benzothiophene, was not adsorbed in this example or in the previous example.

Gei I - ■■ 吋 TO 10 ト N Roro ■ OOk mouth - ■ ω! Experiments were carried out at 120 DEG C. using sodium ZSM-5 and silicalite granulated with an alumina binder according to the method described in the previous example. The results are shown in Table X. .

According to the data, ZSM-5 exhibits similar adsorption behavior to the alumina-bonded silicalite of this example and the previous silicalite. L-n-decene and n-decane are selectively adsorbed. 2,5-dimethylthiophene is adsorbed, but benzothiophene is not. All aromatic hydrocarbons are not adsorbed.

According to the study of adsorption time by silicalite, the treatment is 3
It has been found that the process is substantially complete in 0 minutes or less.

7 Enbenzene 1-n-decene n-decane indane indenaphthalene benzothiophene 25.7 27.9 0.8 11.4 8.0 2.0 7.5 8.8 1.3 15.2 2.8 13 .3 17.4 1.3 13.5 13.3 2.5 Boiling point of narrow C19 fraction of adsorption flexi coke naphtha 1
10/90 mixture of 65 to 171”o about 1.9
9 was added to the acid/base washed silicalite of 19. The resulting test mixture was heated at 150° C. for 4 hours. The feed and supernatant raffinate were then analyzed by GC. The gas chromatogram of the feed is shown in FIG. Compare the feed and raffinate compositions in Table ■.

According to the data in the table, the main 1-n-decene and n-
The concentration of the decane component is significantly reduced by treatment with silicalite. This is apparently due to selective adsorption of these components. As a result of the selective adsorption of linear aliphatic compounds, the concentration of aromatic components generally increases.

Mold-Table 1-n-decene 23.17 0.92 25.18 n-decane 14.86 3.57 4.16 Indane 2.96 5.52 0.54 Indane 0.85 0.90 0.94 Implementation Example 13 Acid-base washed silicalite with layer volume of 511Q approx. 4.51
2 was packed into a stainless steel column 18 inches in diameter and 1 foot long. The resulting adsorption layer was prewetted with n-hexane desorbent at a liquid hourly space velocity (LHSV) of 1.3, or 6.5 mM per hour. After the preferred operating conditions were established, namely 140° C. and 270 psi, a 0.25+aα cis flexi coker feed pulse of the composition shown in the previous example was injected into the column. After injection, the flow of n-hexane desorbent was resumed and the components of the feed were eluted. Effluent samples were collected periodically and analyzed by GC. Their composition is plotted in Figure 2 against the volume of desorbent used for elution.

According to FIG. 2, the aromatic (and branched aliphatic) hydrocarbons of the feed were eluted first, as they were easily driven out of the voids of the silicalite column by the desorbent.

This initial part is the raffinate. The elution of the concentrated extract of n-decane and 1-n-decene components occurred with a distinct delay. These components in the extract were apparently co-eluted since they were simultaneously expelled from the silicalite channels by the desorbent. -n-
Decene is much harder to displace than n-decane. As shown in the figure, there is an intermediary separation of the eluate between the raffinate and the extract (in-between-Cu
t) occurred.

Both the raffinate and the extract were analyzed in some detail by GC. Analysis of the raffinate indicated that substantially all aromatic components of the feed were recovered. The results of GC analysis of the extract are shown in FIG.

FIG. 3 shows that n-decane and 1-n
- In addition to decene, significant amounts of internal linear decene (5-4
-1 and 2-decene) were recovered in the extract. A portion of the latter compound was already present in the feed. Additional amounts were produced by isomerization of l-n-decene during the adsorption-desorption process.

The chromatogram in this figure also shows the presence of a small amount of 2-methyl-1-nonene in the extract, about 0.5%. This compound and related 2- by silicalite
Some adsorption of methylnonane was demonstrated by the model compound experiments described in Example 7.

Example 14 The rates decreased in all the rafts, indicating their selective adsorption. In the raffinate, the concentration of most aromatic hydrocarbons increased as they were rejected. Various silicalites and sodium zeolites showed similar adsorption behavior.

Similar tests with different test times showed that the adsorption was substantially complete within 1 hour.

Approximately 0.8 g each of an approximately 20/80 mixture of the narrow cps fractions of the previous flexi-coker distillate was added to approximately 1 g of the appropriate molecular sieve. The resulting test mixture was
The raffinate was analyzed after heating at ℃ for 1 hour. Results ■
Shown in the table.

The data in the table are 1-n-decene, n-decane, trans-
Concentrations of 2-decene and major identified aromatic hydrocarbon components are shown. Compared to the composition of the feed, the percentage of 1-n-decene and n-decane is 10% of the model compound and heptamethylnonane solution. Approximately 2.5 g of the /90 mixture was added to 1 g of acid/base washed silicalite to make a test mixture.
heated for an hour. The supernatant raffinate and starting feed were then analyzed by GC. Their compositions are compared in Table X■.

According to the data in the table, I n-dodecene and n-dodecane were adsorbed by silicalite, but aromatic hydrocarbons and benzothiophenes in their boiling range were not adsorbed.

tilbenzene naphthalene benzothiophene 1-n-dodecene n-dodecane 22.3 4.3 19.6 24.0 33.8 6.4 3.3 10.0 Narrow CI of light gas oil for flexi coke machine.

Approximately t, 4 g of a 10/90 mixture of distillate fraction (bp, 212° C.) and heptamethylnonane are mixed with 1 g of acid/
Added to base washed silicalite. 15% of the resulting mixture
Heated at 0°C for 2 hours. Samples of the supernatant raffinate and starting feed were then analyzed by GC.

The sound field factors of some of the main components are shown in Table XIV.

The data in the table shows a decrease in the concentration of 1-n-dodecene, and n-dodecane and a concomitant increase in the concentration of 1,2,3.5-tetramethylbenzene and naphthalene in the raffinate. This, of course, represents the selective handling of the two main linear aliphatic hydrocarbon components. Similar results were obtained when the test mixture was heated to 195°C instead of 150°C.

X ■ Thylbenzene naphthalene 1-n-dodecene n-dodecane 3.3 29.1 17.7 6.4 5.0 9.2 0.5 5.8 1.9 Example 17 Fin adsorption C, ~ C13 model compound and heptamethylnonane 1
Approximately 19 of the 5/85 mix was added to the sodium ZSIJ-5.

The resulting test mixture was heated at 120°C for 2 hours.

Samples taken after 1 and 2 hours were analyzed by GC and their composition compared with that of the feed I;
. To illustrate the results, Figures 4 and 5 show the feed and 1
Figure 3 shows a time raffinate capillary gas chromatography column. The quantitative GC composition of the feed and raffinate is shown in Table X7.
show.

According to the data in the table, C1 to CI! The model feed mix contained r equivalents (9% by weight) of C, to Cx*1-n-olefins. In addition, a similar amount (5.7% by weight)
) C1 to C11 n-paraffins were present in the feed. The concentration of the remaining hydrocarbon components was approximately 3.5% by weight. The percentages determined by GC are somewhat different because the factors of GC detection are different, but they are similar.

A comparison of FIGS. 4 and 5 shows that in the raffinate, the concentration of all 1-n-olefins and n-paraffins was reduced due to selective co-absorption.

Surprisingly, the decrease in their concentration increases as their carbon number increases. Within 2 hours, the GC concentration of 1-n-nonene decreased from 9.7 to 9.4% while 1
The GC concentration of -n-dodecene decreased from 9.1 to 1.1%. A similar trend is observed for the n-paraffin component, as shown by the comparison of FIGS. 4 and 5 and the data in the table.

Based on each concentration change, the somewhat branched C
The 4° aliphatic hydrocarbons, 2-methylnonane and 2-methyl-1-nonene, are adsorbed to some extent, but linear CI, aliphatic, n-decane and! -n-decene was found to be much smaller in amount than -n-decene.

The concentration of aromatic hydrocarbon components increased significantly in the raffinate, indicating that they were rejected from the adsorbate. Two aromatic sulfur components, 2,5-dimethylthiophene and benzothiophene, behaved differently depending on their size. The smaller 2,5-dimethylthiophene was adsorbed to some extent, but the larger benzothiophene molecules were not.

Comparison of the composition of the 1 hour and 2 hour raffinate samples showed that most of the adsorption occurred during the first hour. 8
A similar but slower adsorption took place at 0°C. Experiments with mixtures of model compounds from C, to CI3 showed that the effect of molecular weight on the simultaneous adsorption of 1-n-olefins and n-paraffins was similar. The above experiments show that the present separation method is applicable to wide carbon range refinery streams such as heavy flexi-coker naphtha and light coker gas oil.

,,:+ °( Higashi KM 18 Distillates in the boiling point range of 139 to 234 °C are combined in a ratio such that the 1-n-olefin concentration is in the range of 2.1 to 3.1%, and C, to A mixture of C13 7 lexicoke distillates was prepared. This feed was then diluted with heptamethylnonane to create a 21.5% precursor solution. The molecular sieves used for adsorption were Swiss Uechcon (
Sodium ZSM-5 was made by direct synthesis by tJetikon). Approximately 1.29 g of the test solution was added to 1 g of zeolite and the mixture was heated at 120° C. for 1 hour. The supernatant raffinate liquor was then analyzed by GC and its composition compared to that of the feed. Capillary gas chromatograms of the feed and raffinate are shown in Figures 6 and 7, respectively.

A glance at the chromatogram reveals that 1-n-olefin and n-paraffin were selectively adsorbed. Those GO peaks were difficult to see in the raffinate. Quantitative data showing the concentrations of these components and some identified aromatic compounds in the feed and raffinate are shown in Table XVI. According to the data in the table, the concentration of aromatics increased as the concentration of 1-n-olefins and n-paraffins decreased in the raffinate. This decrease in linear aliphatic concentration due to adsorption is due to CI! , C9 to C11 in the range of C10
This was probably due to the greater overlap of the aromatic GC peaks in the high carbon range.

It is thus clear that the present selective adsorption-desorption method is applicable to a wide range as well as a narrow range of carbon feeds.

= Mama ==- α-1+1, :+- 1"L" stopper adsorption of 5% each of i-n-tetradecene, 7-tetradecene,
n-tetradecane, 1% benzothiophene and 84
A mixture of model compounds was made from % decalin. Approximately 2
．． 7 g of this mixture was mixed with 1 g of acid/base washed silicalite and heated at 150° C. for 2 hours. Subsequent analysis of the raffinate showed that all of the CI4 n-aliphatic hydrocarbons were adsorbed onto the silicalite. However, n-tetradecene was removed more selectively than n-tetradecane.

Later analysis showed that as a result of adsorption by silicalite, the concentration of 1-n-tetradecene in the C14 flexi-coke cut decreased from 15.6 to 0.4% (39 min ). The concentration of n-tetradecane was similarly reduced from 19.0 to 0.7% (a 27-fold reduction). However, it should be noted that these values are semi-quantitative because the GC baseline is high. In this high carbon range of coke distillate feeds and raffinates, accurate determination of single compounds is usually not possible with boiling point GC columns.

Approximately 1.5 g of a 10/90 mixture of FLEXICOKER light gas oil narrow C14 distillate fraction (bp, 248-250°C) and decalin was added to 1 g of acid/base washed silicalite. The test mixture was then heated at 200°C for 1
heated for an hour. The isomerization of excess 1-n-decene by unacid/base treated silicalite in the presence and absence of about 5% benzothiophene on the feed and supernatant raffinate was measured at 120° C. in 1 hour. . In the absence of sulfur compounds, 30% internal n
- Decene was detected by GC. When sulfur was present, only 10% of the feed was isomerized.

Example 22 A mixture of C1 to CI3 n-olefins and n-paraffins was separated from the corresponding broad flexi-coke distillate by molecular adsorption of the type described in Example 12. This mixture containing 1-n-olefins from C1 to cls as the main reactive component was then oligomerized using a complex of boron trifluoride with an alcohol, ie neopentyl alcohol. Oligomerization is carried out in the liquid phase at a temperature and pressure sufficient to sufficiently convert not only the terminal 1-n-olefin component but also most of the internal n-olefin to form a polyolefin oligomer containing olefin trimer as the main component. I did it.

The resulting polyolefin-0-paraffin mixture was then separated by distillation to give a sulfur-insensitive transition metal sulfite catalyst rough-in and n-paraffin mixture. N-baraffin and isoparaffin dimer were distilled out. Residual isoparaffin products containing primarily trimers and tetramers are desirable synthetic lubricating oils. Conversion of the n-paraffinic distillate to linear olefin intermediates for the production of biologically degradable alkylbenzene sulfonates by conventional chlorination-dehydrochlorination reactions. Isoparaffin dimers are useful as low volatility solvents.

The presence of significant amounts of linear internal olefins and small amounts of monomethyl branched olefins in the feed distinguishes this polyolefin lubricating oil product from prior art products. The presence of even and odd carbon number carbon reactants in comparable amounts in the feed also converts this product from ethylene to even carbon number 1-n
-Polyσ made using conventional technology via olefin-
This makes it superior to olefin lubricants.

FIG. 1 shows a capillary gas chromatogram of the narrow O1e fraction of the flex distillate, which is most frequently used as a feed for zeolite separation.

Figure 2 shows the n-
Desorption with hexane is shown.

Figure 3 shows the n of the C8° fraction of the 7 Lexi coke distillate.
Figure 2 shows capillary gas chromatograms of -decene and n-decane extracts obtained in a pulse test.

Figures 4 and 5 show capillary gas chromatograms of feed mixtures of C5 to C13 model compounds and raffinates made from the mixtures.

Figures 6 and 7 show gas chromatograms of the flexi-coker distillate feed C, to CtS and its raffinate product.

patent application agent

Claims (1)

[Claims] 1. A mixture of C_6 to C_1_■ aliphatic and aromatic hydrocarbons with a neutral molecular sieve adsorbent, and conditions sufficient to selectively adsorb n-olefins and n-paraffins. contacting the n-olefin with n
- contacting the sieve product containing the concentrated extract with adsorbed paraffins with a more volatile desorbent under conditions sufficient to drive the extract from the sieve; From the mixture of aliphatic and aromatic hydrocarbons, C_5 to C_1_9 n-olefins and n
- A method for separating a mixture of paraffins. 2. The method of claim 1, wherein both adsorption and desorption are carried out within a temperature range of 10°C to 250°C. 3. The method of claim 1, wherein the adsorption and desorption occur in the liquid phase. 4. The molecular sieve adsorbent is silicalite (silica-
lite). 5. The method according to claim 4, wherein the silicalite adsorbent is previously treated with an acid and a base. 6. The method according to claim 1, wherein the desorbent is an n-olefin and/or an n-paraffin. 7. The method of claim 1, which is selective for the separation of mixtures of 7,1-n-olefins and n-paraffins. 8. Claim 1, wherein the hydrocarbon feed contains organic sulfur compounds in a concentration corresponding to 0.05% to 3% sulfur.
The method described in section. 9. The process of claim 1, wherein the hydrocarbon feed is a distillate produced from petroleum residues by high temperature pyrolysis. 10. A mixture of aliphatic and aromatic hydrocarbons is mixed with a neutral molecular sieve in the liquid phase at a temperature range of 80°C to 200°C for a period of time sufficient to effect the adsorption of a mixture of n-olefins and n-paraffins. , and desorbing the resulting concentrated mixture of n-paraffins and n-olefins from the sieve with a more volatile n-olefin. A method of separating such a mixture of n-paraffins. 11. The method according to claim 10, wherein the molecular sieve adsorbent is silicalite. 11. The method of claim 10, which is selective for the separation of mixtures of 12,1-n-olefins and n-paraffins. 13, a feed of C_5 to C_1_9 olefins of cracked petroleum distillates, produced from petroleum residues by high temperature pyrolysis and as the main type of olefin component.
n-olefin and 0.05% organic sulfur compound
of sulfur in a neutral molecular sieve for a period sufficient to effect adsorption of n-olefins and n-paraffins in the liquid phase at a temperature range of about 10°C to about 250°C; contacting step, and the generated 1-n
- Olefins - The concentrated mixture of n-paraffins is sieved from the more volatile n-olefins or n-paraffins.
- desorption of C_ from a mixture of aliphatic and aromatic hydrocarbons under adsorption conditions with paraffin.
The 1-n-olefin of ■ to C_1_9 and the n-
How to separate paraffin mixtures. 14. The method according to claim 13, wherein the molecular sieve adsorbent is silicalite. 15. made from vacuum residue by high temperature pyrolysis in a fluidized coke or flexi-coke apparatus, containing more than 20% of olefins, more than 30% of the olefins being of type I, and A feed of cracked petroleum distillate C_9 to C_1_9 olefins containing organosulfur compounds at concentrations greater than 0.3% sulfur is heated from about 80°C to about 200°C with a neutral molecular sieve.
contacting the n-olefin with the n-paraffin in a liquid phase in a temperature range for a sufficient period of time to adsorb the n-paraffin;
and the resulting concentrated mixture of 1-n-olefins-n-paraffins is sieved from the more volatile n-paraffins.
- A method for separating a mixture of the 1-n-olefin and the n-paraffin of C_9 to C_1_■ from a mixture of aliphatic and aromatic hydrocarbons, including a step of desorption using an olefin and/or n-paraffin. . 16. The method according to claim 15, wherein the molecular sieve adsorbent is silicalite. 17. The method of claim 15, wherein the molecular sieve adsorbent is sodium ZSM-5. 18.C_5 to C_1_9 aliphatic and aromatic hydrocarbon mixtures are heated at about 10°C to about 20°C using a neutral molecular sieve.
a step of contacting the 1-n-olefin and n-paraffin components in a gas phase or liquid phase at a temperature range of 0° C. for a time sufficient to selectively adsorb the n-paraffin component;
- a concentrated mixture of olefins and n-paraffins,
Desorption with a more volatile n-olefin or n-paraffin and converting the olefinic component of the mixture into less volatile products by reactions selected from the group consisting of oligomerization, alkylation, and carbonylation. A selective separation-conversion process comprising the steps of converting and separating unconverted paraffin components from the olefin derived product by distillation. 19. Claim 1, wherein the adsorbent sieve is silicalite.
The method described in Section 8. 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 by carbonylation. 22, a feed of C_9 to C_1_3 olefins of a cracked petroleum distillate made from the vacuum residue by high temperature pyrolysis in a fluidized coke or flexi-coke apparatus, containing more than 20% olefins; More than 30% of the olefins are of type I and also contain organic sulfur compounds at concentrations greater than 0.3% sulfur, with a neutral molecular sieve adsorbent and approximately 100% of the olefins.
contacting the 1-n-olefin with the n-paraffin component in a liquid or gas phase at a temperature ranging from 250°C to about 250°C for a period sufficient to effect selective adsorption of the 1-n-olefin and n-paraffin components; desorbing the enriched mixture of n-paraffins from the sieve with a more volatile n-olefin or n-paraffin, and desorbing the olefin component in the mixture thus separated in the presence of an acid catalyst. selectively reacting the oligomers containing 2 to 6 monomer units, hydrogenating the olefinic unsaturation of the oligomers to produce isoparaffin lubricating oil, and unreacted n-paraffin components, A selective separation-oligomerization method comprising the step of removing by distillation from a reaction mixture containing isoparaffins. 23. Claim 1, wherein the oligomerization of the olefin component is carried out in the presence of boron trifluoride alcohol.
The method described in Section 9.