DE2117857C3 - Process for upgrading reformates and reformers effluents Mobil Oil Corp., New York, N.Y. (V.StA.) - Google Patents

Description

The invention relates to a method for upgrading reformates and reformer effluents by contacting them with a crystalline aluminosilicate zeolite under conversion conditions brings.

The improvement of reformates to increase the octane number of gasoline, as well as the ratio of Yield to octane number has been the target of much activity in the petroleum industry for many years. In Recently, however, due to the greater attention paid to the problem of environmental protection as well the air pollution investigations with regard to the increase of the octane number of gasoline special Pay attention. Procedures that increase the octane number of gasolines are important as well this either avoids the use of lead or increases the product to higher levels Octane levels required amount of lead is brought to a minimum.

hs has long been known to be a reformate through various To improve methods including treatment with crystalline aluminosilicate zeolites. The previously carried out treatment of reformates with crystalline aluminosilicate zeolites included both physical treatments such as selective adsorption and chemical treatments, like selective conversion.

In virtually all known processes crystalline aluminosilicates with a pore size of about 5 A units are applied.

So is in U.S. Patents 28 51970 and 28 86 508 describes a reforming process in which a heavy fuel is reformed and the reformate or a part of the same with an aluminosilicate having a pore size of 5 A for the selective adsorption of the η-paraffins is contacted.

U.S. Patent 3,114,696 discloses one Improvement of the problem of upgrading a reformate and describes the treatment of a reformate with a crystalline aluminosilicate with a pore size of 5Ä under cracking conditions, so that the η-paraffins are cracked selectively.

From the United States patent 33 95 094 isL the Hydrokrackimg of n-paraflins from a reformate with a crystalline aluminosilicate with a pore size of about 5Λ and with a hydrogenation activity limited to the inner Poreiibtrukttir known. Overall, however, the known methods do not meet all of the requirements that a Upgrading of reformates or the like are to be provided. The task of the Jfr / i / ulung is therefore to create a Process for upgrading reformates and reformists using a crystalline Alumiiiosilikat / .colilhen, the improved results delivers both in terms of octane number and overall yield.

The process according to the invention for upgrading reformates and reformer effluents, in which they are brought into contact with a crystalline aluminosilicate zeolite under conversion conditions, is characterized in that an _{aluminosilicate zeolite having an SiO 2} : AljOs ratio of greater than 15 is used, which has been crystallized from a solution containing organic cations and contains organic cations in the synthesized form and has a pore size such that it sorbs methyl paraffins under the conversion conditions, and optionally has an associated hydrogenation-dehydration component.

The reasons why the particular zeolites give the process according to the invention improved results with regard to the upgrading of reformates or outflows from reformers are not complete clear.

The effectiveness of the method according to the invention for upgrading a reformate or a Reformer effluent is presumably based on careful control of the desired reactions and on a minimization of undesirable reactions. Normal paraffins are generally unfavorable for the octane number of the gasoline. With the method according to the invention more than just is achieved the removal of normal paraffins, since a simultaneous alkylation of at least part of the dei aromatic rings of aromatic feed with products of cracking of normal and / orei slightly branched paraffins occurred and fell this creates more highly alkylated aromatic rings in the product. In the procedure according to de Invention not just merely the undesirable! Removes materials as in known methods That was the case, but the undesirable materials are both direct to the formation of alkylaromatics as well as by alkylation of aromatics used in the loading, so that there is a high yield au desired products.

/ to achieve a successful procedure is e

necessary that the catalyst used to carry out the above functions for long periods of time and with a great deal of effectiveness and selectivity is capable, since otherwise an extraordinarily frequent regeneration would have to take place, whereby the overall economy of the operation would be impaired.

It is known that the alkylation of aromatics can be controlled with large-pore zeolites. For example include large-pore zeolites known for their alkaline activity, zeolites of the Faujasii fans, especially zeolites X and Y. However, keep under the reaction conditions as they are in the upgrading of reforinates or reformer effluents are used, large-pore zeolites, for example X and Y, their alkylating activity not during any noticeable period of time so that they are in technical operation at which Reaction conditions are used as they are usually used for upgrading or improvement were used by reformates, quickly useless will.

Presumably the fact that the previous large pore size catalysts are unsuitable for upgrading reformates is due to the fact that, in order to achieve maximum effectiveness, the catalyst must have cracking activity so that it is capable of cracking normal paraffins and must also have an alkylation activity, so that ·. · ( alkylaromatic bi'det. In fact, all previous catalysts show the disadvantage that a good cracking catalyst was usually a very poor alkylation catalyst under certain operating conditions, the reverse of the all that is, a good alkylation catalyst under specific operating conditions is a poor cracking catalyst. In order for a catalyst to be useful in improving a reformate, it is necessary that it exhibit both a cracking and alkylation function and that the cracking and alkylation function over long periods of time stable l remains so that the catalyst does not age in a short period of time.

lis is also not sufficient to be a catalyst too which is capable of forming the desired products, but it is also necessary that the desired Products are preserved during the course of implementation. That's how he is. for example with regard to the formation of alkyl aromatics is not only necessary for the catalyst to be able to form them, but rather that the alkyl aromatics are retained during the course of the reaction.

From BE-PS 6 91 493 and NL patent application 66 17 850 hydrocrystalline conversion processes are known in which crystalline aluminosilicate zeolites with a molar ratio of SiO ₂ : Al ₂ O ₃ greater than 14: 1 or 16: 1, as Kataly \ - tors serve. These zeolites are not intended as catalysts for upgrading reformates or reformer effluents. As tests have shown, the known catalysts are also unsuitable for solving the problem on which the invention is based, since they are unsatisfactory when applied to reformals, both with regard to the octane number and the overall yield.

It has been found that zeolites which crystallize from a solution containing organic cations and which contain an organic cation in the synthesized form, the organic Cations at least partially account for the electronegative properties of the aluminum atoms in the crystal lattice meet, actually se!., are effective catalysts for upgrading reformates, if they also have the other properties listed above, namely with regard to the ratio from silica to alumina and the

ίο pore size, so that methyl paraffins in the reaction conditions be sorbed. The effectiveness of catalysts of this type can vary from a variety of Factors arise, but most importantly, they help maintain their selectivity are capable of the desired reaction products for long periods of time; d. that is, these materials are extremely stable and extremely selective during the reaction conditions at which they are used Need to become. The formation of crystalline aluminosilicates from containing organic cations Solutions are known in the art as manufacturing processes and it has been found that all organic cations are usable provided the zeolite has the others above also has specified properties. However, those aluminosilicates are particularly preferred which from solutions, the alkyl ammonium and alkyl phosphonium cations contained, were synthesized.

Examples of crystalline aluminosilicate zeolites which have the properties given above, are zeolite beta, TEA-mordenite, ZSM-12 and a family of zeolites referred to as the ZSM-5 type, including the ZSM-5, ZSM-S and ZSM-11 belong.

Zeoliih Beta is a well-known zeolite which is synthesized from a solution which contains tetraethylammonium ions and is described in US Pat. No. 33 08 069.
TEA mordenite is also synthesized from a solution containing tetraethylammonium ions and has the following formula as the molar ratio for oxides in the synthesized form:

M ₂ O: Al ₂ O ₃ : 15 to 100 SiO ₂ : O to 15 H ₂ O

wherein M is a mixture of the cations, at least one of which consists of tetraalkylammonium, and /; represents the valence of M.

TEA mordenite has the crystal structure of mordenite.

ZSM-12 in its synthesized form has the following formula as a molar ratio of oxides:

1.0 ± 0.4 M ₂ O: Al ₂ O ₃ : 20 to 100 SiO ₂ :: HO

wherein M is a mixture of cations, at least one of which consists of tetraalkylammonium, /; the value of the cations M and; means a number from 0 to 60.

The most preferred zeolites used in the reformer process of the present invention are those zeolites commonly referred to as ZSM-5 type zeolites. The zeolites ZSM-5 type generally have a pore size greater than 5 Å and less than the large pore zeolites such as zeolite X, zeolite beta or the like.

The ZSM-5 type zeolites used in Ver

ears are used according to the invention, eraubcn the entry of normal aliphatic compounds and slightly branched aliphatic compounds Compounds, in particular monomethylsubstituted compounds, in their inner pore structure, however an essential barrier for the diffusion of all compounds that are at least one quaternary Contain carbon atom or a minimum molecular dimension equal to or significantly larger as a quaternary carbon atom, some may also contain aromatic and naphthenic Compounds with side celts similar to the normal aliphatic compounds and those above listed slightly branched aliphatic compounds in the inner pore structure of the present catalysts occur.

The crystalline zeolitic materials of the ZSM-5 type used in the present invention cannot be characterized simply by specifying the pore size from a range of pore sizes will. It appears that the uniform pore openings of these are made of zeolites is not about circular, as is usually the case with the zeolites used hitherto, but that they are roughly elliptical. Thus, the pore openings of these zeolites have both a major axis and also a minor axis, and that is the reason that the unusual and new molecular sieve effects be achieved. This elliptical shape can be called a "keyhole". It would appear that the minor axis of the elliptical pores of the zeolites has an effective size of about 5.5 Å units. The major or major axis appears to have a value between 6 and 9Ä. The unique The keyhole molecular sieve effect of these materials is believed to be due to the presence of these approximately elliptically shaped windows that give access to the inner crystalline pore structure steer. Definitely, even considering the specific molecular dimensions or the pore sizes of the catalysts of the ZSM-5 type, the simple fact that excellent results remain are obtained when Reformatc or reformer effluents over a catalyst from ZSM-5 type can be converted.

In one embodiment of the invention, a C ₅ hochpararfinische ^J can -Schwerbenzin fraction are deliberately added to a reformate or Reformerabstrom before its conversion over a catalyst of the ZSM-5 type. A process of this type results in increased formation of alkyl aromatics both directly and by alkylation of the aromatic components to provide an even more valuable product.

It is well known that a highly paraffinic heavy gasoline fraction is never subjected to a reformate could be mixed if the known reformate upgrading method have been applied since the entire purpose of this previous \ 'experienced in the Removal of the η-paraffins existed; therefore η-paraffins were not added deliberately. Therefore exists overall the fundamental difference between the method according to the invention and the previous ones applied upgrading method in the fact that not only certain undesirable compounds be selectively removed, d. H. normal and slightly branched paraffins, but that these paraffins alkylate the aromatic part of the reformate.

whereby an increased yield of cheaper products is obtained.

Another valuable result of this chemical reaction is that it does so at the expense of the more valuable Ben / ins produced dry gas is very low. Methane formation is particularly low; this has the advantage of a minimal dilution of the circulating hydrogen and thus an optimal reforming operation.

ίο The zeolites of the ZSM-5 type, which are used in the crlind according to Methods used include not only ZSM-5 but also the ZSM-8 zeolites and ZSM-11.

The family of ZSM-5 zeolites has the characteristics given in Table 1 below X-ray diffraction pattern. The composition of ZSM-5 can also be expressed in terms of the molar ratio of the oxides specify in the following way:

0.9 I 0.2 M ₂ O: W ₂ O,: 15 to 100 YO ₂ : ζ H ₂ O

Ti

where M is a cation, η is the valence of the cation, W is aluminum or gallium, Y is silicon or germanium and ζ is a number from 0 to 40. In the preferred synthesized form, the zcolith has the following formula as a molar ratio of the oxides:

0.9! 0.2 M ₂ O: Al ₂ O.,: 15 to 100 SiO ₂ : ζH ₂ O

wherein M is a mixture of alkali metal cations, in particular sodium, and tetraalkylammonium metal ions, where the alkyl groups preferably contain 2 to 5 carbon atoms.

In the preferred embodiment of ZSM-5, W is aluminum, Y is silicon, and the molar ratio of silica / alumina is at least 15, preferably 20, and ranges up to about 60. The members of the ZSM-5 zeolite family have a distinctly distinctive crystalline structure Structuring X-ray diffraction pattern which shows the following significant lines:

Table I.

In-planar distance d (A) Relative intensity 11.1 ί 0.2 S. 10.0 ' 0.2 S. 7.4 4 0.15 W. 7.1 J-0.15 W. 6.3 i 0.1 W. 6.04 + 0.1 W. 5.97 -t 0.1 W. 5.56 J- 0.1 W. 5.01 + 0.1 W. 4.60 -j 0.08 W. 4.25 i 0.08 W. 3.85 + 0.07 VS 3.71 + 0.05 S. 3.64 J 0.05 M. 3.04 -i 0.03 W. 2.99 I 0.02 W. 2.94 4- 0.02 W.

These values as well as the other X-ray values ν obtained by standard methods. The beam consisted of the K-aipha doublet of copper,

an S / intillier counting spectrometer with a spring mounted on a strip fat card was used. The peak heights / and the positions as a function of 2 * f), where (-) represents the Rragg angle, were read from the spectrometer dial. From this the relative intensities, IfK) ///, in which / the intensity of the strongest line or the peak and </ (obs.) The inlerplanar distance in A, according to the recorded lines, were calculated. In Table I the relative intensities are S strong, M - medium. MS medium strong, MVV medium soft and VS very strong indicated. It should be noted that this X-ray diffraction pattern is characteristic of all types of ZSM-5 masses. Due to the ion exchange of the sodium ion with cations, practically

table follows the same pattern with some minor shifts in interplanar spacing and variation the relative intensity obtained. Other minor variations may depend on the ratio from silicon to aluminum of the particular sample as well as depending on one if appropriate performed thermal treatment occur.

Her ZSM-5 zeolite can be conveniently prepared by adding a solution of water, tetra propylammopium hydroxide and elements made of sodium oxide, an oxide of aluminum or gallium, and an oxide of silicon that has a composition, given as MoI ratio of oxides, within the following ranges:

OH / SiO ₂ . .
R., N '/ (R, N
H, Ο / ΟΙΓ. .

Na ¹ )

Tables

Wide

0.07 to 1.0 0.2 to 0.95 10 to 5 to Preferred

0.1 to 0.8
0.3 to 0.9
10 to 300
10 to 60

Particularly preferred

0.2 to 0.75
0.4 to 0.9
10 to 300
10 to 40

wherein R is the propyl group c. W is aluminum and Y is silicon. This mixture is used in the Reaction conditions held until the crystals of Zcoliths are formed. The crystals are then separated from the liquid and recovered. Typical reaction conditions are a temperature of 75 to 175C for a period of time from 6 hours to 60 days. The particularly preferred temperature range is between 90 and 150 C, the period of time at a temperature in this range between about 12 hours and 20 days lies.

The digestion of the gel particles is carried out until the crystals form. The solid product will of the reaction medium, for example by cooling the total amount to room temperature, Filtration and washing with water, separated.

The ZSM-5 zeolite is preferably used as an aluminosilicate educated. The composition can be made using materials which provide the elements of the corresponding oxide. Such masses include for an aluminosilicate, for example Sodium aluminate. Aluminum oxide, sodium silicate, silicic acid hydrosol, silica gel, silica, Sodium Hydroxide and Tclrapropylammonium Hydroxide. Of course, any oxide component used in the reaction mixture can be used for the preparation of a member of the ZSM-5 family are delivered by one or more exit participants, and these can be mixed in any order. For example, the sodium oxide by an aqueous solution of sodium hydroxide or by an aqueous solution of sodium silicate to be delivered; the tetrapropylammonium cation can be provided by the bromide salt. That The reaction mixture can be prepared either batchwise or continuously. The crystal sizec and the crystallization time of the ZSM-5 zeolite varies depending on the type of reaction mixture used.

The ZSM-8 zeolites can also be expressed as the molar ratios of the oxides in the following manner reproduce:

0.9 j 0.2 M ₂ O: Al ₂ O ₃ : 15 to 100 SiO,: r 11..O

in which M is at least one cation, η its valence and r a number from 0 to 40. In the preferred synthesized form, the zeolite, expressed as the molar ratio of the oxides, has the following formula:

0.9! 0.2 M ₂ O: Al ₂ O ₃ : 15 to 60 SiO ₂ : rH ₂ O

wherein M consists of a mixture of alkali cations, in particular sodium ions, and / or tetraethylammonium cations consists.

The ZSM-8 zeolite can be suitably prepared by reacting an aqueous solution containing either Tetraethylammonium hydroxide or tetraethylammonium bromide together with the elements of sodium oxide, aluminum oxide and an oxide of Contains silicon.

The relative proportions of the various ingredients that can be used have not been fully investigated and clarified. In fact, completely different zeolites can be produced using the the same starting materials are prepared depending on their relative concentration and the reaction conditions, as can be seen from the U.S. Patent No. 33 08 069 gives. In general however, it was found that if tetraethylammonium hydfoxide is used, the zeolite ZSM-8 from this hydroxide, sodium oxide, aluminum oxide, silica and water can be prepared by reacting these materials in such proportions can that the batch solution is a composition.

509 647/174

given as molar ratios of the oxides, within the following ranges:

SiO ₂ / AI ₂ O _;> -

from 10 to 200
Na ₂ O / tetraethylammonium hydroxide -

from 0.05 to 0.020
Tetraethyammonium hydroxide / SiO ₂

from 0.08 to 1.0
U ₂ O / tetraethylammonium hydroxide -from 80 to 200

Then the crystals are removed from the liquid separated and won. The typical reaction conditions are that the above Reaction mixture at a temperature of 100 to 175 "C for a period of 6 hours to is held for 60 days. A more preferred temperature range is between 150 and 175 "C, the period of time at a temperature in this range being between 12 hours and 8 days.

The ZSM-II zeolite can be used as a molar ratio of the Oxides can be represented by the following formula:

0.0 I 0.3 M ₂ O: Al ₂ O ₃ : 20 to 90 SiO ₂ : -H ₂ O

where M is at least one cation, η its valence and ζ a number from 6 to 12. In the preferred synthesized form, the zeolite has the following formula as a molar ratio of the oxides:

0.9 I-0.3 M ₂ O: AUO ₃ : 20 to 90 SiO ₂ : ζ H ₂ O

wherein M is a mixture of alkali metal cations, in particular Means sodium and / or tetrabutylammonium cations.

The zeolite ZSM-11 can be conveniently prepared by preparing a solution containing (R ₁ X) ₂ O, sodium oxide, an oxide of aluminum or gallium, an oxide of silicon or germanium and water, and a composition given as a molar ratio of the Oxides, within the following ranges:

T ibeiie III Preferred Porridge l 20 to 90 YO ₂ 10 to 150 WOj 0.05 to 0.40 Na ₂ O 0.05 to 0.7 YO ₂ 0.02 to 0.15 (R ₁ X) ₂ O 0.02 to 0.20 YO ₂ 100 to 600 H ₂ O 50 to SOO Na ₈ O

wherein R ₄ X is a cation of a quaternary compound of an element of Group 5A of the Periodic Table, W is aluminum or gallium and Y is silicon or germanium, and the mixture is held until crystals of the zcolith are formed. The crystallization is preferably carried out under pressure in an autoclave or a static bomb reactor. The reaction temperature is between 100 and 200 ° C., while at lower temperatures, for example about 100 ° C., the crystallization time is longer. The crystals are then separated from the liquid and recovered. The new zeolite is preferably formed in the aluminosilicate form.

It is particularly important to note that although one of the characteristic properties of all Crystalline aluminosilicate zeolites used according to the invention lies in the fact that they were made from a solution containing organic cations, so that in the synthesized state they contain an organic cation, despite the presence of one organic cation during the actual use of these materials in the reforming process is not necessary.

It has been found that zeolites which have certain properties in terms of cics ratio of Silica to aluminum oxide and possess the ability to sorption of methyl paraffins and from solutions, containing organic cations were crystallized, so that the zeolite in the synthesized ao form has an organic cation, excellent are useful for upgrading reformats.

These zeolites can be subjected to conventional base exchange treatments by methods known per se be all or part of the originally associated with these materials replace organic cations before use. Furthermore, these materials can be increased Temperatures for the decomposition of the organic cations present in the synthesized state be heated. Therefore, the requirement that the zeolite contain an organic cation is only one Requirement for the synthesis of the zeolite and not for the use of the zcolith. Flour is thus used in the context of the invention Zeolites includes those with organic cations following their crystallization from solutions that contained no organic cations, were base exchanged.

In the zeolites used according to the invention are preferably the cations originally associated therewith through a wide variety of others Replaced cations according to methods known per se. Typical replacing cations include hydrogen, Ammonium and metal cations, including mixtures thereof. From the replacing cations the cations of hydrogen, ammonium, rare earths, magnesium, zinc, calcium, Nickel and mixtures thereof are preferred.

Typical ion exhaustion processes consist of 5 <j Contacting the special zeolite with a salt of the desired replacing cation or cations. Although a wide variety of salts can be used, the chlorides, nitrates and sulfates are particularly preferred.

Examples of ion exchange processes are e.g. B. in U.S. Patents 31 40 249, 31 40 251 and 31 40 253 described.

¹ C zeolites washed with water and at temperatures in the range of 66 to 315 'dried and then in air or other inert gas at temperatures ranging from 260 to K15 "- subsequent to the contact with the solution of the salt of the additional cations may ι ¹ C heated for periods of between 1 hour up to 48 hours or more.

It is also possible to steam the zeolites at elevated temperatures in the range from 425 to S70 ° C and preferably to treat 540 to 815 ° C if

I / ÖO /

nan wishes this. Treatment can take place in atmospheres which consist partly or wholly of steam.

A similar treatment can take place at lower temperatures and elevated pressures, for example 175 to 370 ° C at 10 to 200 at.

A preferred embodiment of the invention resides in the use of a porous support together with the zeolites described above. The zeolites can with the porous support in combined, dispersed or otherwise intimately mixed in such proportions that the product obtained 1 to 95 percent by weight and preferably 10 to 70 percent by weight of the eolite in the final composition contains.

The expression "porous carrier" means inorganic Understood masses with which the aluminosilicals are united, dispersed or otherwise intimate can be mixed, wherein the carrier can be active or inactive. The porosity of the carrier Applied masses can either be specific to the specific material, or they can be mechanical or chemical measures are introduced. Examples of carriers that can be used include Metals and alloys thereof, sintered metals and sintered glass, asbestos, silicon carbide aggregates, Pumice, chamotte, diatomaceous earth, aluminum oxide and inorganic oxides. Inorganic Compounds, particularly those based on silica, are preferred. Of these are called Carriers: inorganic oxides such as ion, chemically treated clay, silica, silica-alumina or the like, particularly preferred because of their superior porosity, abrasion resistance and stability.

The methods of incorporating the zeolites in a carrier are described, for example, in U.S. Patent 31 40 253 described.

The reformate or the Reformer abstroni which is treated according to the method according to the invention, preferably contains only aromatic and paraffinic components, although it is also possible to use naphthenc and to tolerate olefins in the feed.

Reformates or reformer effluents, which are composed essentially of aromatics and paraffinic constituents, can by contacting all suitable materials, for example heavy gasoline charges with a boiling range of about C ₅ and preferably about C ₀ to about 193 C and higher, with hydrogen by the usual methods in contact, at least initially, with any conventional reforming catalyst. This represents a common reforming operation involving net production of hydrogen and is described in detail in U.S. Pat. No. 3,395,094.

Usual reforming catalysts include, for example, aluminum oxide in the /, y, or y form and mixtures thereof in combination with chromium, molybdenum or noble metals. The platinum type metals include e.g. B. the metal series containing platinum, palladium, osmium iridium, ruthenium or rhodium, and mixtures thereof, deposited on a suitable support. Group VIl B metals including rhenium can be used in combination with metals of the platinum type. Generally, the majority of the catalyst will be alumina, which can also constitute up to about 95 percent by weight or more of the catalyst. Other constituents can be associated with the aluminum oxide as a carrier, for example the oxides of silicon, magnesium, zirconium, thorium, vanadium, titanium, boron or mixtures thereof. The combination of platinum-aluminum oxide, either with or without one or more of the components listed above, such as silica, can also be used with small amounts of ilalogens, such as

ic chlorine or fluorine, be activated in amounts ranging from 0.1 to 5 percent by weight. In general, less than about 3, "" halogen when catalysts are employed platinum type. In a preferred embodiment, the reforming catalyst support material is composed of a material having a relatively high surface area, preferably a jy-alumina material with at least about 100 m ² per g.

In the reforming process, the typical reforming working conditions include temperatures in the Bc-

2 "ranging from 425 to 540 C, preferably 470 to 527" C, liquid hourly space velocities in the range from 0.1 to 10, preferably 0.5 to 5, a pressure in the range from atmospheric pressure to Λ9 atmospheres and higher, preferably 7 to 42 atm and a ratio of hydrogen to hydrocarbon in the range from 0.5 to 20 and preferably from 1 to 10. In the process according to the invention, the reformate or the reforming effluent is contacted with or without the addition of hydrogen over a catalyst of the ZSM-5 type. As can be seen from the examples, the chemical process appears to be the same with or without the presence of hydrogen. Although there is no apparent reason that hydrogen is necessary for upgrading the Rcformat according to the process according to the invention, the hydrogen which always occurs in the formation of a reformate via a reforming reaction is not a problem, and it is neither necessary nor advantageous to separate this hydrogen because it actually does additional advantages, in particular with regard to the stability of the catalyst, can result. In practice it is unfavorable to separate off the water, since this would result in additional labor costs, and since the reduced dilution of the hydrogen expediently returned to the reforming device improves the previous reformer operation. However, it is not necessary that a hydrogenation / dehydrogenation component be associated with the catalyst, although this is a preferred embodiment of the invention.

The amount of hydrogenation-Z-dehydrogenation component used is not critical and can range from 0.01 to 30 percent by weight based on entire catalyst. A variety of hydrogenation components can be used with either the Zeolite and / or the carrier in any suitable manner that intimate contact of the components allowed to be combined, using known processes, such as base exchange, impregnation, coprecipitation, joint gelation, mechanical mixing of one ingredient with the other, was used can be. The hydrogenation component can be metals, oxides and sulfides of metals Group VIB of the periodic table including chromium, molybdenum, tungsten, group IIB under Inclusion of zinc, cadmium, group VIl B including manganese and rhenium and group VIII including cobalt, nickel, platinum, palladium

um, ruthenium, rhodium and the like, and combinations of metals, sulfides and oxides of metals of the Group VIB and VIII, such as nickel-tungsten sulfide, Cobalt oxide-molybdenum oxide.

The pre-treatment before use varies according to the existing hydrogenation content. With components such as B. nickel-tungsten and cobalt-molybdenum, the catalyst is sulfur-activated, for example by sulphidation. With metals such as platinum or palladium, there is a hydrogenation stage applied. These procedures are known in the art and are conventional.

The conversion according to the present process is generally carried out at temperatures between 260 and 540 ^° C, preferably from 25 ° to 455 ° C. The hydrogen pressure, if used, is generally in the range from 7 to 210 atmospheres and preferably from 24 to 141 aiii. The hourly liquid space velocity, ie the liquid volume of hydrocarbon per hour per volume of catalyst, is between 0.1 and 250 and preferably between 1 and 100. In general, the molar ratio of hydrogen to hydrocarbon charge is between 1 and 80 and preferably between 2 and 15.

The conditions of temperature and pressure listed above for carrying out the process according to the invention are generally applicable over their entire scope, if the applied Zeolite catalyst no hydrogenation / dehydrogenation activity owns.

If the zeolite catalyst has a hydrogenation / dehydrogenation activity owns, must de; Conditions of temperature and pressure greater Care should be taken so that the aromatics present in the reformate or reforming effluent are not be hydrogenated.

Fs was found to be within the range of that used to carry out the conversion Process conditions the latter zeolite catalysts have certain ranges of temperature and pressure are within the broad range at which it is thermodynamically possible, the aromatics to hydrogenate, and that there are certain ranges of temperature and pressure at which it is thermodynamically is impossible. Hydrogenate aromatic compounds. Although the selective Hydrocraeken of normal paraffins and the hydrogenation of olefins at fairly wide ranges of temperatures and pressures can take place, the hydrogenation of aromatic compounds is thermodynamic only within a narrower range of temperature and pressure when used for conversions with the present catalysts, which have hydrogenation activity, possible.

In the process according to the invention, hydrogenation / dehydrogenation components of any strength which do not cause destructive hydrogenolysis of aromatics in situations in which it is thermodynamically impossible are used. To hydrogenate aromatics, and in the application of hydrogenation ,. ¹ Dehydrogenation components with poor hydrogenation activity when such conditions of temperature and pressure are used that it is thermodynamically possible. Hydrogenate aromatics / u.

For further explanation of this point of view, ciic drawing is used, which shows three curves and one graphical representation of those working conditions in which the selective conversion was carried out with a type B catalyst. The three Kunen give the required temperature and pressures to hydrogenate 10 percent by weight of the aromatics in a feedstock Hydrogen to aromatics ratios of 2.5: 1, 10: 1 and 40: 1.

To the left of these curves, an area labeled A indicates those temperature and pressure conditions under which it is thermodynamically possible to hydrogenate more than 10 percent by weight of aromatics, and to the right of the curves an area labeled B is shown, in which it is thermodynamically impossible to hydrogenate aromatic compounds, i.e. less than 10 weight percent conversion.

When working with a set of conditions corresponding to area B , all hydrogenation *, dehydrogenation components of any strength can be used, since no destructive hydrogenation of the aromatics occurs. When working in area B , metals of groups 1 B, HB, ^v , VI and VII of the periodic table, including the oxides and sulfides, can be used in any amount and in any concentration, since under these conditions all olefins are hydrogenated and the Aromatics remain practically inegrated. As already stated, it is not possible to use metals from group VIII of the periodic table, since these metals have too high an activity and cause destructive hydrogenolysis of benzene. It should be noted, however, that Group VIII metals and their compounds can be employed if their activity is reduced or deactivated by pretreatment, coking, or the addition of a deactivating agent to the charge such that negligible benzene conversion occurs.

When the work is carried out at temperature and pressure conditions within area A of the graph, the choice of hydrogenation / dehydrogenation component becomes more critical. In this type of operation it is possible to use hydrogenation components within groups Ib and HB of the periodic table in any concentration, since it has been found that these materials do not have sufficient hydrogenation-dehydrogenation activity to hydrogenate aromatics under these conditions. If, however, hydrogenation components from groups V, VI and VII of the periodic table are used, these materials must be used at sufficiently low concentrations so that they only have negligible hydrogenation activity for aromatics. To this end, it has been determined that the amount of these materials should be in the range from 0.05 to 4.5 percent by weight, based on the total weight of the hydrogenation component and the aluminosilicate. Particularly preferred concentrations are 0.2 to "S weight percent of the I lydrierungskomponente.

It goes without saying that the metals of Group VIII are iles of the periodic table and their oxides or sulfides not suitable for use because of the activity of this

fi5 materials is so high that hydrogenation of the aromatics occurs. However, in the same way as in the procedure under the conditions according to A , it is possible to use these compounds, if their

/ ίο

\ activity has been reduced enough so that only : a negligible hydrogenation of aromatic Connections occurs.

To determine whether the hydrogenation activity of an IU investigating catalyst is such that only negligible hydrogenation of> n aromatic compounds occurs, i.e. as a result of the voluntary deactivation of a group VIII metal catalyst or the use of low concentrations of groups V., VI and VH a convenient test procedure has been developed so that it can be determined very quickly and easily whether a particular catalyst is suitable or not

In this test method animal / u investigating catalyst, ie a / eolite with hydrogenation / dehydrogenation activity, is contacted with a hydrocarbon mixture containing about 50 percent by weight benzene, 25 percent by weight n-hydroxane and 25 percent by weight isohcxane, at a pressure of ! 4.1 atü. a temperature of 371 ¹¹ C. a constant liquid space velocity of 4.0 (in terms of total hydrocarbons) and a molar ratio of hydrogen to benzene of 30: 1. The contact becomes true! Performed 60 minutes and then periodically analyzed the Reaktorahstroni, for example at 15 minutes and 45 minutes. If less than 10% by weight of benzene has been converted by the hydrogenation, the catalyst is suitable for use in the new process according to the invention with regard to the hydrogenation activity

When working in such conditions where thermodvnamisih is impossible. To hydrogenate aromatics, ie corresponding to area A of the drawing, a simple test procedure has also been developed to determine whether the activity of metals of group VIII and compounds thereof has been sufficiently reduced so that no destructive hydrogenolysis of aromatics occurs.

In this test procedure, a / eolith is used with a Group VIII metal or compound the same on its outer ear surface with one Mixture of 50 percent by weight benzene. 25 percent by weight n-Hc \ an and 25 percent by weight isohcxane contacted in the same way as above, but the Konlakltcinpciaiur is 4X2 C. The other conditions are the same; H. Pressure 14,1 aiii, hourly Ilü ^ ij'keilstaunigeschwindigkcit 4.0, hydrogen benzene ratio 30: 1. The reactor effluent is analyzed, and if less than 10 piozcnl by weight of benzene seem to have been used the catalyst applicable to hydrogenolysis for aromatics in the standard process.

The method according to the invention can be in a A variety of forms are carried out using the above-mentioned procedures will. It is thus possible to carry out this selective conversion in a separate reactor. A common reformer is used in this embodiment operated to produce a reformate of the type specified above, and then the reformate or the Reaklorahsirom together with added Hydrogen fed into a separate reactor, the the above / eolite catalyst with or without hydrogenation component in the contains manner indicated above. In a further embodiment of the invention no separate reactor can be used, but the latter reactor can be used in a conventional three-reactor reforming operation be filled with a conventional platinum reforming catalyst and with the above-mentioned zeolite analyzer, so that the hydrocarbon feed first contacts the usual platinum reforming catalyst and then the zeolite catalyst. The feed material is in the usual way in the first

ίο reformed both stages of the usual reactor and then enters a third stage in which the conventional reforming catalyst is attached to the top of the reactor and then the sebive transformation takes place in the bottom part of the reactor with the zeolite catalyst. This embodiment has the Advantage that the existing equipment to carry out the new method according to the invention can be used.

As stated, in one embodiment of the invention a highly paraffinic C ₅ ⁾ heavy gasoline fraction can be diverted into the reformate or the reformer effluent for conversion using a catalyst of the ZSM-5 type. The introduction of a highly paraflinic material such as Udex raffinate results in an increase in the level of alkylation achieved thereby and an improvement in the valuable products.

In addition to the increase in the octane number of the reformate and the Ausbeiuc-Oktan-Bezichung, there is also further advantages of the method according to the invention over the methods previously used in practice. A significant advantage resides in the fact that in practice of the invention Process a greater purity of the hydrogen is obtained than with the corresponding known procedures. For a given octane rating improvement, the upgrade results in one Reformats the method according to the invention due to a higher degree of hydrogen purity the fact that only an extremely small amount of methane is formed in those used in accordance with the invention Catalysts occurs. A higher hydrogen purity represents a significant technical advantage. In the following, some methods of manufacture for the formation of those to be used according to the invention are described Catalysts specified.

Manufacturing method 1

The following example serves to explain the production of the hydrogen ZSM-5 zcolith, which is described in Examples 1 and 23 was used. Ice cream were made the following solutions:

(a) 0.56 kg of aluminum aluminate containing 44.7 "of aluminum oxide and 14 kg of water;

(b) 44.7 kg of sodium silicate and 56 kg of H ₂ O;

(c) 5.6 kg of tetrupropvlammonium imbromide and 21.5 kg of H ₂ O;

(d) 4.47 kg of sulfuric acid in 14 kg of water.

Solution (c) was added to solution (b) and then solution (a) was added to the mixture of (c) and (b). Then the solution (d) became the mixture of (C). (b) and (a) given with rapid stirring / u . I in solid gel formed at the end of the addition of solution (d).

The gel was heated to a temperature of ⁽ ) 3 to ⁽ ) ¹ ) C for a total time of ', 67 hours.

21

heats until the crystalline aluminum silicate identified as ZSM-5 was educated.

The ZSM-5 zeolite was dried, calcined in air for 10 hours at 538 ° C. and then calcined base-exchanged with an aqueous 1.0 N ammonium chloride solution at room temperature until the sodium content was reduced to 0.01 weight percent.

The ammonium exchanged ZSM-5 zeolite was made to a particle size of about 0.246 to Brought 0.542 mm and then calcined at 538 C overnight.

Manufacturing method 2

The following describes the preparation of the in the examples 2 through 22 and 24 through 33 used nickel H-ZSM-5 zeolites explained.

The following solutions were made:

(α) 1 kg of sodium aluminate with a content of

41.8 percent by weight of AUO; and 25 kg of water;

(b) 79.9kg sodium silicate in 100kg water, i.e.

28.9 percent by weight SiO ₂ , 9.0 percent by weight Na ₂ O, 62.1 percent by weight ILO;

(c) 10.0 kg of tetrapropylammonium bromide and 50 kg Water;

(d) 7.97 kg of sulfuric acid in 24 kg of water. * ⁵

The solution (c) was added to solution (B) and then the solution (a) i \\ added to a mixture of (c) and (b). Solution (d) was then added to the mixture of (a), (b) and (c) with rapid stirring. A gel was formed and the mixture was heated at a temperature of 9! held at 99 ° C for about 267.5 hours, until crystallization was complete and the ZSM-5 was formed. After the filtration, the moist cake was mixed with water, washed and then dried at 121.degree. After drying, c was calcined at 371 ° C. for 3 hours.

The calcined ZSM-5 material was then exchanged for 4 hours with a 1.0N ammonium nitrate solution subjected at room temperature.

The ammonium-exchanged zeolite was then a 4-hour exchange with a 0.5N N-nitrate solution subjected at 88 C.

The exchanged material was then washed free of the nickel solution, dried at 121 C, brought to a particle size of about 0.246 to 0.542 mm and then calcined at 538 ° C. for 10 hours.

The calcined ZSM-5 material was then mixed with a mixture of about 2 percent by weight hydrogen sulfide sulphurized in hydrogen at 393 C.

The catalyst contained 0.11 percent by weight sulfur, 0.32 percent by weight nickel and 0.02 percent by weight Sodium.

Creation wcise 3

1 ^: A typical preparation of the ZSM-5 used in Example 35 is described.

22.9 g of SiO ₂ were partially dissolved in 100 ml of 2.18 n-tetrapropylaminonium! Iydro. \ Id by Γrhit / .cn to a temperature around 100 (', a mixture of 3.19 g NaAlOo (composition: 42.0 percent by weight Al ₂ O; "30.9""Na ₂ C), 27.1""ILO), dissolved in 53, SmI Ii ₅ O, was added. The mixture obtained had the following composition: 0.3X2 mol SiO. ,, 0.01 3 I mol ALO ₁ , 0.01 59 mol Na..O, 0.118 mol | (CH, C! IX'l l,), N], O>, 30 moles ILO. The mixture is wound into a hard glass

Al

857

given into an autoclave and heated to 150 C for 6 days. The solid product obtained became cooled to room temperature, removed, rilted, washed with 11 H, O and dried at 110.degree. A Part of this product was x-rayed and identified as ZSM-5. Part of the Product was heated to 538 C in air for 16 hours calcined and obtained the following analyzes:

Weight percent SiO ₂ 93.62

Weight percent ALO ₁ 4.9

Weight percent Na. (> 1.48

100.00

SiO ₂ Zal ₂ O ₁ ³² · ⁵

Na ₄ O / ALO ₁₁ ° ' ⁵

Weight percent adsorbed

η-hexane K), 87

Weight percent adsoi bioi tes

Cyclohexane 3.60

Weight percent adsorbed H ₂ O 9.15

Manufacturing method 4

The general procedure for making that used in Examples 34, 42 and 44 is followed Materials H-ZSM-5 explained.

A ZSM-5 Zcoliih was made according to the manufacturing process 3 manufactured; this was then with a saturated solution of ammonium chloride contacted to replace the cations originally associated therewith, and then with water washed, dried and in air at about 538 ° C calcined to convert it into the water-based form, d. H. 1 l-ZSM-5, to convict.

I lerunusweise 5

A catalyst from /.^M-S-Ivp was accordingly the general procedure according to 1 starting procedure 3 manufactured. The reaction mav-.e and the properties of the finished product were as follows:

Temperature, C 150

Time, days 5

Reaction composition:

SiO, / ALO, 2 ¹ U

Na, O / A "l ₂ O, L 19

TPAjO / ALO-, 9

H ₂ O / TPA ₂ O \ _Na; O 47

Composition:

Na ₂ O, weight percent 2.42

Well, weight percent 1.8

Al ₂ O _{: l} , weight percent 6.1

SiO ₂ , weight percent 90.6

SiO., / Al ₂ O, ·. 25.2

Na ₂ b / AL _():, 0.65

Adsorption:

Cyclohexane, weight percent 3.07

η-hexane, weight percent .... 9.88

ILO, weight percent 7.51

The above material was then calcined at about 53 ° C 'for 16 hours and in two Shares (A and H) divided. The part A was with 100 ml of an aqueous 0.5 N ammonium chloride solution exchanged at room temperature for 1 hour with formation of the Ammoru'umsalzes. He was called Catalyst A 1 is designated. 3 g of the catalyst A 1 wimleu with 35 ml of a 0, S n-2.9 / Lzinc / NH, -chloid solution exchanged at 43 C for 4 hours.

The material was then washed with water and dried η air and a catalyst with a Zinc content of 0.9 percent by weight and a sodium content of 0.2 percent by weight. After calcination at 538 ° C. for 16 hours, it was used in Example 36.

Part B was treated with anhydrous ammonia (100 cm ³ per minute) at room temperature to restore the NH _r spots. This catalyst was designated as B 1. 3 g of the catalyst B1 were exchanged with a 0.5 N solution of zinc and ammonium chloride as shown. The finished catalyst contained 1.2 percent by weight zinc and 0.3 percent by weight sodium. After calcination at 538 ^° C. for 16 hours, it was used in example 38.

The catalysts used in Examples 37 and 39 were prepared in the same way, however a nickel salt was used for the base exchange of the zeolite instead of the zinc salt.

Production method 6

In the following the production of the Nickel-ZSM-5-Zeolite, the one in example 4? is used.

The following solutions were made:

(a) 1.0 kg of sodium aluminate with a content of

41.8 percent by weight AloO ₁ , and 25 kg of water;

(b) 79.9kg sodium silicate in 100kg water, i.e.

28.9 percent by weight SiO ₂ , 9.0 percent by weight Na ₂ O, 62.1 percent by weight IL ₂ O;

(c) 10.0 kg of tetrapropylammonium broniide and 50 kg of water;

(d) 7.97 kg of sulfuric acid in 24 kg of water.

The solution (c) was added / 11 of the solution (b), and then the solution (α) / u was added to the mixture of (c) and (b). Solution (d) then became added to the mixture of (a), (b) and (c) with rapid stirring. A gel was formed and the 4 » Mixture was kept at a temperature of 91 to 99 C for 267.5 hours until crystallization was finished and the ZSM-5 material was formed. After the filtration, the cake became wet mixed with water, washed and then dried at 171 ° C. After drying he was during Calcined at 371 ° C. for 3 hours.

The calcined ZSM-5 material was then left for 4 hours exchanged with a 1.0 n ammonium nitrate solution at room temperature and the ammonium balanced s < > exchanged zeolite then subjected to a 4 south exchange with a 0.5N nickel nitrate solution at SK C.

The exchanged material was then released from the Washed nickel solution and dried at 121 C, to a particle size of about 0..246 to 0.542 mm brought and then calcined for 10 hours at 538 <".

The calcined ZSM-5 material was then siliconized with a mixture of about 2 percent by weight hydrogen sulfide in hydrogen at Υ> ^{ > C.

The catalyst contained 0.11 percent by weight Sulfur, 0.32 percent by weight nickel and 0. (P percent by weight Sodium.

Manufacture 7

The following is the preparation of the in the examples 46, 47 and 4S used hydrogen ZSM-5 zeolites described. The following solutions were made:

(a) 0.56 kg of sodium aluminate containing 44.7 ", ', alumina and 14 kg of water;

(b) 44.7 kg of sodium silicate and 56 kg of H ₂ O;

(c) 5.6 kg of tetrapropylammonium bromide and 28 kg of water;

(d) 4.47 kg of sulfuric acid in 14 kg of water.

Solution (c) was added to solution (b), and then solution (a) to the mixture of (c) and (b) added. Solution (d) was then added to the mixture of (c), (b) and (a) with rapid stirring. At the end of the addition of solution (d) a solid gel had formed.

The gel was heated to a temperature of 93 to 99 C for a total of 167 hours, until the crystalline aluminosilicate identified as ZSM-5 was educated.

The ZSM-5 zeolite was dried, calcined in air for 10 hours at 53 ° C. and then calcined base-exchanged with an aqueous 1.0 N ammonium chloride solution at room temperature until the sodium content was decreased to 0.01 weight percent.

The ammonium exchanged ZSM-5 zeolite was made to have a particle size of about 0.246-0.542 and then calcined at 538 ° C. overnight.

example 1

This example illustrates the new chemical reactions that take place when catalysts are dated ZSM-5-Iyp can be used.

In example 1, a mixture of 50 percent by weight n-octane and 50 percent by weight was used in a model experiment Benzene introduced. The hydrogen form of ZSM-5 was used, and it became the following reaction conditions are used:

Pressure 35.5 atm

Temperature, C 275

Hourly air traffic

space velocity 1

Hydrogen without

The following results were obtained:

25th

³ ° Skin care
g / HW) loading

C ₁

Butane

Peniane

C _e -paraftins

C, paraffins

C "paraffins

benzene

Alkylbenzenes (C _{7 l: 1} )

Tetrahydronaphtheline. ImIanc

Naphthalenes

Naphthenes

Olefins

example 1

■ 0.1

■ 0.1

4.0

9.9

6.4

1.2

0.2

13.5

33.3

26.2

3.8

0.6

0.1

0.9

100.0 g

While the feed had 50 weight percent Ai paint, as ·, the product d3.9 weight percent Aromatics on.

21 22nd

Pressure, atü

Ho / liC molar ratio Temperature, "C .... hourly liquid

vokimcn

Working time, hours ... Liquid product Weight, oAPl. ..

RON, of course

Material matching,

Weight percent. C ₁ , weight percent C _a , (i _{weight percent C 2} , weight percent C ₁₁ , weight percent C _a , weight percent total dry gas,

("Weight percent. iC ₄ , Volume percent. C ₄ ". Volume percent. HC _1. Volume percent i-Cr,. Volume percent. Cr,. Volume percent. nC · ,, Volume percent C _4. Volume percent. Cr _{,, Volume percent. C 6} , Volume percent.

RON, clear, C ₅ ⁽

RON. clear, C _e ^!

Example no.

Re-

slack

2 3 4th 5 (l 7th S. 9

54.5

0.7

2.8

8.1

0.1

8.1

100

96.5

80.1

90.3

92.4

288 315 343 343 346 342 352 375 V, 5 5 5 10 20th 30th 40 40 51.5 5 6th 6th 3 1 97.4 52.0 51.3 48.1 50.7 51.9 51.9 52.4 100.0 94.7 97.5 100.7 98.7 97.0 95.9 95.2 0.03 102.5 97.3 96.2 96.2 102.0 101.2 103.9 0.03 - 0.03 0.03 0.04 0.02 0.02 0.02 0.16 0.01 0.05 0.03 0.02 0.08 0.08 0.26 0.26 0.29 0.15 0.06 0.10 2.53 . - - 0.01 0.04 0.01 2.83 1.22 2.85 7.51 5.70 2.35 1.60 1.47 2.5 1.30 3.15 7.90 6.07 2.54 1.72 1.60 0.2 2.3 3.1 4.6 5.1 2.4 1.9 2.0 3.4 _- - .... 0.1 0.1 0.1 0.1 7.1 2.7 3.9 5.1 5.0 3.6 3.2 3.0 0.2 6.2 6.3 6.5 7.3 7.1 6.9 7.2 4.8 0.1 0.1 0.2 0.1 0.1 0.1 93.8 5.0 4.1 2.6 3.7 4.8 5.2 5.6 87.7 95.4 93.2 87.5 91.1 ¹ M. 1 95, i 95.7 75.5 90.4 86.0 77.8 80.9 88.0 90.0 90.6 97.4 79.2 75.6 68.7 69.7 76.0 77.8 77.7 99.8 94.6 97.6 101.1 98.8 97.0 95.9 95.1 96.5 99.7 103.2 101.1 99.3 98.1 97.4

12 13

14th

Example no.
I Hi I 17

IS

19th

20th

21

Pressure, atü

Hj / HC molar ratio Temperature, "C ....

Hourly Liquid volume

Trial time, hours. . .

Liquid product weight, oAPl. ..

RON. clear

Material determination, weight percent. C ₁ , weight percent C ₂ . Weight percent C ₂ . Weight percent C ₃ . Weight percent C ₃ . Weight percent

Total dry gas,

Weight percent. iC ₄ , percent by volume. C ₄ ". Volume percent. NC ₄ , Volume percent iC ₅ , Volume percent. C ₅ ", Volume percent. nC ₅ , volume percent C ₄ ', volume percent. C _r , \ volume percent. C ₀ , percent by volume.

RON, clear, C ₅ '

RON. clear. C _e ^!

5 910

207 2

49.3 97.3

102.6 0.27 0. () l 0.80

1.25 3.27

6.20

0.7

3.2

5.1

0.5

4.6

89.4

84.6

74.4

97.1

99.3

I 1917

212

48.3

110.2 0.19 0.70 0.42 1.38 2.74

90.4

84.4

75.8

"5.9

97.4 2
909

208

49.7
9p.4

94.5
0.57
0.74
1.40
1.35
8.00

12.06

3.3

1.2

4.6

6.5

0.4

2.6

85.6

76.5

67.0

98.4

100.2

-
5
911

215
5

49.3
97.5

101.3
0.23
0.59
0.61

1.24
3.51

6.18

2.0

0.8

2.6

5.8

0.4

3.9

89.9

84.6

74.5

97.6

99.4

- ^ 17

5
933

215

V ₃

49.8
97.6

102.7
0.33
0.76
0.85
1.56
4.54

8.04
2.5

1.3
3.2
5.5
0.5
3.4
88. (.

72.3
97.6
99.4

5 K) O 10 20th 10 H) 855 215 917 800 699 S05 215 2``V 215 99 10 103 71 /
<-, 1 49.6 2'Λ 5 18th 4 '/. 50.1 97.3 47.3 47.5 48.3 51.4 96.2 102.7 97.7 96.1 97.3 95.4 106.9 0.19 109.1 100.6 112.8 0.10 0.53 0.28 0.06 0.08 0.39 0.46 0.61 0.01 0.27 0.23 1.08 0.52 0.35 1.05 3.69 1.03 0.33 3.48 5.95 3.66 4.28 2.50 5.25 2.8 6.10 4.35 3.53 3.0 1.1 3.3 3.5 3.2 0.9 2.9 0.8 0.1 0.7 2.6 5.6 1.7 2.5 1.9 5.0 0.5 4.3 5.5 6.2 0.3 3.8 0.3 0.1 0.3 3.3 90.6 2.5 3.1 4.1 91.3 83.8 89.0 92.1 94.7 84.8 74.0 83.2 86.0 88.9 76.2 97.3 76.2 77.4 78.3 96.2 99.1 97.7 97.3 95.3 97.6 98.9 98.9 97.0

I I \ J KJ ι

Examples 2 to 22

The above examples serve to further illustrate the processes according to the invention. In each In the case, a reformate was used as the charge, which was produced by contacting a heavy gasoline from With continent type together with hydrogen over a platinum reforming catalyst at 427 to 538 ° C and a pressure of about 35.5 aiii.

The reformate was exchanged together with the hydrogen with one with nickel-hydrogen Contacted ZSM-5 zeolite which was sulfidized prior to use. The other working conditions and the results obtained are shown in the following table.

C ₁ , weight percent

C ₂ , weight percent

C ₂ , weight percent

C ₃ ", weight percent

C ₃ , weight percent

Total dry gas.
Weight percent
iC ₄ , percent by volume
C ₄ ", percent by volume
nC ₄ , percent by volume
C ₁ ¹ . Volume percentage
C _r , ^f , percent by volume
C ₀ ', percent by volume
C ₅ '. RON, of course ...
C ₀ ¹ , RON, clear ....

Example 23 Iro
, I ₁₁ I ( Ex H-ZSM-5 ClUKl Ni / H- He- 0.03 Loading chic- 0.01 chic- kung 0.01 kung 3.98 4.03 4.9 0.1 7.0 2.0 93.1 0.7 81.1 - 4.8 71.3 2.8 100.0 98.9 100.0 93.2 101.0 96.5 77.2 80.1 90.3 90.3 92.4 92.4

product

0.03 0.01

2.85

3.15 3.1

3.9 93.2 86.0 75.6 97.6 99.7 The above comparison was made at 316 C, 28 atm, a liquid hourly space velocity of 5, and an HJHC molar ratio of 2. The feed butane content was not the same and these are listed separately. The yields the two catalysts do not differ significantly when the high octane number (1 unit) is above H-ZSM-5 is being considered.

B e i s ρ i e 1 e 25 and 26

These examples explain the effect of the working conditions with hydrogen and the results obtained using a Ni / H-ZSM-5 zeolite prepared according to the I ler position 2.

Examples 23 and 24

These examples demonstrate that improved results are obtained whether hydrogenation * / dehydrogenation metals connected to the ZSM-5 type zcolith or not.

Pressure, atü

HJHC molar ratio
Hourly Liquid space velocity

Temperature, "C

Drying gas,
Weight percent
C ₄ , volume percentage ...
C ₅ ¹ , volume percent ..
C ₅ ¹ , RON, clear

Delivery

6.8
93.2
90.3

Example 25
hydrogen

28
2

5
316

4.03
12.0
81.1
98.9

Example 2 (>

without
hydrogen

35.5

1
618

7.38
16.8
76.0
98.9

0.26 As can be seen from the above results, the liquid yield is far higher and that Dry gas far lower in the presence of hydrogen.

Examples 27 to 33

The following table shows the fate of the C ₅ 'paraffins that were converted. As can be seen, the alkyl aromatics increased in all cases. A Ni / H-ZSM-5 zeolite prepared according to the method of manufacture was used.

Tabel

g / 100 g
feed 27
316 "C. 28
341 "C 29
376 ° C example
30th
43O ¹ C 31
482 ° C 32
492 'C 502 ¹ C Disappearance of the C ₅ ⁴ paraffins ...
Occurrence of: 18.03
3.15 14.04
2.54 14.34
2.83 12.39
3.53 16.22
5.95 18.21
6.10 18.24
8.04 Increase in C * 2.74
4.96
3.54 1.99
3.64
2.77 1.99
3.96
2.67 1.73
4.31
1.88 2.53
4.35
1.41 1.73
6.83
2.34 2.73
5.49 Increase in alkylbenzyl
ring carbon atoms 14.40 10.94 11.45 11.45 14.24 17.00 1.22 Increase in alkylbenzene
scitenketten 17.48

509 647/174

2 1 17öö /

Examples 34 to 39

A C-Reformatahslroni was made by mixing on .SO "- ,, Hcn / .ol with 25" ,, η-hexane and 25 / ,, isohexane , imulicrl. The material then became mil different mines of ZSM-5 catalysts at 14 aiii, one Volume ratio of water / carbon to hydrogen .on 15: 1 with an hourly liquid space Ueschwiiuligkcit of 4 and contacted at 37 Γ C. 1 me high conversion with removal of the components with a low octane number and a Λη-i protection of the components with a high octane number was observed:

I) e ι s ρ i e I e 4! to 44

To compare the behavior of ZSM-5 with the previously known shape-selective acidic cracking catalysts was cm WasserstolT T material that was exchanged by calcining with ammonium / eoliths I had been exposed, with the same synthetic Refoimatgeniiscli, which in the examples 34 to 39 was used, and contacted ίο the Rcaktorahsirom after a period on the river analyzed for 15 minutes or 3 hours.

The following results were obtained:

(icwiclH catalyst ii-l tuxan HZSM-5 97.9 NallZSM-5 28.5 Zn / H / ZSM-5 0, H7 ': "/ n 81.2 Ni / H / ZSM-5 0.20 "; Ni 73.4 Zn / H / ZSM-5 1.21 ", ', Zn 41.8 Ni / II / ZSM-5 0.31 ';;, Ni 98.0

2-Mcihylponlaii

4U

31.5
23.4
14.0
55.7

licn / .ol

12.5
4.2

14.0

5.7

4.5

15.5

Example 40

catalyst

Ni, II / erionite

Weight pio / cnl conversion

2-methyl pentane

n-Hoxane

85.4

3.1

benzene

2.6

composition

of the liquidity profile

from example 37

J-methylpentane

it I lexan

benzene

toluene

C ₈ aromatics ..
CV aromatics.

Haspid

41

au 42

43
44

catalyst

ΙΕΓ
H / ZSM-5

H / l
ll / ZSM-5

it-hexiiii

2-methyl pcntiine

Ilen / ··!

Weight percent conversion (15 minutes on stream)

5H, 5
97.9

3.3

43.3

0.6 12.5

(weight per / ent conversion (3 hours on electricity)

29.7
97.8

0.5-4.5

12.1

To compare the behavior of ZSM-5 mild known shape-selective 5-A-Kalalysatoren was a nickel-hydrogen-F.rionite with the same synthetic Contact formatting mixture used in Examples 34 through 39 and the following results obtain:

From these expanses, the remarkable activity and non-aging of H / ZSM-5 without Additive, an Ilydration-Z-Dehydration component under I lydiokraekbedinguiigen. The material I l / T andcier ropes aged considerably in 3 hours.

Example 45

In this example the effect is absence of hydrogen, with the following results being obtained:

The feed was exchanged over a Ni / 11 / ZSM-s.type zeolite. The properties the loading as well as the operating conditions and the results are summarized below:

The ZSM-5 catalysts are more active in the II, ZN / H and Ni / H forins than the nickel / 1! Erionite for cracking n-1 lexane, and in contrast to nickel / H erionite they also convert 2-methylpentane and benzene to a significantly greater extent. In the liquid product collected from the ZSM-5 experiments, large amounts of C ₇ ¹ -alkylaroniates were found, which are apparently produced from the alkylation of Henzene with the cracked fragment. A typical analysis of the collected liquid product at room temperature is given below:

j Pressure, aiii. . dispatch Example 4 "> M oil ratio 1I ₂ MIC .... 35.5 Hourly 1 liquid wedge space velocity. . . Temperature, "C 1 Drying gas, 318 _{r (i} percent by weight C ₁ , percent by volume 7.38 C ,, ¹ , volume percent 6.8 16.8 CV, RON, of course 93.2 76.0 90.3 98.9

(weight pro / tiit

1.5
4I, H

12.2

1.2

30.2

54.1

HK), 0

Example 46

In this experiment a synthetic C ₉ reformate was converted over an acid exchanged ZSM-5 zcolith catalyst. The CVReformatbe · destiny had the following Zusamme ¹ ctzung:

component

2,2-dimethylbutane
2,3-dimethylbutane
2-methylpentane. ..

n-hexen-1

benzene

n-Hcxan

Volume percentage

10.5 6.2

15.3 5.8

40.4

21.8

This composition holds an octane number (OZ) of 77.1.

In this experiment the above batch was used by one pass over the acid-exchanged ZSM-5 zcolith at 100 to 200 WHSV converted at 482 to 510 C. In particular, was the implementation carried out at 100 WIISV and 482 C and the properties of the end product below listed.

OktanverbessciiiiU 'The synthetic reformate had a calculated clear octane number (R; O) of 77.1. The measured micro-octa / ehl was 77.6 (R ^L OV At 100 VVIISV and 48: C, the modified fuel obtained had an initial clear octane number of ⁽ * 2.3, calculated from the composition of the products. An increase of 15 , 2 octane values achieved through the conversion via the zeolite.

This octane increase was obtained by:

(1) Cracking of 62.9 percent by weight of the n-hexane and 12.5 percent by weight of the 2-methylpentane and 2,3-dimethylbiitane to give C ₁ oils and paraffins, and (2) by alkylating 19.5 percent by weight of the benzene

in C

until

("," - alkyl aromatics. A

Example 48

In this experiment, a reformate with H1.2 (R I O) from a platinum reformer using the same experimental procedure as in Example 45 was used became. The loading mass had the following analysis:

Average molecular weight 89.2

Paraffins, weight percent 68.3

Oleline, weight percent 1.5

Alkylbenzenes, weight percent 29.4

Others (by difference),

Weight percent 0.8

100.0

negligible amount of 2,2-1) iniethylbiitan was converted.

The modified fuel thus contained 20.3 percent by volume · C '_; , and 3.6 volume percent C ₁ and 76.1 volume percent C ₈ .

The octane rating of the liquid product and that of the modified fuel (liquid plus gas) are given below:

Time on the stream

20 minutes

3 hours, 40 min.

Only
! liquid

¹ J 1.3

88.7

Modified RrennstolV

93.8
90.8

Example 47

In this attempt, a reformate with an octane rating of 86.0 (R j O) and an endpoint was used of 204 "C from a platinum reformer over the acid-exchanged Z.SM-5 zeolite catalyst converted. The catalyst had a value of 13,000. The feed mass had the following analysis

Average
Molecular weight .... 96.5

Octane number (blcifrci) Rcscarch-Mcthode

86.0

Paraffins, weight percent 57.3

Olefins, weight engine method

percent 1.1 79.5

Alkylbenzenes,

Weight percent 38.6

Others (through

Difference),

Weight percent 3.0

100.0

There was an increase of 12.6 and 9.6 octane values received compared to the reformate charge.

In the following, sorting tests are used Evaluation of whether or not a zeolite to be examined is effective in the method according to the invention, described.

In these experiments, equal parts by weight of benzene and n-heptane were used over the different ones 4 <> investigating catalysts and the conversion determined by benzene and heptane.

The conditions used were as follows:

Temperature 316 to 482 C

Pressure 0 to 28 aiii

Space velocity

(WHSV) 0.4 to 62

Hj / HC 0 to 7

The reason for the wide variation in operating conditions was to try to get the best results for each examined catalyst. All of the catalysts to be examined were thereby initially examined under the following conditions:

The experiment was carried out in the same manner as in Example 1. The liquid product became collected and its octane rating with a standard 6 » Octane rating engine determined. The gas product was determined by the gas chromatographic method analyzed. Fine calculated octane number of 92.4 (R; O) was obtained by combining the octane values of the individual gases with the measured octar value of the liquid product. Thus, there was an increase in 6.4 octane values achieved by converting above the zeolite.

399 ° C

28atü

62 WHSV
7/1 H ₂ / HC

Those who failed this attempt were reverberated under different conditions of the above broad range are reexamined to improve their performance.

The following table shows the best results * in the examination and the temperatures used specified.

Zeolite

Organic
Κίΐ tion SiO ₂ ZAl ₁ O, Cracked
n-heptane Converted
benzene temperature Weight percent Weight percent ⁰ C Yes 8.0 15th 1.5 427 Yes 6.7 8th 0.1 399 no 24 9 2 399 Yes 32 61 18.5 482 Yes 30th 68 10.5 482 Yes 30 to 70 80 28 316 Yes 53 61 15th 399 Yes 76 38 15.5 316 Yes 52 52 18th 399

TMA Offretit *)

ZSM-4

Mordenite (dealuminized)

TEA mordenite **)

Beta***)

ZSM-5

ZSM-8

ZSM-Il

ZSM-12

·) Tetramethylammonium-OiTretit.
* ·) Tetraethylammonium mordenite.
·· ♦) Crystalline zeolite (US-PS 33 08 069).

From the table above it can be seen that there is a marked difference in the catalytic behavior existed between the examined zeolites. First of all, it should be noted that all of the above examined the ability to sorb monomethyl paraffins in the applied zeolites Had conversion conditions. The differences between the zeolites consisted in whether they were so synthesized as to contain an organic cation and in their proportion of silica to aluminum oxide.

It can be seen from the table that materials such as TMA-Offretite, ZSM-4 and Mordenite do not work in the desired way. With regard TMA offretite can be seen that the cracking themselves are of heptane and the conversion of benzene was too low at temperatures of 427 ⁰ C. As can be seen, TMA offretite is not one of the zeolites to be used according to the invention, since its ratio of silica to aluminum oxide is below 15. Likewise, while ZSM-4, while containing an organic cation and capable of sorbing monomethyl paraffins, was not found to be a good catalyst in terms of its conversion of heptane and benzene and, as can be seen from the table above, it too had a silica ratio to aluminum oxide below the required value of 15,

From the table above it can also be seen that it is not just the ratio of silica to aluminum oxide, which ensures improved catalytic properties. It's going to be on mordenite pointed out, which was synthesized in the usual manner and then dealuminized so that its ratio rose from silica to alumina to 24. As can be seen from the table, he was inferior Catalylic properties in terms of the conversion of heptane and benzene, making it ineffective proved to be a catalyst for upgrading a reformate according to the teachings of the invention.

The remaining zeolites gave good results as evidenced by the fact that they were substantial Converted amounts of heptane and benzene.

1 sheet of drawings

Claims (5)

Patent claims: 1. A process for upgrading reformates and reformer effluents, in which they are brought into contact with a crystalline aluminosilicate zeolite under conversion conditions, characterized in that an aluminosilicate zeolite having an SiO ₂ : Al ₂ O ₃ ratio of greater than 15 is obtained from a solution containing organic cations has been crystallized and contains organic cations in the synthesized form and has a pore size such that it burbizes methyl paraffins under the conversion conditions, and optionally has a hydrogenation / dehydrogenation component associated therewith. 2. The method according to claim 1, characterized in that a crystalline aluminosilicate / eoliih with a silica to alumina ratio greater than 20 is used. 3. The method according to claim 2, characterized in that a crystalline aluminum silicate is used that has been base-exchanged with ammonium or hydrogen cations. 4. The method according to claim 2, characterized in that the crystalline aluminosilicate ZeoHth Beta, TEA-Mordenil or the zeolites ZSM-5, ZSM-S, ZSM-Il or ZSM-12 are used will. 5. The method according to claim 4, characterized in that one with ammonium or hydrogen cations base-balanced zeolite is used.