BENZENE REMOVAL FROM

GASOLINE BOILING RANGE STREAMS

FIELD OF THE INVENTION

The present invention relates to the production of gasoline boiling range streams which are substantially reduced in benzene. At least a portion of the gasoline boiling range stream is passed through an adsorption zone containing an adsorbent which will selectively adsorb benzene from the stream, which can then be desorbed from the adsorbent with an appropriate desorbent. The treated stream is then passed to a distillation zone wherein a benzene concentrate stream is separated from the desorbent. The desorbent can then be recycled.

BACKGROUND OF THE INVENTION

Motor gasolines are undergoing ever changing formulations in order to meet ever restrictive governmental regulations and competition from alternative fuels, such as methanol. One requirement for modern gasolines is that they be substantially benzene free.

While various techniques can be used to selectively remove benzene from gasoline boiling range streams, the use of solid adsorbents, such as molecular sieves, presents advantages over other techniques such as distillation and solvent extraction. Distillation is not suitable primarily because benzene, which has a normal boiling point of about 80° C, forms low boiling azeotropes with normal hexane and naphthenes, such as methyl cyclopentane and cyclohexane. Efficient separation of the benzene from the paraffinic compounds by distillation is not possible because the azeotropes tend to come overhead with the paraffinic compounds. These azeotropes boil in the same range as do normal hexane in a light naphtha cut, i.e., 65 to 70° C. Once the benzene is removed, this separation becomes simple. Extraction with a solvent, such as sulfolane, is technically feasible, but is not as economically attractive as the use of solid adsorbents.

Solid adsorbents have been used in the past for removing all aromatics from the non-aromatic fraction of a mixed hydrocarbon stream. For example, U.S. Patent No. 2,716,144 teaches the use of silica gel for separating all aromatics from gasoline or kerosene fractions. The

silica gel containing adsorbed aromatics can then be desorbed with a suitable desorbent, such as an aromatic containing hydrocaroon having a boiling point different than the benzene-containing process stream which is passed over the adsorbent. Other U.S. patents which teach the use of siϋca gel for adsorbing aromatics from a process stream, followed by desorption by use of a liquid hydrocarbon include U.S. Patent Nos. 2,728,800; 2,847,485; and 2,856,444.

The separation of aromatics from process streams by use of a molecular sieve is taught in U.S. Patent No. 3,963,934. In that patent, a 13X molecular sieve is taught to adsorb not only aromatics, but also olefins and sulfur from a C ₅ /C ₆ naphtha stream prior to isomerization. U.S. Patent No. 3,992,469 also teaches the use of molecular sieves for separating all aromatics from process streams. Type X and type Y crystalline aluminosilicates zeolites are taught as preferred molecular sieves. Also, U. S. Patent No. 4,014,949 discloses that partially hydrated NaY gives a separation factor of 1.6 for benzene (adsorbed) with toluene.

While much work has been done to separate aromatics from non-aromatics in process streams, there is still a need in the art for selectively removing benzene from both the aromatic and non-aromatic components of the stream. The need to remove benzene from gasoline boiling range streams is more critical today in order to meet stringent government requirements.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a process for selectively removing benzene from paraffins and other aromatic gasoline boiling range process streams. The process comprises:

(a) passing at least a portion of a gasoline boiling range hydrocarbonaceous process stream to an adsorption zone containing a solid adsorbent comprised of an aluminosilicate zeolite material having a silica to alumina ratio of less than about 10, and an average pore diameter greater than the size of the benzene molecule;

(b) passing a desorbent capable of extracting benzene from the adsorbent and having an average boiling point which is at least 5°C different than the boiling point of benzene, through the bed of benzene-containing adsorbent in the adsorption zone, thereby removing benzene from the adsorbent;

(c) passing the benzene-containing desorbent to a distillation zone to separate benzene from the desorbent, thereby resulting in a benzene rich stream and a desorbent stream; and

(d) recycling the desorbent stream back to the adsorption zone.

In a preferred embodiment of the present invention, only a heartcut fraction of the hydrocarbonaceous process stream is passed to the adsorption zone. Said heartcut fraction will preferably have an average boiling point from about 50° C to about 90° C, and contain a higher concentration of benzene than the hydrocarbonaceous process stream.

In another preferred embodiment of the present invention, the zeolite material is a 12 ring or greater zeolite selected from:

(a) Zeolite L framework (code LTL) containing Group IA cations (lithium, sodium, potassium, rubidium, cesium) or mixtures thereof.

(b) Zeolite X framework (code FAU) containing Group IA cations or mixtures thereof.

(c) Zeolite Y framework (code FAU) containing Group IA cations or mixtures thereof.

(d) Zeolite mordenite framework (code MOR) containing Group IA cations or mixtures thereof.

The zeolite framework codes are taken from the publication "The Zeolite Cage Structure" by J. M. Mervsa , Science, 7 March 1986, Volume 231, pp 1093-1099, which is incorporated herein by reference.

In other preferred embodiments of the present invention, the aluminosϋicate zeolite material is a NaY zeolite, especially one that is at least partially dehydrated.

In another preferred embodiment of the present invention, the desorbent is a stream which already exists in the refinery or chemical plant which may be passed directly to the adsorption zone.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 hereof is a simplified flow diagram of the process of the present invention wherein the entire gasoline boiling range hydrocarbonaceous stream is sent to the adsorption zone.

DETAILED DESCRIPTION OF THE INVENTION

Process streams on which the present invention can be practiced include those in the gasoline boiling range. In general, the gasoline boiling range can be considered to be in the temperature range of about 80 to 190° C. Preferred process streams include reformates and hydrocrackates, especially reformates.

Turning now to Figure 1, a preferred flow scheme is shown for the situation wherein the entire gasoline boiling range process stream is fed via line 10 into adsorption zone 1, which contains a solid adsorbent capable of selectively adsorbing benzene from the stream, even in the presence of other aromatics, such as xylene and toluene, and non-aromatics, such as paraffins. The adsorption zone is operated at any suitable set of conditions, preferably including the temperature of the feedstream, which will typically be from about ambient temperatures (20° C) to about 150° C. The adsorption zone can be comprised of only one adsorption vessel, or two separate vessels, as depicted in the sole figure hereof. It can also be comprised of three or more vessels with the appropriate plumbing for continuous adsorption and regeneration of the adsorbent. The adsorption/desorption zone can be run under any suitable mode, examples of which include fixed bed, moving bed, simulated moving bed, and magnetically stabilized bed.

In another preferred mode of operation of the present invention, the process stream is first be fractionated so that only a heartcut of said process stream is passed to the adsorption zone. The heartcut fraction will have an average boiling point from about 50° C to

about 90° C, and contains a higher concentration of benzene than the hydrocarbonaceous process stream, is passed to the adsorption zone.

The product stream which leaves the adsorption zone via line 12 is a substantially benzene-free gasoline boiling range stream.

The solid adsorbent is a cation exchanged zeolitic material which is capable of selectivity adsorbing benzene from the stream. Preferably, the zeolite adsorbents of the present invention: (a) have a silica to alumina ratio of less than 10, especially from 1 to 3; (b) an average pore diameter from about 6 to 12 Angstroms (A), preferably from about 6 to 8 A ; and (c) having a separation factor greater than 1 for benzene versus toluene. That is, it will have a preference for adsorbing benzene than it will for adsorbing toluene. The cation is selected from alkali metals: lithium, sodium, potassium, rubidium and cesium. Preferred is sodium. Preferred cation exchanged zeolites are the 12 ring or greater zeolites. Non-limiting examples of such zeolites include: L-type zeolites, X-type zeolites, Y-type zeolites, and mordenite type zeolites, all of which contain one or more different Group IA cation. By "L-type" zeolite is meant those zeolites which are isostructual zeolite L. The same holds true for the X-type, Y-type, and mordenite-type. That is, the X-type zeolites are isostrutual to zeolite X, etc.

More preferred is NaY. Especially preferred zeolites are those that are at least partially dehydrated. They can be dehydrated by calcining them at an effective temperature and for an effective amount of time. Effective temperatures will generally be from about 90° C to 150° C, preferably from about 150° C to 200° C, and more preferably from about 200° C to 260° C. An effective amount of time will be for a time which will be effective at reaching the desired level of dehydration at the temperature of calcination. Generally this amount of time will be from 1 to 4 hours, preferably from about 2 to 3 hours.

The solid adsorbent is regenerated by treating it with a suitable desorbent. Suitable desorbents are organic solvents, both aromatic and non-aromatic, which have a boiling point different than

benzene by at least 5°C, preferably by at least 10° C. Preferred desorbents are aromatic solvents, more preferred are toluene and xylene, and most preferred is toluene. It is also to be understood that refinery streams, having substantial concentrations of such aromatic solvents can also be used. The desorbent enters the adsorption zone via line 14 where it contacts the benzene-containing adsorbent and desorbes the benzene. The desorbent can be either a liquid or vapor, with liquid being preferred.

The desorbent, which now carries the desorbed benzene, leaves the adsorption zone via line 16 and is passed to distillation zone 2 where a benzene-rich stream is separated from the desorbent and passed via line 18 to one of three options. One option would be to collect the benzene-rich stream as is, via line 20, which can be sent to existing extraction facilities. This benzene-rich stream will typically be comprised of at least 50 wt.%, preferably at least 75 wt.% benzene. Another option would be to pass the benzene-rich stream to a distillation zone 4 where benzene is separated from any lighter components, thereby collecting a substantially pure, chemical grade, benzene stream via line 22. The lighter components can then be recycled via line 24 to the adsorption zone. The third option is to pass the benzene-rich stream to hydrogenation zone 5, where the benzene is hydrogenated to cyclohexane. It can also be converted to toluene in another unit. The cyclohexane can be collected via line 26. The regenerated desorbent from distillation zone 2 is passed via line 19 to distillation zone 3 where it is separated from heavier components. The heavier components are passed via line 21 to line 12 where they can be blended with the substantially benzene-free gasoline stock. The desorbent is passed overhead via line 14 to the adsorption zone. It is understood that this particular process scheme is for the case when the desorbent has a higher boiling point than the desorbed benzene. Of course, the scheme would be different if the desorbent had a lower boiling point than benzene. In such a case, the desorbent would exit distillation zone 2 from the top and the benzene concentrate stream from the bottom.

Having thus described the present invention, and preferred embodiments thereof, it is believed that the same will become even more apparent by the examples to follow. It will be appreciated, however, that the examples are for illustrative purposes and are not intended to limit the invention.

EXAMPLE 1

Various cation-exchanged forms of zeolite L powder were con¬ tacted at 25° C in sealed vials with a hydrocarbon mixture which contained 3.0 g. of benzene, 3.0 g. of toluene, 60.0 g. of decalin and 2.0 g. of tri-tertiarybutyl benzene. The contacting was carried out by shaking the vials for a period of over 4 hours. This was long enough for the zeolite and hydrocarbon phases to come to equilibrium. The hydrocarbon phase was analyzed by gas chromatography before and after contacting with the zeolite. From the analyses, calculations were made of the zeolite separation factor for benzene versus toluene, and the zeolite capacity to adsorb benzene plus toluene.

Separation factor is defined as _{αB/τ =} [(benzene)/(to1uene)] _{in zgo e} [(benzene)/(toluene)]. _{n solution}

at equilibrium. Capacity is defined as weight percent benzene plus toluene on zeolite at equilibrium.

The following results were obtained:

TABLE I

Capacity, Separation Factor Zeolite SiJAl Ratio Weight % «B/T

LiL 2.6 8 1.3

KL 2.6 2 1.6

This example shows that LiL and KL zeolites show a separation factor in favor of benzene adsorption over toluene, i.e., «B/T > 1.0.

EXAMPLE 2

The experiment of Example 1 was repeated using various cation-exchanged forms of zeolite X powder. The results obtained are shown in Table II.

TABLE II

Capacity, Separation Factor

Zeolite SiJAl Ratio Weight % «B/T

LiX 1.5 7 5.5

NaX 1.0 20 1.4

NaX 1.5 18 1.0

NaRbX 1.5 6 10.0

NaCsX 1.5 8 3.0

MgX 1.5 14 1.4

This example shows that a number of X-type zeolites show a separation factor in favor of benzene adsorption in preference to toluene.

EXAMPLE 3

The experiment of Example 1 was repeated using various cation-exchanged forms of zeolite Y powder. The results obtained are shown in Table III.

TABLE III

Capacity, Separation Factor

Zeolite Si :A1 Ratio Weight % «B/T

LiY 2.5 28 1.6

KY II 17 1.5 NaY II 17 2.9

MgY II 19 1.2

LiNaY II 15 1.3

CsKY II 6 1.6

RbKY II 16 1.2

LiKY II 24 1.7

NaLaY II 21 1.3

This example shows that a range of Y zeolites gives a selective separation of benzene versus toluene by adsorption. It also show that Y zeolite, with mixed cations, show a preference to adsorb

benzene over toluene. Furthermore, the data show that NaY zeolite has a very favorable combination of capacity and separation factor.

EXAMPLE 4

The experiment of Example 1 was repeated using various cation-exchanged forms of zeolite Mordenite. The results obtained are shown in Table IV.

TABLE IV

Capaci ty, Separati on Factor

Zeol i te SiJAl Ratio Wei ght % ^« B/T

Li MOR 6.2 6 1.9 Cs MOR 6.2 8 1.6

This example shows that mordenites also preferentially adsorb benzene over toluene.

COMPARATIVE EXAMPLE

The experiment of Example 1 was followed except several other zeolites were used. The zeolites used and the results obtained are shown in Table V.

TABLE V

Capacity, Separation Factor Zeolite Si:Al Ratio Weight % ^« B/T

ZSM-5 3 5 0.33

Cu ⁺² Y 2.5 8 0.38

Li LZ-; no ~5 16 ~1

BaECR- -32* ~6 16 ~0.6

* ECR-32 is a faujasite type of zeolite and its description is found in U.S. Patent No. 4,931,267 which is incorporated herein by reference.

The above table evidences that not all zeolites are selective for the adsorption of benzene over toluene.

EXAMPLE 5

A feed comprised of 5 wt.% benzene, 5 wt.% toluene, 5 wt.% xylene, with the remainder being methylcyclopentane (MCP), was passed through an adsorption column comprised of a bed of 300 g. NaX zeolite

adsorbent at room temperature (72° F) . Samples of treated feed, as it exited the column, were analyzed in time intervals indicated in Table VI below for the individual components of the feed.

TABLE VI

Time, min Benzene Toluene Xylene MCP

5 0 0 0 100

10 0 0 0 100

15 0 0 0 100

20 0 0 0 100

25 0 0 0 100

28 0 0.5 1 98.5

32 0 2 5 93

35 0.1 4.5 8* 87.4

* concentration greater than feed because of it being displaced with benzene and toluene in the adsorption column.

The adsorbent was desorbed by passing toluene through the bed of adsorbent at a flow rate of 20 cc/min. and the concentration of benzene was monitored at the time intervals set forth in Table VII below.

TABLE VII

Time, min. Benzene, wt.%

10 5

15 30

18 10

20 7

30 1

35 0.5

40 0

EXAMPLE 6

The procedure of Example 5 was followed except that the feed was a refinery reformate comprised of 6 wt.% benzene and 25 wt.% C ₈ aromatics (xylenes and ethyl benzene). The results are set forth in Table VIII below. The results show that benzene is more selectivity adsorbed than C ₈ aromatics as the C ₈ aromatics exit earlier than benzene.

lTiABLE VIII Time. Min. C Aromatics, Wt.% Benzene, Wt.%

5 0 0

10 0 0 14 1.0 0 16 2.0 0 18 4.0 0 20 6.3 0 22 8.8 0 24 10.5 0.4 26 10.8 0.8 28 11.8 1.7 30 20.0 2.4 35 25.0 4.0 40 25.0 5.4 45 25.0 5.8 50 25.0 6.0

The adsorbent was desorbed by passing toluene through the bed of adsorbent at a flow rate of 20 cc/min and the concentration of benzene of C ₈ aromatics was monitored at these time intervals set forth in Table IX below.

TABLE IX

Time. Min. C ₈ Aromatics, Wt.% Benzene. Wt.%

0 25 6.0

5 25 6.0

10 18.5 6.8 11 15.0 7.0 14 10.0 0 15 3.0 2.4 20 0.6 0.4 25 0 0.03 30 0 0 40 0 0

EXAMPLE 7

A feed comprised of 10 wt.% benzene and the remainder being methylcyclopantane (MCP), which represents a heartcut fraction of a gasoline boiling range stream, was passed through an adsorption column comprised of a bed of 300 g. NaX zeolite adsorbent at room temperature. Samples of treated feed, as it exited the column, were analyzed in time intervals indicated in Table X below for the individual components of the feed.

TABLE X

Time. Min. Benzene, Wt.% MCP. Wt.%

5 0 100

10 0 100

20 0 100

30 0 100

40 0 100

50 0 100

60 0.01 99.99

62 0.1 99.99

64 1.6 98.4

65 3.0 97.0

66 7.0 93.0 68 9.0 91.0 70 9.3 90.7 75 10.0 90.0

The adsorbent was desorbed by passing toluene through the bed of adsorbent at a flow rate of 20 cc/min and the concentration of benzene was monitored at the time intervals set forth in Table XI below.

TABLE XI

Time. Min. Benzene, Wt.%

0 10

5 10

10 30

12 20

14 9

16 6

18 5

20 4

30 1

38 0

40 0

EXAMPLE 8

The procedure of Example 7 was followed except that the feed was a refinery stream (hydrocrackate) comprised of ~5 wt.% benzene and ~5 wt.% paraffins, isoparaffins, naphthene, etc. For the sake of simplicity the non-benzene portion of the feed is designated as paraffins, the results are set forth in Table XII below.

TABLE XII Time. Min. Benzene, Wt.% Paraffins Wt.%

5 0 100

10 0 100 15 0 100 20 0 100 25 0 100 30 0 100 35 0 100 40 0 100 45 0 100 50 0.10 99.9 60 0.25 99.75 65 0.40 99.6 70 0.80 99.2 75 1.0 99.0 80 1.6 98.4 90 2.5 97.5 100 3.5 96.4 120 4.3 95.7 140 4.7 95.3 180 5.0 95.0

The adsorbent was desorbed by passing toluene through the bed of adsorbent at a flow rate of 20 cc/min and the concentration of benzene was monitored at the time intervals set forth in Table XIII below.

TABLE XIII Time, Min. Benzene. Wt.%

5 5

8 5

9 20

10 33

11 57

12 40

13 14.5

14 6

15 4.5 20 0.1 30 0 35 0 40 0

EXAMPLE 9

A sample of NaY zeolite were fully saturated with water by keeping them over a saturated solution of NaCl in a desiccator for 4 days. The sample was then calcined at a temperature of 100° C for 2

hours and portion was taken for benzene adsorption experiments, which will be discussed below. The remainder of the zeolite sample was then calcined at 200° C for 2 hours and a sample taken for a benzene adsorption experiment. This procedure was repeated at 300° C, 400°C, and 500° C. The benzene adsorption experiments were conducted on a model mixture comprised of 60.06 g. of decalin(cis) as a solvent, 2.02 g. of tritertiary butyl benzene (TTBB) as an unadsorbed internal standard for gas chro atograph analyses, 3.03 g. benzene, and 3.02 g. toluene. This represented a 1/1 benzene/toluene mix. The pure liquids used to prepare the model mixture were dried thoroughly over zeolite 4A pellets and the TTBB, which was a solid, was dried for one hour in a hot air oven at 35° C. The calcined zeolite samples were dried for 4 hours at 400° C then transferred to a desiccator at 130° C which had been purged with dry nitrogen. All weighing of zeolite samples were carried out in balance case free of atmospheric moisture. New air tight vials were used to contain the zeolite and solution phase. The model mixture was contacted with the zeolite sample overnight at room temperature(about 22° C). The model mixture phase and the zeolite phase were separated by filtration and a gas chromatographic analysis was performed using the TTBB as the internal standard. The results of benzene adsorption are shown in Table XIV below.

TABLE XIV

Calcination Benzene + Toluene Sep<aration Factor

Temperature ° C Wt, .% Adsorbed «B/T

100 9.4 1.3

200 18.8 2.7

300 18.6 2.7

400 17.3 2.9

500 17.8 2.8

EXAMPLE 10

The above conditions for the adsorption experiments were used to test the adsorption characteristics of NaY and

NaX for selectively removing benzene from a model mixture containing benzene (B), toluene (T) , and 1-methyl naphthalene (1-MN). The results are shown in Table XV below.

TABLE XV

Benzene + Toluene Separation Separation + 1-Methyl Naphthalene, Factor Factor

Zeolite Wt. % Absorbed B/T B/l-Mfi

NaX 16.1 1.2 1.4

NaY 25.7 2.3 11.1

The above table shows that NaY zeolite is superior to NaX zeolite for selectively removing benzene over 1-methyl naphthalene. Benzene and 1-methyl naphthalene compete approximately equally for NaX zeolite. These results are evidence that NaY zeolite is a absorbent of choice for benzene separation from a refinery stream which contains some alky naphthalenes, such as a reformate stream.