AT312776B - Process for the preparation of reformates and products from reforming plants - Google Patents

Description

  

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   The invention relates to a process for improving the ratio of yield to octane number in a reformate or in a product from a reforming plant by bringing the reformate or product into contact with crystalline aluminosilicate zeolites under conversion conditions in the presence of hydrogen , which is characterized in that these 5 1. have a ratio of silica to alumina of more than 15, preferably more than 20,
2. were crystallized from a solution containing organic cations, so that the synthesized aluminosilicate contains organic cations, and
3. Have a pore size that the aluminosilicate absorbs methyl paraffins under these conversion conditions.



  The reformate can be processed with or without added hydrogen and with or without a hydrogenation / dehydrogenation component.



   The preparation of reformates to improve the octane number of gasoline and the ratio of
The yield to octane number has been the subject of many years of work in the petroleum industry. Recently, however, as a result of the recognition of the problem of environmental control and air pollution, this work has been intensified. Such processes in which the octane number of gasoline could be increased are therefore extremely desirable because they eliminate the use of lead or on a Could reduce minimum, which previously had to be added in order to achieve higher octane values.



   It is already known to prepare a reformate by the most varied of processes in which crystalline aluminosilicate zeolites are used. The treatment of a reformate with crystalline aluminosilicate zeolites has hitherto comprised both physical treatments, such as, for example, selective adsorption, and chemical treatments, such as selective conversion.



   Although the prior art processes for treating a reformate differed from one another, they had the common feature that all crystalline aluminosilicates with a
Pore size of about 5 Angstrom units used. In other words, this can be expressed that essentially in all known processes for the preparation of reformates with zeolites such
Zeolites were used which allowed normal paraffins and excluded isoparaffins. This was not surprising since, according to the prior art, the undesired component in a reformate was usually the normal paraffins, whereas the other components of the reformate, for example the aromatic fractions and isoparaffins, were valuable products.

   Accordingly, the work so far has been on the
Directed use of zeolites with which the normal paraffins could be selectively removed and the aromatic components and / or isoparaffins remained in the reformate.



   U.S. Patent Nos. 2, 851, 970 and No. 2, 886, 508 relate to reforming processes in which a
Petroleum first reformed and the reformate or part thereof with aluminosilicate of 5 angstrom units in
Is brought into contact to selectively adsorb the normal paraffins.



   U.S. Patent No. 3, 114, 696 represents a significant improvement on the problem of
Preparation of a reformate, since it involves treating a reformate with a crystalline aluminosilicate with a pore size of 5 Angstrom units under cracking conditions, so that the normal
Paraffins were selectively cracked out.



   U.S. Patent No. 3,395,094 represents yet another improvement on the general
This patent describes the removal of normal paraffins from a reformate by hydrocracking with a crystalline aluminosilicate with a pore size of about 5 Angstrom units and a hydrogenation activity limited to the internal pore structure. According to this patent it was determined that it was no longer necessary to crack out normal paraffins but also to protect the aromatic components of the charge while this process was being carried out.



   It has now been found that further improvements can be achieved with the method according to the invention.



   The reason why the particular zeolites used in the process of the invention are to be improved
Leading results in the preparation of reformats is not entirely understandable. As already stated, the measure, a reformate with a crystalline aluminosilicate zeolite, has been known for a long time. In the previously known reformate preparation processes, however, crystalline aluminosilicate zeolites were always used, which had a pore size of about 5 Angstrom units. Furthermore, it has long been known that normal paraffins form an undesirable component of a reformate, and attempts have been made to use crystalline aluminosilicate zeolites to remove these undesired paraffins.

   The previously known processes for the catalytic removal of normal paraffins have been carried out either in the absence of hydrogen, as described, for example, in the aforementioned US Pat. No. 3, 114, 969, or in the presence of hydrogen, as described, for example, in accordance with US Pat 3,395,094.



   All zeolites used in the process according to the invention have such a pore size that they allow methyl-substituted paraffins, they therefore have a pore size of more than 5 Angstrom units. So if one uses the previously applied measure of selective absorption of normal paraffin from a plant

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 Mixing the same with an isoparaffin would apply, then all the catalysts used in the process according to the invention would be useless, they would not correspond in the experiment and are usually referred to as "non-selective", since this term usually refers to zeolites with a pore size of about
5 Angstrom units is applied, but it is known that the selectivity, as far as the shape is concerned, can theoretically be applied to any shape or size,

   although the selectivity does not necessarily have to lead to an advantageous catalyst for a particular hydrocarbon conversion reaction.



   However, it was immediately recognized that the difference between the catalyst used in the process according to the invention and the catalyst according to the prior art is not only to be seen in the pore size, since, as is understandable, zeolites with large pore sizes have been known for a long time and have been found to be extremely effective in a wide variety of hydrocarbon conversion processes such as the catalytic cracking of gas oil to produce gasoline. The use of large pore zeolites in the conversion of hydrocarbons is described, for example, in U.S. Patent Nos. 3, 140, 251, No. 3, 140, 252, No. 3, 140, 253 and No. 3, 140, 249 described.



  It seems like the key to achieving an extremely effective method of reprocessing a
Reformats would lie in the careful control of the desired reactions and in reducing the undesired reactions to a minimum. As mentioned earlier, the normal paraffins can be viewed as undesirable components, and therefore an effective method should be a selective one
Removal of these normal paraffins. The inventive method goes beyond the sole removal of paraffins, since it appears that at the same time an alkylation of at least one
Part of the aromatic ring of the aromatic feed takes place with cracking products of normal and / or weakly branched paraffins, whereby more highly alkylated aromatic rings are obtained in the product.

   Accordingly, in the method according to the invention, to put it simply, not just one occurs
Removal of undesirable materials, as has been the case with previous processes, but rather removal of these undesirable materials and use of them to form alkylaromatic products directly and through alkylation of the aromatics in the feed, thereby producing a high yield of the desired Products is obtained.



   To make a process effective, it is necessary that the catalyst used has the ability to perform the aforementioned functions over long periods of time and with great effectiveness and selectivity, since otherwise an excessive amount of regeneration would have to take place, which would make the process economically viable would seriously affect.



   For example, it is known that the alkylation of aromatic products can be carried out with large-pore zeolites which were not synthesized from a solution with an organic cation content and which do not contain any organic cations. Typical large-pore known zeolites, which are available in different
Ion exchange forms having alkylation activity are materials of the faujasite family, in particular
Faujasite X and Y. However, under the reaction conditions prevailing during the preparation of a reformate or a product from the reforming plant, the known large-pore materials, such as X and Y, do not retain their alkylating activity for a long time, which means that they are used in an industrial process which the reaction conditions usually prevailing for the preparation of reformates are useless.



   It seems - without wanting to be bound by a theory through the following considerations - that the
The reason why the previously known large-pore catalysts were ineffective in the preparation of reformates is that, in order to achieve maximum effectiveness, a catalyst must have cracking activity in order to crack out normal paraffins, but it must also have an alkylating activity in order to be alkylaromatic Forming products.

   Usually, all known catalysts have the disadvantage that a good cracking catalyst was usually a very poor alkylation catalyst under the respectively prescribed operating conditions, which was also the case with the opposite, i. H. a good alkylation catalyst was a poor cracking catalyst under the respective process conditions to be used. So a
Catalyst is useful in the environment prevailing in the preparation of a reformate, it must have both a cracking function and an alkylation function, both functions must be stable over long periods of time so that the catalyst does not age in an unusually short time.



   Furthermore, it is not only sufficient if a catalyst has the ability to produce the desired products, it is also necessary that the desired products remain unchanged during the course of the reaction. For example, with regard to the alkyl aromatic hydrocarbons, it is not only necessary that the catalyst generates them, but that these alkyl aromatic hydrocarbons also remain unchanged during the course of the reaction.



   It has been found that zeolites, which are crystallized from a solution containing organic cations and contain an organic cation in the synthesized state, so that the organic cations at least partially saturate the electronegative property of the aluminum atoms in the crystal lattice, are actually very effective catalysts for the Represent the preparation of reformates, even if they are also used by the others

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 the aforementioned properties relating to the ratio of silica to alumina and the pore size, so that methyl paraffins are adsorbed under the reaction conditions.

   The effectiveness of such a catalyst is resistant to a variety of factors, but what is important is the fact that they are able to maintain their selectivity for certain reaction products over long periods of time, i.e. H. that these materials are extremely stable and selective during the reaction conditions to be used. The
Formation of crystalline aluminosilicates from solutions which contain organic cations is already considered
Synthetic art is known and it has been found that any organic cation is suitable provided that the zeolite possesses the other characteristics described above.

   In particular, would be on in this context
To refer to aluminosilicates, which are synthesized from solutions containing alkylammonium and alkylphosphonium cations.



   Examples of crystalline aluminosilicate zeolites which have the aforementioned properties are
Zeolite-ss, TEA Mordenit ZSM-12 and a zeolite group called ZSM-5, which are members
ZSM-5, ZSM-8 and ZSM-11.



   6-Zeolite is a well-known zeolite which is synthesized from a solution containing tetraethylammonium ions and is described in U.S. Patent No. 3,308,069.



   TEA mordenite is also synthesized from a solution containing tetraethylammonium ions and, expressed as the molar ratios of the oxides, in its synthesized form has the following formula:
 EMI3.1
 wherein M represents a mixture of cations, at least one of which is tetraalkylammonium, and n represents the valence of M.



   TEA mordenite has the crystal structure of mordenite.



   ZSM-12 has the following formula in the synthesized state, expressed as the molar ratios of the oxides:
 EMI3.2
 where M is a mixture of cations, at least one of which is tetraalkylammonium, n is the valence of the cation M and z is 0 to 60.



   However, the preferred zeolites used in the reforming process of the present invention are those which are commonly referred to as ZSM-5 types. The ZSM-5 zeolites which can be used in the process according to the invention usually have a pore size of more than 5 Angstrom units and less than
 EMI3.3
 linen aluminosilicates come under one of two general types. They either had pore sizes of about
5 Angstrom units or pore sizes from about 6 to about 15 Angstrom units. The aluminosilicates with a pore size of 5 Angstrom units were usually referred to as shape-selective because they are the most selective
Conversion of normal aliphatic compounds from a mixture of the same isoaliphatic compounds and cyclic compounds allowed.

   The second type of aluminosilicate, that is the one with a pore size of 6 to 15 Angstrom units, allows both normal and isoaliphatic compounds. Accordingly, a useful method for identifying a well shape-selective catalyst was to show that it selectively absorbs hexane from a mixture of the same with 2-methylpentane, since the first-mentioned compound was able to penetrate into its internal pore structure, which the last-mentioned iso-compound was not able to do.



   The ZSM-5 zeolites used in the process according to the invention can be regarded as lying between the two aforementioned types of aluminosilicates. Therefore, the ZSM-5 types used according to the invention allow entry into their internal pore structure of both normal aliphatic compounds and weakly branched aliphatic compounds, in particular compounds substituted by monomethyl, but they form an essential barrier against the extent of diffusion of all compounds, which at least have a quaternary carbon atom or have a minimum molecular dimension equal to or greater than that of the quaternary carbon atom,

   Furthermore, some aromatic and naphthenic compounds with side chains similar to those of normal aliphatic compounds and weakly branched aliphatic compounds of the aforementioned type can enter the inner pore structure of the catalysts used according to the invention.



   Without wanting to set up any theory, it appears that the crystalline ZSM-5 zeolites used according to the invention can not only be characterized in a simple manner by stating a pore size or a pore size range, but the uniform pore openings are these new ones

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 EMI4.1
 
 EMI4.2
 Openings where M is a cation, n represents the valence of the cation, W is selected from the group aluminum and gallium, Y is selected from the group silicon and germanium and z is 0 to 40.



   According to a preferred synthesized form, the zeolite, expressed as the molar ratios of the oxides, has the following formula:
 EMI4.3
 
 EMI4.4
 

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 EMI5.1
 
 EMI5.2
 
<tb>
<tb>: Interplanar <SEP> distance <SEP> d <SEP> (A) <SEP> Relative <SEP> intensity
<tb> 11, <SEP> 1 <SEP> 0, <SEP> 2 <SEP> S <SEP>
<tb> 10, <SEP> 0 <SEP> 0, <SEP> 2 <SEP> S <SEP>
<tb> 7, <SEP> 4 <SEP> 0, <SEP> 15 <SEP> W <SEP>
<tb> 7, <SEP> 1 <SEP> 0, <SEP> 15 <SEP> W <SEP>
<tb> 6, <SEP> 3 <SEP> 0, <SEP> 1 <SEP> W <SEP>
<tb> 6, <SEP> 040, <SEP> 1 <SEP> W <SEP>
<tb> 5.97 <SEP> ¯ <SEP> 0.1 <SEP> W
<tb> 5.56 <SEP> ¯ <SEP> 0.1 <SEP> W
<tb> 5.01 <SEP> ¯ <SEP> 0.1 <SEP> W
<tb> 4.60 <SEP> ¯ <SEP> 0.08 <SEP> W
<tb> 4, <SEP> 25 <SEP> 0, <SEP> 08 <SEP> W <SEP>
<tb> 3, <SEP> 85 <SEP> ¯ <SEP> 0, <SEP> 07 <SEP> VS
<tb> 3, <SEP> 71 <SEP> 0, <SEP> 05 <SEP> S
<tb> 3,

   <SEP> 64 <SEP> for <SEP> 0, <SEP> 05 <SEP> M
<tb> 8.04 <SEP> ¯ <SEP> 0.03 <SEP> W
<tb> 2, <SEP> 99 <SEP> 0, <SEP> 02 <SEP> W
<tb> 2, <SEP> 940, <SEP> 02 <SEP> W <SEP>
<tb>
 
 EMI5.3
 
 EMI5.4
 
<tb>
<tb> far <SEP> preferred <SEP> particularly <SEP> preferred
<tb> OH '/ SiO <SEP> 0, <SEP> 07-], <SEP> 0 <SEP> 0, <SEP> 1- <SEP> 0, <SEP> 8 <SEP> 0, <SEP> 2- <SEP> 0, <SEP> 75
<tb> RN + / <SEP> (R <SEP> N + <SEP> + Na +) <SEP> 0, <SEP> 2 <SEP> - <SEP> 0, <SEP> 95 <SEP> 0, <SEP> 3- <SEP> 0, <SEP> 9 <SEP> 0, <SEP> 4- <SEP> 0.9
<tb> H2O / OH- <SEP> 10 <SEP> - <SEP> 300 <SEP> 10 <SEP> - <SEP> 300 <SEP> 10 <SEP> - <SEP> 300
<tb> YC / W <SEP> 5-100 <SEP> 10-60 <SEP> 10-40 <SEP>
<tb>
 where R is propyl, W is aluminum and Y is silicon.

   This mixture is kept under reaction conditions until they have formed the zeolite crystals. The crystals are then separated from the liquid and recovered. Under typical reaction conditions, the temperature is about 75 to 1750 ° C. for a period of about 6 to 60 days. A preferred temperature range is from 90 to 150 ° C., the time duration in such a range being approximately 12 hours to 20 days.



   The disintegration of the gel particles is carried out until crystals form. The solid product is obtained from the reaction medium, for example by cooling to room temperature, filtering off and washing with water.



     ZSM-5- is preferably formed as a luminosilicate. The composition can be made using materials which provide the elements of the corresponding oxide. Such accom-

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 Compositions are, for example, in the case of an A luminosilicate, sodium aluminate, clay, sodium silicate, silica hydrosol, silica gel, silica, sodium hydroxide and tetrapropylammonium hydroxide. It goes without saying that each oxide component used in the reaction mixture for the preparation of the respective ZSM-5 zeolite can be supplied by one or more initial reaction components which are mixed with one another in any order.

   For example, sodium oxide can be obtained by an aqueous solution of
Sodium hydroxide or an aqueous solution of sodium silicate. The tetrapropylammonium cation can be provided by the bromide salt. The reaction mixture can be prepared batchwise or continuously. The crystal size and the crystallization time of the ZSM-5 composition changes with the type of reaction mixture used.



    I ZSM-8, expressed in terms of the molar ratios of the oxides, can be identified as follows:
 EMI6.1
 where M is at least one cation, n is the valence thereof and z is 0 to 40. According to a preferred synthesized form, the zeolite, expressed as the molar ratios of the oxides, has the following formula:
 EMI6.2
 wherein M is selected from the group comprising mixtures of alkali metal cations, in particular sodium and tetra-ethylammonium cations.



   Zeolite ZSM-8 can be prepared by reacting an aqueous solution containing either tetraethylammonium hydroxide or tetraethylammonium bromide with the elements of sodium oxide, aluminum oxide and an oxide of silicic acid.



   The relative proportions of the various ingredients have not been carefully determined, and it will be understood that not any or all of the proportions of reactants will be suitable to give the desired zeolite. In fact, completely different zeolites can be made using the same starting materials but changing their mutual concentration and reaction conditions, as outlined in U.S. Patent No. 3,308,069.

   Usually, however, when tetraethylammonium hydroxide is used, ZSM-8 can be prepared from the hydroxide, sodium oxide, aluminum oxide, silica and water by reacting these materials in such proportions that the reaction solution of a composition, expressed as molar ratios of the oxides , which falls into the following area:
 EMI6.3
 
<tb>
<tb> SiO / AO <SEP> from <SEP> about <SEP> 10 <SEP> to <SEP> about <SEP> 200
<tb> Na2 <SEP> 0 / tetraethylammonium hydroxide <SEP> from <SEP> about <SEP> 0.05 <SEP> to <SEP> 0.020
<tb> Tetraethylammonium hydroxide / SiO <SEP> from <SEP> about <SEP> 0.08 <SEP> to <SEP> 1, <SEP> 0
<tb> l \ <SEP> 0 / tetraethylammonium hydroxide <SEP> from <SEP> about <SEP> 80 <SEP> to <SEP> about <SEP> 200
<tb>
 
The crystals are then separated from the liquid.

   Typical reaction conditions are that the aforementioned reaction mixture is kept at a temperature of 100 to 1750 ° C. for a period of time from about 6 hours to 60 days. A preferred temperature range is approximately 150 to 175 ° C., and the duration in such a temperature range is approximately 12 hours to 8 days.



     ZSM-11 can be identified as follows, expressed as the molar ratios of the oxides:
 EMI6.4
 
 EMI6.5
 Formula:
 EMI6.6
 wherein M is selected from the group comprising a mixture of alkali metal cations, in particular sodium and tetrabutylammonium cations.

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 EMI7.1
 of aluminum or gallium, an oxide of silicon or germanium and water which, expressed as molar ratios of the oxides, has a composition which lies within the following ranges:
 EMI7.2
 
 EMI7.3
 The zeolite crystals are left to stand. The crystallization is preferably carried out under pressure in an autoclave or in a pressure reactor.

   The temperature range from 100 to 2000C can be used for this reaction; at lower temperatures, for example around LOOC, the crystallization takes longer. The crystals are then separated off and recovered. The new zeolite is preferably formed in an aluminosilicate form.



   As already mentioned, the ZSM-5 types of zeolite are the preferred catalysts in the preparation process according to the invention. For reasons that are not entirely clear, these materials give higher yields and products with a higher octane number, while being extraordinarily stable over long periods of time.



   Although one of the features of the crystalline aluminosilicate zeolites used in the process according to the invention is that they are synthesized from a solution containing organic cations so that they contain an organic cation, the presence of an organic cation during the actual use of these materials in the reforming process is not necessary.



   As already mentioned, it has been found that zeolites have certain properties with regard to the ratio of silica to alumina, the ability to adsorb methyl paraffins, and because they are made of
Solutions which contain organic cations have been crystallized so that the zeolite in its synthesized state contains an organic cation are particularly useful in the preparation of a reformate.
It should be noted, however, that such zeolites require a conventional base exchange in the course of known
Measures can be taken so that all or some of the organic cations are replaced before they are used. Furthermore, these materials can be heated to elevated temperatures so that the organic cations decompose in their "synthesized state".

   Therefore the requirement is that the
Zeolite contains an organic cation, only in relation to the synthesis of the zeolite and not mandatory for the use of the same.



   It should also be noted that the invention does not encompass zeolites which have been exchanged for bases with organic cations after their crystallization from solutions which did not contain any organic cations.



   Thus, the invention does not encompass the use of a zeolite such as, for example, zeolite Y, which has been dealuminized in order to increase the ratio of silica to alumina and then brought into contact with a solution, for example of tetrapropylammonium chloride.



   Such a material was not crystallized from a solution containing an organic cation, as is necessary to achieve an optimal reformate according to the invention.



   In the case of the zeolites used in the process according to the invention, the originally attached cations have preferably been replaced by a large number of other cations in the course of procedures known per se. Typical replacement cations are, for example, hydrogen, ammonium and metal cations and
Mixtures of the same. Preferred such replacement cations are hydrogen, magnesium, rare earths, ammonium, zinc, calcium, nickel and mixtures thereof.



   A typical ion exchange process consists in bringing the respective zeolite into contact with a salt of the corresponding replacement cation or replacement cations. Although a variety of salts can be used, the chlorides, nitrates and sulfates are preferred.

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 EMI8.1
 



    After contact with the salt solution of the desired replacement cation, the zeolite can be washed with water, dried at a temperature in the range of 65 to about 3150C, and then in air or in an inert gas at a temperature in the range of about 260 to 8000C for a period of time heated for 1 to 48 hours or more.



   It is also possible to treat the zeolite with steam at an elevated temperature in the range from 415 to 840 ° C, preferably 35 to 800 ° C. The treatment can be carried out in an atmosphere consisting partially or entirely of steam.



  A similar treatment can be carried out at lower temperatures and higher pressures, for example at 175 to 3700C and 0.7 to 14 kg / cm2.



   According to a preferred embodiment of the invention, a porous structure is used together with the aforementioned zeolite. The zeolite can be combined with a porous structure in such proportions, dispersed therein or otherwise closely mixed therewith that the resulting product in the final composition is 1 to 95% by weight, preferably 10 to 70% by weight, of zeolite contains.



   The term “porous structure” encompasses organic compositions with which the aluminosilicates can be combined, dispersed or intimately mixed in some other way, it being possible for the structure to be active or inactive. Of course, the porosity of the compositions used as a structure can already be from
Be naturally present or be generated mechanically or chemically in the respective material. Examples of structures which can be used are metals and alloys thereof, sintered metals and sintered glass, asbestos, silicon carbide aggregates, pumice stone, chamott stone, diatomaceous earth, alumina and inorganic oxides.



   Inorganic compositions, in particular those based on silica, are preferably used.



   Of these types of structures, inorganic oxides such as clay, chemically treated clay, silica, silica-alumina, etc. are preferable because of their superior porosity, abrasion resistance and stability.



   The introduction of zeolites into a structural material is known and is described, for example, in US Pat. No. 3, 140, 253.



   It has already been mentioned that the process according to the invention consists in converting a reformate or a product from the reforming plant by bringing the same into contact with crystalline aluminosilicate zeolites under conversion conditions in the presence of hydrogen. The method is characterized in that
1. the ratio of silica to alumina is greater than 15, preferably greater than 20,
2. that the zeolites were crystallized from a solution containing organic cations, so that the synthesized aluminosilicate contains organic cations, and
3. that the pore size is such that the aluminosilicate under the mentioned conversion conditions
Methyl paraffins adsorbed.



   The reformate or the product from the reforming plant which is treated according to the process according to the invention is preferably such that it is essentially only aromatic and paraffinic
Contains ingredients, although naphthenes and olefins can also be tolerated in the feed.



   Reformates, which essentially consist of aromatic and paraffinic components
 EMI8.2
 treated hydrogen and at least initially in contact with some reforming catalyst. This is a conventional reforming process which involves the pure production of hydrogen and is disclosed in U.S. Patent No. 3,395,094.



   Conventional reforming catalysts are, for example, alumina in the eta, chi or gamma form and mixtures thereof in combination with chromium, molybdenum or noble metals. Examples of platinums are the metal series containing platinum, palladium, osmium, iridium, ruthenium or rhodium and mixtures thereof deposited on a suitable carrier. In combination with the platinum metals, Group VIIB metals, including rhenium, can be used. Usually the major part of the catalyst consists of alumina, which may be present in an amount of 95% of the catalyst, based on its weight, or more. Other constituents can be combined with the alumina carrier, such as oxides of silica, magnesium, zirconium, thorium, vanadium, titanium, boron or mixtures thereof.



  The platinum-alumina combination, either with or without one of the components listed above, such as silica, etc., can be mixed with small amounts of a halogen, such as chlorine or fluorine, in amounts ranging from about 0.1 to about 5 gel. % accelerated. Usually less than Wo halogen is used in the platinum catalysts. According to a preferred embodiment, the support material of the reforming catalyst is one with a relatively large surface, such as preferably eta-alumina with a surface of at least 100 m 2 / g.

 <Desc / Clms Page number 9>

 



   Typical reforming conditions are temperatures in the range of about 415 to 540 C, preferably 475 to 526 C, liquid space velocities in the range of 0.1 to 10, preferably about 0.5 to about 5,
Pressures in the range from atmospheric pressure to about 49 kg / cm2 and higher, preferably from about 7 to about 42 kg / cm2, and a ratio of hydrogen to hydrocarbon in the range from 0.5 to about 20, preferably from about 1 to about 10 .



   In the process according to the invention, the reformate or the product from the reforming plant is brought into contact with or without added hydrogen via a ZSM-5 catalyst. As the examples show, the chemistry should be the same with or without hydrogen. Although there appears to be no chemical reason for the necessary presence of hydrogen for the purpose of processing the reformate in the course of the process according to the invention, in practice the production of the reformate via a reforming reaction always takes place with the production of hydrogen, and it does is not necessary or appropriate to this
To separate off hydrogen, which can actually only be advantageous as far as the catalyst is concerned, in particular with regard to the stability of the same.



   A separation of the hydrogen is particularly inexpedient because it would increase the process costs and because the reduced dilution of hydrogen, which is returned to the reforming plant, together with the implementation of the process according to the invention improves the previous reforming procedure . It goes without saying, of course, that it is not necessary to have one
Assign the hydrogenation / dehydrogenation component to the catalyst, although this measure represents a preferred embodiment of the invention. Accordingly, in its broadest interpretation, the invention comprises the preparation of a reformate, either in the absence or in the presence of hydrogen over the previously described zeolite catalyst with or without added hydrogenation component.



   The amount of hydrogenation / dehydrogenation component is not critical and can vary in a range from about 0.01 to 30 gel%, based on the total catalyst. A large number of hydrogenation components can either be combined with the zeolite and / or the structure in any way that ensures intimate contact of the components, using known measures, such as, for example, base exchange, impregnation, simultaneous precipitation, simultaneous gelation, mechanical mixing of a Component with the other u. Like. Can be used.

   Examples of hydrogenation components are metals, oxides and sulfides of metals from the periodic table, which are included in group VIB, which includes chromium, molybdenum, tungsten and the like. Like. Includes group IIB, which zinc and cadmium, group VIIB, which
Includes manganese and rhenium, and Group VIII which includes cobalt, nickel, platinum, palladium, ruthenium, rhodium and the like. The like. Includes, fall, and combinations of such metals, sulfides and oxides of metals
Groups VIB and VIII, such as nickel-tungsten sulfide, cobalt oxide, molybdenum oxide and the like. like



   The pretreatment before use changes depending on the kind of the hydrogenation component. For example, with components such as nickel-tungsten and cobalt-molybdenum, the catalyst will through
Sulfidation activated by sulfur. A hydrogenation stage is used for metals such as platinum or palladium.



  These procedures are generally known and are carried out in a manner known per se.



   The conversion is carried out in the course of the process according to the invention at a temperature between 260 and about 540 ° C., preferably 287 to 454 ° C. When hydrogen pressure is used, it is usually in a range from about 7 to about 210 kg / cm2, preferably from about 24.5 to 140 kg / cm2. The liquid space velocity, i.e. H. the liquid volume of hydrogen per hour per volume of catalyst is about 0.1 to 250, preferably 1 to 100. Usually the molar ratio of hydrogen to hydrocarbon feed is between about 1 and about 80, preferably between about 2 and about 15.



   The aforementioned temperature and pressure conditions specified in connection with the process according to the invention can usually be used over their entire range if the zeolite catalyst used has no hydrogenation / dehydrogenation effect.
 EMI9.1
 Greater attention should be paid to temperature-pressure conditions so that aromatic components which are present in the reformate or in the product from the reformer are not hydrogenated.



   It has now been found that within the range of process conditions for carrying out the conversion according to the process according to the invention, there are certain temperature and pressure ranges within the wide range within which it is thermodynamically possible to hydrogenate the aromatic constituents, and that on the other hand temperature and pressure ranges are present in which hydrogenation of the aromatic constituents is not possible.

   It was found that, although the selective hydrocracking of normal paraffins and the hydrogenation of olefins can be carried out in a fairly wide temperature and pressure range, the hydrogenation of aromatic compounds thermally only within a narrow range of applicable temperatures and pressures in the conversion according to the invention with the catalysts which have hydrogenation activity is possible.



   The only exception to this general principle lies in the fact that certain hydrogenation components cannot be used, which lead to destructive hydrogenolysis of the aromatic constituents

 <Desc / Clms Page number 10>

 lead and in this context the materials which have an excessively high activity and fall under group VIII of the periodic table should be avoided.



   The second way in which an effective process control can be achieved consists in the use of such temperature and pressure conditions under which it is actually thermodynamically possible to hydrogenate the aromatic constituents, but with such low proportions of hydrogenation components works that there is insufficient hydrogenation / dehydrogenation activity to catalyze the hydrogenation of the aromatic constituents.



   In the process according to the invention, therefore, hydrogenation / dehydrogenation components of any strength are used which, however, do not cause destructive hydrogenolysis of the aromatic constituents in situations in which the temperatures and pressures that are used do not allow thermodynamic hydrogenation of the aromatic constituents and where the Hydrogenation / dehydrogenation components have a mild hydrogenation effect when they are used under such temperature and pressure conditions at which it is thermodynamically possible to hydrogenate the aromatic constituents.



   These considerations can be better understood in connection with the drawing in which the figure shows three
Shows curves and is a graphical representation of those process conditions under which the selective conversion is carried out with a type B catalyst.



   The three curves represent the temperatures and pressures required to hydrogenate 10 weight percent aromatics in a feed at a hydrogen to aromatics ratio of 2, 5: 1, 10: 1 and 40: 1, respectively.



   To the left of these curves, an area labeled -A- represents those temperature and pressure conditions under which it is possible to thermodynamically hydrogenate more than 10% by weight of aromatic constituents.



   The area on the right-hand side of these curves, which is labeled -B-, includes a thermodynamic hydrogenation of aromatic compounds, i. H. a conversion of less than 10 wt. -0/0.



   So if one works under the conditions given by the area - B--, any hydrogenation / dehydrogenation component of any strength can be used as long as no destructive hydrogenation of the aromatic constituents occurs. Therefore, if one works in area-B-, metals of group IB,
IIB, V, VI and VII of the Periodic Table, including the oxides and sulfides thereof, can be used in any amount and in any concentration, since under these conditions all olefins are hydrogenated and the aromatic ones
Components are essentially unaffected. As already mentioned, it would not be possible to use metals from group VIII of the periodic table, since these metals have too high an activity and would lead to destructive hydrogenolysis of benzene.

   It is noted, however, that the metals are the
Group VIII and compounds thereof can be used if their activity is reduced by a pretreatment, by charring or by adding a deactivating agent to the charge so that only a negligible benzene conversion takes place.



   If the process is carried out under the temperature and pressure conditions which fall within the area --A-- of the graph, the selection of the hydrogenation / dehydrogenation component becomes more critical. In this procedure, it is possible to use hydrogenation components which fall under groups IB and IIB of the periodic table, these components can be used in any concentration, since it has been found that these materials do not have sufficient hydrogenation / dehydrogenation to be included under these Conditions to hydrogenate the aromatic substances. If hydrogenation components of groups V, VI and
VII of the Periodic Table are to be used, then they must be used in a correspondingly low concentration so that the hydrogenation of the aromatic constituents drops to a negligible value.

   In this regard, it has been found that the amount of these materials is in a range of approximately
0.05 to about 4.5 gel%, based on the total weight of the hydrogenation component and the luminosilicate, should be. A particularly preferred concentration range is from 0.2 to about 3% by weight of the hydrogenation component.



   Of course, the metals of Group VIII of the periodic table, as well as their oxides and sulfides, are not useful, since the activity of these materials is so high that hydrogenation of the aromatic compounds would take place. However, it is possible to use these compounds in the same way as under the conditions described in connection with A, provided that their activity has been reduced to such an extent that the hydrogenation of aromatic compounds can be neglected.



   In order to determine whether the hydrogenation activity of a catalyst used is such that "negligible hydrogenation of the aromatic compounds takes place", u. As a result of a voluntary deactivation of a group VIII metal catalyst or using a low concentration of groups V, VI and VII, an appropriate test method has been developed so that it can be determined very quickly and easily whether a catalyst is suitable or not Not.
 EMI10.1
 

 <Desc / Clms Page number 11>

 



   25% by weight of n-hexane and 25% by weight of isohexane, with a pressure of 14 kg / cm, a temperature of 370 ° C., a liquid space velocity of 4.0 (based on the total hydrocarbons) and a hydrogen to benzene molar ratio of 30: 1 can be used. The contact time is 60 minutes and the reactor effluent is then analyzed periodically, for example at 15 minutes and 45 minutes. If less than 10% by weight of benzene is converted by hydrogenation, the catalyst is suitable for use in the process according to the invention in terms of hydrogenation activity.



   When working under conditions where it is impossible to hydrogenate aromatic compounds, i. H. In area-A- of the figure, a simple test method has also been developed to determine whether the activity of the Group VIII metal and its compounds have been decreased sufficiently to prevent destructive hydrogenolysis of the aromatic compounds.



   In this test, a zeolite containing a Group VIII metal or a compound thereof is
 EMI11.1
 speed 4.0, the hydrogen to benzene molar ratio 30: 1. The product from the reactor is analyzed and if less than 10% by weight benzene is found to have decomposed, the catalyst is considered to be for the hydrogenation aromatic compounds considered suitable in the process according to the invention.



   The method according to the invention can be carried out in the most varied of ways using the aforementioned
Process parameters are carried out. For example, it is possible to carry out the conversion in a separate reactor. In this embodiment, a conventional reforming plant is operated to provide a reformate of the aforementioned type, after which the reformate or the product from the reactor is introduced together with added hydrogen into a separate reactor, which the aforementioned zeolite catalyst with or without a Contains hydrogenation component.

   According to a further embodiment of the invention, a separate reactor does not have to be used, but the last reactor in a conventional three-stage reforming reactor, the last reactor being filled with a conventional platinum reforming catalyst and with the aforementioned zeolite catalyst, so that the hydrocarbon feed is first fed with the conventional platinum reforming catalyst and then comes into contact with the zeolite catalyst.



  In this way, the feed in the first two stages of a conventional reactor is reformed in the usual way, after which the product enters the third stage, in which the conventional reforming takes place in the area of the reactor head, after which a selective conversion at the bottom of the reactor with the zeolite catalyst takes place. This embodiment has the advantage that existing systems can be used to carry out the method according to the invention.



   As already stated, according to one embodiment of the invention, a Cs + high paraffinic petroleum fraction can be added to the reformate and the product from the reformer, which are then converted with the ZSM-5 catalyst. As previously stated, it appears that the process of the present invention involves alkylation of the aromatic constituents of the feed to result in significantly upgraded products of greater economic value. The addition of strongly paraffinic material such as Udex raffinate leads to an increase in the degree of alkylation, whereby more valuable products are obtained.



   Although the invention has only been described in connection with the achievement of a better octane number in the reformate and with an increase in the ratio of yield to octane number, the process according to the invention offers further advantages compared to the previous procedure. One of these advantages can be seen in the fact that when the method according to the invention is carried out, a greater hydrogen purity is obtained than in conventional methods. Accordingly, with a given increase in the octane number during the preparation of a reformate, the process according to the invention results in a higher degree of hydrogen purity due to the fact that the tendency for methane formation in the presence of the catalysts used according to the invention is extremely low.

   The greater purity of hydrogen offers obvious economic advantages.



   The invention is illustrated in more detail by the following examples:
Examples 1 and 2: These examples illustrate the new chemical reactions that occur when ZSM-5 catalysts are used. The charge in Example 1 consisted of n-octane, in Example 2 of equal parts by weight of n-octane and benzene.

   In each case the hydrogen form of ZSM-5 was used and the following reaction conditions were observed:
 EMI11.2
 
<tb>
<tb> pressure <SEP> 35 <SEP> kg / cm <SEP>! <SEP>
<tb> temperature, <SEP> C <SEP> 122
<tb> LHSV <SEP> (liquid space velocity) <SEP> 1
<tb> hydrogen
<tb>
 The following results were obtained:

   

 <Desc / Clms Page number 12>

 
 EMI12.1
 
<tb>
<tb> Total yield <SEP> example <SEP> 1 <SEP> example <SEP> 2
<tb> g / 100 <SEP> loading
<tb> Cl <SEP> <<SEP> 0, <SEP> 1 <SEP> <<SEP> 0, <SEP> 1 <SEP>
<tb> C2 <SEP> 0, <SEP> 1 <SEP> <<SEP> 0, <SEP> 1 <SEP>
<tb> Cs <SEP> 4, <SEP> 1 <SEP> 4, <SEP> 0 <SEP>
<tb> butane <SEP> 12.8 <SEP> 9.9
<tb> Pentanes <SEP> 16, <SEP> 4 <SEP> 6.4
<tb> C paraffins <SEP> 4.8 <SEP> 1.2
<tb> C paraffins <SEP> 2.4 <SEP> 0.2
<tb> C paraffins <SEP> 49.7 <SEP> 13, <SEP> 5
<tb> Benzene <SEP> 1, <SEP> 1 <SEP> 33.3
<tb> Alkylbenzenes <SEP> (C) <SEP> 4,3 <SEP> 26,2
<tb> Tetraline, <SEP> Indane <SEP> 0.6 <SEP> 3.8
<tb> Naphthalenes <SEP> 0.2 <SEP> 0.6
<tb> Naphthenes <SEP> 2,2 <SEP> 0, <SEP> 1 <SEP>
<tb> Olefins <SEP> 1.8 <SEP> 0.9
<tb> 100.0 <SEP> g <SEP> 100.0 <SEP> g
<tb>
 
Of the 50.3 g of n-octane,

   which disappeared from the feed of n-octane alone (Example 1), 40.6 g (81%) went to low carbon paraffins and 6.2 g (12%) to aromatics.



  Smaller amounts were converted to naphthenes (50/0) and olefins (2 o).



   In Example 2, the feed had a content of aromatic compounds, the content of aromatic compounds in the product obtained was 63.9%.



     Examples 3 to 23: The following examples serve to further illustrate the process according to the invention. In each case the feed was a reformate which was obtained by splitting a mid-continent petroleum together with hydrogen over a platinum reforming catalyst at 415 to 5400C and a pressure of about 35 kg / cm 2.



   The reformate, along with hydrogen, was then contacted with a nickel-hydrogen exchanged ZSM-5 which had previously been sulfided. Further process conditions and the results obtained can be found in the following table:

 <Desc / Clms Page number 13>

 table
 EMI13.1
 
<tb>
<tb> Example <SEP> No. <SEP> loading <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 6 <SEP> 7 <SEP> 8 <SEP> 9 <SEP> 10 <SEP> 11
<tb> pressure, <SEP> psig <SEP> 400
<tb> H2 / HC <SEP> molar ratio <SEP> 2
<tb> C <SEP> 287 <SEP> 258 <SEP> 343 <SEP> 343 <SEP> 346 <SEP> 347 <SEP> 350 <SEP> 371 <SEP> 315
<tb> LHSV <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 10 <SEP> 20 <SEP> 30.

   <SEP> 40 <SEP> 40 <SEP> 5
<tb> Throughput time, <SEP> h <SEP> 5 <SEP> 6 <SEP> 6 <SEP> 3 <SEP> 11/2 <SEP> 1 <SEP> 2/3 <SEP> 2/3 <SEP> 6th
<tb> liquid product, <SEP> density
<tb> 0 <SEP> API <SEP> 54.5 <SEP> 52.0 <SEP> 51.3 <SEP> 48.1 <SEP> 50, <SEP> 7 <SEP> 51. <SEP> 9 <SEP> 51, <SEP> 9 <SEP> 52, <SEP> 4 <SEP> 51,5 <SEP> 50, <SEP> 9 <SEP>
<tb> RON, <SEP> pure <SEP> 94.7 <SEP> 97.5 <SEP> 100.7 <SEP> 98.7 <SEP> 97.0 <SEP> 95, <SEP> 9 <SEP > 95, <SEP> 2 <SEP> 97, <SEP> 4 <SEP> 98, <SEP> 8 <SEP>
<tb> Material compensation <SEP> 102, <SEP> 5 <SEP> 97, <SEP> 3 <SEP> 96, <SEP> 2 <SEP> 96, <SEP> 2 <SEP> 102.0 <SEP> 101 , <SEP> 2 <SEP> 103, <SEP> 9 <SEP> 100.0 <SEP> 97.7
<tb>% by weight, <SEP> C <SEP>.

   <SEP> wt .- <SEP> -0, <SEP> 03 <SEP> 0.03 <SEP> 0.04 <SEP> 0.02 <SEP> 0, <SEP> 02 <SEP> 0, <SEP > 02 <SEP> 0.03 <SEP> 0.02
<tb> Ca, <SEP> gel .-% - 0, <SEP> 01 <SEP> 0.05 <SEP> 0.03 <SEP> 0, <SEP> 02 <SEP> - <SEP> - <SEP > 0.03
<tb> C <SEP>% by weight <SEP> 0.08 <SEP> 0.26 <SEP> 0.26 <SEP> 0.29 <SEP> 0.15 <SEP> 0.06 <SEP> 0, <SEP> 10 <SEP> 0, <SEP> 16 <SEP> 0.05
<tb> C3, <SEP>% by weight <SEP> - <SEP> - <SEP> - <SEP> 0.01 <SEP> - <SEP> 0, <SEP> 04 <SEP> 0.01 < SEP> 0, <SEP> 08
<tb> Ca, <SEP>% by weight <SEP> 1, <SEP> 22 <SEP> 2, <SEP> 85 <SEP> 7.51 <SEP> 5.70 <SEP> 2.35 <SEP > 1, <SEP> 60 <SEP> 1, <SEP> 47 <SEP> 2.53 <SEP> 2, <SEP> 26 <SEP>
<tb> Total dry gas, <SEP>% by weight <SEP> - <SEP> 1.30 <SEP> 3.15 <SEP> 7.90 <SEP> 6.07 <SEP> 2.54 <SEP> 1 , <SEP> 72 <SEP> 1, <SEP> 60 <SEP> 2, <SEP> 83 <SEP> 2, <SEP> 33 <SEP>
<tb> i-C, <SEP> Vos .-% <SEP> 0.7 <SEP> 2.3 <SEP> 3.1 <SEP> 4.6 <SEP> 5.1 <SEP> 2,

  4 <SEP> 1.9 <SEP> 2.0 <SEP> 2.5 <SEP> 2.9
<tb> C4, <SEP> Vol .-% <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 0.1 <SEP> 0.1 <SEP> 0.1 <SEP> 0 , 1 <SEP> 0.2
<tb> n-C4, <SEP> Vol .-% <SEP> 2.8 <SEP> 2.7 <SEP> 3.9 <SEP> 5.1 <SEP> 5, <SEP> 0 <SEP> 3, <SEP> 6 <SEP> 3, <SEP> 2 <SEP> 3.0 <SEP> 3, <SEP> 4 <SEP> 3.8
<tb> i-C5, <SEP> Vol .-% <SEP> 8.16.2 <SEP> 6.3 <SEP> 6.5 <SEP> 7.3 <SEP> 7.1 <SEP> 6 , 9 <SEP> 7.2 <SEP> 7.1 <SEP> 7.2
<tb> Cg, <SEP> Vol .-% <SEP> 0.1 <SEP> - <SEP> 0.1 <SEP> 0.1 <SEP> 0.2 <SEP> 0.1 <SEP> 0 , 1 <SEP> 0.1 <SEP> 0.2 <SEP> 0.1
<tb> n-C5, <SEP> Vol.-50 <SEP> 8, <SEP> 1 <SEP> 5,0 <SEP> 4, <SEP> 1 <SEP> 2, <SEP> 6 <SEP> 3.7 <SEP> 4, <SEP> 8 <SEP> 5, <SEP> 2 <SEP> 5.6 <SEP> 4, <SEP> 8 <SEP> 4.8
<tb> C4 +, <SEP> Vol .-% <SEP> 100 <SEP> 95.4 <SEP> 93.2 <SEP> 87.5 <SEP> 91.1 <SEP> 94.1 <SEP> 95 , 1 <SEP> 95.7 <SEP> 93, <SEP> 8 <SEP> 93, <SEP> 8 <SEP>
<tb> C5 +, <SEP> Vol .-% <SEP> 96,

  5 <SEP> 90.4 <SEP> 86.0 <SEP> 77.8 <SEP> 80.9 <SEP> 88.0 <SEP> 90.0 <SEP> 90.6 <SEP> 87.7 < SEP> 87.1
<tb> C @ +, <SEP> Vol .-% <SEP> 80, <SEP> 1 <SEP> 79, <SEP> 2 <SEP> 75.6 <SEP> 68.7 <SEP> 69.7 <SEP> 76.0 <SEP> 77, <SEP> 8 <SEP> 77.7 <SEP> 75.5 <SEP> 74, <SEP> 9 <SEP>
<tb> RON, <SEP> pure, <SEP> C + <SEP> 90, <SEP> 3 <SEP> 94.6 <SEP> 97.6 <SEP> 101, <SEP> 1 <SEP> 98.8 <SEP> 97.0 <SEP> 95, <SEP> 9 <SEP> 95, <SEP> 1 <SEP> 97.4 <SEP> 98, <SEP> 9 <SEP>
<tb> RON, <SEP> pure, <SEP> C6 + <SEP> 92.4 <SEP> 96.5 <SEP> 99.7 <SEP> 103.2 <SEP> 101.1 <SEP> 99.3 <SEP> 98.1 <SEP> 97.4 <SEP> 99.5 <SEP> 101.6
<tb>
 

 <Desc / Clms Page number 14>

   Table (continued)
 EMI14.1
 
<tb>
<tb> Example <SEP> No.

   <SEP> 12 <SEP> 13 <SEP> 14 <SEP> 15 <SEP> 16 <SEP> 17 <SEP> 18 <SEP> 19 <SEP> 20 <SEP> 21 <SEP> 22 <SEP> 23
<tb> pressure, <SEP> psig <SEP> 250 <SEP> 400 <SEP> 250
<tb> H2 / HC <SEP> molar ratio <SEP> 5 <SEP> 10 <SEP> 2 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 10 <SEP> 20 <SEP> 10 <SEP> 10 <SEP> 5
<tb> C <SEP> 488 <SEP> 491 <SEP> 487 <SEP> 489 <SEP> 500 <SEP> 457 <SEP> 482 <SEP> 491 <SEP> 426 <SEP> 370 <SEP> 429 <SEP > 486
<tb> LHSV <SEP> 207 <SEP> 212 <SEP> 208 <SEP> 215 <SEP> 215 <SEP> 215 <SEP> 215 <SEP> 215 <SEP> 99 <SEP> 10 <SEP> 103 <SEP > 206
<tb> Throughput time, <SEP> h <SEP> 2 <SEP> 2 <SEP> 1/3 <SEP> 2 <SEP> 1/2 <SEP> 5 <SEP> 21/3 <SEP> 21/4 < SEP> 21/6 <SEP> 21/4 <SEP> 5 <SEP> 18 <SEP> 4 <SEP> 1/6 <SEP> 2 <SEP> 1/4
<tb> liquid product, <SEP> density
<tb> <SEP> API <SEP> 49.3 <SEP> 48.3 <SEP> 49.7 <SEP> 49.3 <SEP> 49.8 <SEP> 50.1 <SEP> 49.6 < SEP> 47.3 <SEP> 47.5 <SEP> 48,

  3 <SEP> 51.4 <SEP> 50.0
<tb> RON, <SEP> pure <SEP> 97, <SEP> 3 <SEP> 96.0 <SEP> 98, <SEP> 4 <SEP> 97, <SEP> 5 <SEP> 97.6 <SEP > 96, <SEP> 2 <SEP> 97, <SEP> 3 <SEP> 97, <SEP> 7 <SEP> 96, <SEP> 1 <SEP> 97, <SEP> 3 <SEP> 95.4 < SEP> 96.7
<tb> Material compensation <SEP> 102.6 <SEP> 110.2 <SEP> 94.5 <SEP> 101.3 <SEP> 102.7 <SEP> 106.9 <SEP> 102.7 <SEP> 109 , 1 <SEP> 100,6 <SEP> 112, <SEP> 8 <SEP> 104, <SEP> 9 <SEP>
<tb>% by weight, <SEP> C1, <SEP>% by weight <SEP> 0.27 <SEP> 0.19 <SEP> 0.57 <SEP> 0.23 <SEP> 0.33 <SEP> 0.10 <SEP> 0.19 <SEP> 0.28 <SEP> 0, <SEP> 06 <SEP> 0.08 <SEP> 0, <SEP> 1 <SEP>
<tb> C.

   <SEP> Weight- "<SEP> 0.61 <SEP> 0.70 <SEP> 0, <SEP> 74 <SEP> 0, <SEP> 59 <SEP> 0.76 <SEP> 0, <SEP > 39 <SEP> 0.53 <SEP> 0.61 <SEP> 0, <SEP> 01 <SEP> 0, <SEP> 27 <SEP> 0.5
<tb> C2, <SEP>% by weight <SEP> 0.80 <SEP> 0.42 <SEP> 1.40 <SEP> 0.61 <SEP> 0.85 <SEP> 0.23 <SEP > 0.46 <SEP> 0.52 <SEP> - <SEP> 0, <SEP> 35 <SEP> 0, <SEP> 4 <SEP>
<tb> C, <SEP>% by weight <SEP> 1, <SEP> 25 <SEP> 1.38 <SEP> 1, <SEP> 35 <SEP> 1, <SEP> 24 <SEP> 1, 56 <SEP> 1.05 <SEP> 1.08 <SEP> 1, <SEP> 03-0, <SEP> 33 <SEP> 1.0
<tb> C, <SEP>% by weight <SEP> 3, <SEP> 27 <SEP> 2.74 <SEP> 8.

   <SEP> 00 <SEP> 3, <SEP> 51 <SEP> 4, <SEP> 54 <SEP> 3, <SEP> 48 <SEP> 3.69 <SEP> 3, <SEP> 66 <SEP> 4 , <SEP> 28 <SEP> 2.50 <SEP> 2.7
<tb> total dry gas, <SEP> wt .-% <SEP> 6.20 <SEP> 5.43 <SEP> 12.06 <SEP> 6, <SEP> 18 <SEP> 8.04 <SEP> 5, <SEP> 25 <SEP> 5, <SEP> 95 <SEP> 6, <SEP> 10 <SEP> 4, <SEP> 35 <SEP> 3,53 <SEP> 4, <SEP> 9 <SEP>
<tb> i-C4, <SEP> Vol .-% <SEP> 0.9 <SEP> 2.6 <SEP> 3.3 <SEP> 2.0 <SEP> 2.5 <SEP> 3.0 <SEP> 2.3 <SEP> 3.3 <SEP> 3.5 <SEP> 3.2 <SEP> 1.9
<tb> C4, <SEP> vol .-% <SEP> 0.7 <SEP> 1.0 <SEP> 1.2 <SEP> 0.8 <SEP> 1.3 <SEP> 0.9 <SEP > 1.1 <SEP> 0.8 <SEP> 0.1 <SEP> 0.7 <SEP> 0.9
<tb> nC, <SEP> Vol .-% <SEP> 3.2 <SEP> 2.4 <SEP> 4.6 <SEP> 2, <SEP> 6 <SEP> 3, <SEP> 2 <SEP > 2.6 <SEP> 2, <SEP> 9 <SEP> 1.7 <SEP> 2.5 <SEP> 1, <SEP> 9 <SEP> 2, <SEP> 2 <SEP>
<tb> i-Cs'Vol.

   <SEP> -0/0 <SEP> 5, <SEP> 1 <SEP> 5, <SEP> 0 <SEP> 6, <SEP> 5 <SEP> 5, <SEP> 8 <SEP> 5, <SEP > 5 <SEP> 5.0 <SEP> 5.6 <SEP> 4.3 <SEP> 5, <SEP> 5 <SEP> 6, <SEP> 2 <SEP> 5, <SEP> 0
<tb> C6. <SEP> Vol .-% <SEP> 0.5 <SEP> 0.3 <SEP> 0.4 <SEP> 0.4 <SEP> 0.5 <SEP> 0.3 <SEP> 0.5 < SEP> 0.3 <SEP> 0.1 <SEP> 0.3 <SEP> 0.4
<tb> n-C5, <SEP> Vol .-% <SEP> 4.6 <SEP> 3.3 <SEP> 2.6 <SEP> 3, <SEP> 9 <SEP> 3, <SEP> 4 <SEP> 3, <SEP> 3 <SEP> 3, <SEP> 8 <SEP> 2.5 <SEP> 3, <SEP> 1 <SEP> 4, <SEP> 1 <SEP> 3.5
<tb> C4 +, <SEP> Vol .-% <SEP> 89.4 <SEP> 90.4 <SEP> 85.6 <SEP> 89, <SEP> 9 <SEP> 88.6 <SEP> 91, <SEP> 3 <SEP> 90.6 <SEP> 89.0 <SEP> 92, <SEP> 1 <SEP> 94.7 <SEP> 92, <SEP> 2 <SEP>
<tb> Cs +, <SEP> Vol.

   <SEP> -0/0 <SEP> 84.6 <SEP> 84, <SEP> 4 <SEP> 76.5 <SEP> 84, <SEP> 6 <SEP> 81.6 <SEP> 84.8 < SEP> 83.8 <SEP> 83.2 <SEP> 86.0 <SEP> 88, <SEP> 9 <SEP> 87, <SEP> 1 <SEP>
<tb> Cl +, <SEP> Vol .-% <SEP> 74.4 <SEP> 75, <SEP> 8 <SEP> 67.0 <SEP> 74, <SEP> 5 <SEP> 72, <SEP> 3 <SEP> 76, <SEP> 2 <SEP> 74.0 <SEP> 76, <SEP> 2 <SEP> 77.4 <SEP> 78.3 <SEP> 78.2
<tb> RON, <SEP> pure, <SEP> C5 + <SEP> 97.1 <SEP> 95.9 <SEP> 98.4 <SEP> 97.5 <SEP> 97.6 <SEP> 96, < SEP> 2 <SEP> 97, <SEP> 3 <SEP> 97.7 <SEP> 97, <SEP> 3 <SEP> 95.3 <SEP> 96.7
<tb> RON, <SEP> pure, <SEP> C6 + <SEP> 99.3 <SEP> 97.4 <SEP> 100.2 <SEP> 99.4 <SEP> 99.4 <SEP> 97.6 <SEP> 99.1 <SEP> 98.9 <SEP> 98.9 <SEP> 97.0 <SEP> 98.3
<tb>
 

 <Desc / Clms Page number 15>

 
 EMI15.1
 
Examples 24 and 25:

   These examples show that improved results can be obtained regardless of whether a hydrogenation / dehydrogenation metal is used with the ZSM-5 zeolite.



   The following comparison was made at 315 ° C, 24 kg / cm2, 5 LHSV, 2 H / HC molar ratio.



  5 The butane content of the feed was not the same, these are listed separately. The yields achieved with the two catalysts do not differ significantly from one another, although the higher octane number (one unit) compared to H-ZSM-5 must be taken into account.
 EMI15.2
 
<tb>
<tb>



  Example <SEP> 24 <SEP> Example <SEP> 25
<tb> H-ZSM-5 <SEP> Ni / H-ZSM-5 <SEP>
<tb> Loading <SEP> product <SEP> Loading <SEP> product
<tb> Cl <SEP>% by weight <SEP> 0.03 <SEP> 0, <SEP> 03
<tb> C2, <SEP>% by weight <SEP> 0.01 <SEP> 0.01
<tb> C2 <SEP>% by weight <SEP> 0.01 <SEP> 0, <SEP> 26 <SEP>
<tb> C3, <SEP> -0/0 <SEP> - <SEP> - <SEP>
<tb> C, <SEP>% by weight <SEP> 3, <SEP> 98 <SEP> 2, <SEP> 85
<tb> Total drying gas, <SEP>% by weight <SEP> 4.03 <SEP> 3, <SEP> 15 <SEP>
<tb> iC, <SEP> Vol .-% <SEP> 2, <SEP> 0 <SEP> 4, <SEP> 9 <SEP> 0, <SEP> 7 <SEP> 3, <SEP> 1 <SEP >
<tb> C4, <SEP> Vol .-% <SEP> - <SEP> 0.1
<tb> n-C4, <SEP> Vol .-% <SEP> 4, <SEP> 8 <SEP> 7, <SEP> 0 <SEP> 2, <SEP> 8 <SEP> 3, <SEP> 9 <SEP>
<tb> C, <SEP> +, <SEP> Vol.

   <SEP> -0/0 <SEP> 100, <SEP> 0 <SEP> 93.0 <SEP> 100, <SEP> 0 <SEP> 93, <SEP> 2 <SEP>
<tb> C5 +, <SEP> Vol .-% <SEP> 93, <SEP> 2 <SEP> 81, <SEP> 1 <SEP> 96.5 <SEP> 86.0
<tb> C6 +, <SEP>% by volume <SEP> 77.2 <SEP> 71.3 <SEP> 80.1 <SEP> 75.6
<tb> Cg + <SEP> RON, <SEP> pure <SEP> 90, <SEP> 3 <SEP> 98, <SEP> 9 <SEP> 90.3 <SEP> 97.6
<tb> C + <SEP> RON, <SEP> pure <SEP> 92, <SEP> 4 <SEP> 101, <SEP> 0 <SEP> 92, <SEP> 4 <SEP> 99.7
<tb>
 
 EMI15.3
 Results obtained:

   
 EMI15.4
 
<tb>
<tb> Loading <SEP> example <SEP> 26 <SEP> example <SEP> 27
<tb> hydrogen <SEP> no <SEP> hydrogen
<tb> pressure, <SEP> kg / cm2 <SEP> 28 <SEP> 35
<tb> H2 / HC <SEP> molar ratio <SEP> 2
<tb> LHSV <SEP> 5 <SEP> 1
<tb> temperature, <SEP> OC <SEP> 315 <SEP> 318
<tb> drying gas, <SEP> gel. <SEP> 4, <SEP> 03 <SEP> 7, <SEP> 38
<tb> C4, <SEP> Vol .-% <SEP> 6.8 <SEP> 12.0 <SEP> 16, <SEP> 8
<tb> C5 +, <SEP> Vol .-% <SEP> 93.2 <SEP> 81.1 <SEP> 76, <SEP> 0
<tb> C5 + <SEP> RON, <SEP> pure <SEP> 90, <SEP> 3 <SEP> 98.9 <SEP> 98.9
<tb> Throughput <SEP> No. <SEP> PS-511 <SEP> CT-144-21-2
<tb>
 
The above results show that the liquid yield is much higher and the dry gas yield is much lower when working in the presence of hydrogen.



   EXAMPLES 28 to 34: The following table shows the fate of the + paraffins that are converted. As can be seen, in all cases there is an increase in the alkyl aromatic compounds.

 <Desc / Clms Page number 16>

 Fate of the C5 + 0 paraffins
 EMI16.1
 
<tb>
<tb> 28 <SEP> 29 <SEP> 30 <SEP> 31 <SEP> 32 <SEP> 33 <SEP> 34
<tb> g / 100 <SEP> g <SEP> loading <SEP> 315 C <SEP> 3460C <SEP> 371 C <SEP> 429 C <SEP> 483 C <SEP> 491 C <SEP> 500 C
<tb> Disappearance <SEP> of
<tb> C + paraffins <SEP> 18.03 <SEP> 14.04 <SEP> 14, <SEP> 34 <SEP> 12, <SEP> 39 <SEP> 16, <SEP> 22 <SEP> 18, <SEP> 21 <SEP> 18, <SEP> 24 <SEP>
<tb> Occurrence <SEP> of <SEP>:

   <SEP>
<tb> C1-C3 <SEP> 3.15 <SEP> 2.54 <SEP> 2.83 <SEP> 3.53 <SEP> 5.95 <SEP> 6.10 <SEP> 8.04
<tb> C4 content <SEP> 2.74 <SEP> 1.99 <SEP> 1.99 <SEP> 1.73 <SEP> 2.53 <SEP> 1.73 <SEP> 2.73
<tb> growth <SEP> on
<tb> alkylbenzene
<tb> Ring carbon <SEP> 4, <SEP> 96 <SEP> 3, <SEP> 64 <SEP> 3, <SEP> 96 <SEP> 4, <SEP> 31 <SEP> 4, <SEP> 35 < SEP> 6, <SEP> 83 <SEP> 5, <SEP> 49 <SEP>
<tb> Part <SEP> on
<tb> alkylbenzene
<tb> Side chain <SEP> 3.54 <SEP> 2.77 <SEP> 2.67 <SEP> 1.88 <SEP> 1.41 <SEP> 2.34 <SEP> 1.22
<tb> 14.40 <SEP> 10.94 <SEP> 11.45 <SEP> 11.45 <SEP> 14.24 <SEP> 17.00 <SEP> 17.48
<tb>
   Example 35:. The following examples illustrate a nickel H-ZSM-5 zeolite as used in Examples 3-23 and 25-34.



  The following solutions were prepared: (a) 0.45 kg of sodium aluminate, containing 41.8% by weight of Al2O3 and 25% by weight of water; (b) 36.2 kg of a Q-mixture of sodium silicate in 45 liters of water, d. H. 28.9% by weight SiO @, 9.0% by weight Na2O, 62.1% by weight H2O: (c) 4.5 kg tetrapropylammonium bromide and 22.5 l water; (d) 3.6 kg of sulfuric acid in 10.8 l of water.



  Solution (c) was added to solution (b), after which solution (a) was added to the 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 held at a temperature of about 90 to 990 ° C. for about 267.5 hours until crystallization was complete and ZSM-5 was formed. After filtering, the wet filter cake was mixed with water, washed and then dried at 1210C. After drying, the material was calcined at 3700 ° C. for 3 hours.



  The calcined ZSM-5 was then exchanged with 1.0N ammonium nitrate solution for 4 hours at room temperature. The ammonium exchanged zeolite was then exchanged for 4 hours with a 0.5N nickel nitrate solution at 880C.



  The exchanged material was then washed free of nickel solution, dried at 1210C, crushed to 30 to 60 meshes and then calcined at 540C for 10 hours.



  The calcined ZSM-5 zeolite was then sulfided with a mixture of about 2% by weight hydrogen sulfide in hydrogen at 4000C.
 EMI16.2
 Examples 1, 2 and 24 was used. The following solutions were prepared: (a) 0.25 kg of sodium aluminate with a content of 44.7% aluminum oxide and 6.3 liters of water: (b) 21 kg of a Q-mixture of sodium silicate and 25.5 liters of HO; (c) 2.5 kg of tetrapropylammonium bromide and 12.6 liters of HO; (d) 2.1 kg of sulfuric acid in 6.3 l of water.



   Solution (c) was added to solution (b), after which solution (a) was added to the mixture of (c) and (d). 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 formed.



   The gel was heated to a temperature of 93 to 990 ° C. for a total of 167 hours until a ZSM-5 identified as a crystalline aluminosilicate was obtained.



   The ZSM-5 zeolite was dried, calcined in air for 10 hours at 5400C and then base exchanged with a 1.0 On solution of ammonium chloride in water at room temperature until the sodium content was reduced to 0.01% by weight.



   The ammonium-exchanged ZSM-5 zeolite was brought to a size of 30 to 60 mesh and then calcined at 5400 ° C. overnight.



   Examples 37 to 42: A C6 reformate product was prepared by mixing 50% benzene with 25%

 <Desc / Clms Page number 17>

 n-hexane and 25% isohexane simulated. The material was then contacted with various forms of ZSM-5 catalysts at 14 kg / cm, a hydrogen / hydrocarbon molar ratio of 15/1, an LHSV of 4 and at 371.degree.

   High conversion to eliminate the low octane components and enrichment in high octane were observed as follows:
 EMI17.1
 
<tb>
<tb> Example <SEP> catalyst <SEP> wt. <SEP> -0/0 <SEP> conversion
<tb> n-hexane <SEP> 2-methylpentane <SEP> benzene
<tb> 37 <SEP> H / ZSM-5 <SEP> 97.9 <SEP> 43.3 <SEP> 12.5
<tb> 38 <SEP> NaH / ZSM- <SEP> 5 <SEP> 28.5 <SEP> 2, <SEP> 1 <SEP> 4.2
<tb> 39 <SEP> Zn / H / ZSM-5
<tb> 0, <SEP> 8710 <SEP> Zn <SEP> 81, <SEP> 2 <SEP> 31.5 <SEP> 14.0
<tb> 40 <SEP> Ni / H / ZSM-5
<tb> 0, <SEP> 2 <SEP> <SEP> o <SEP> Ni <SEP> 73.4 <SEP> 23.4 <SEP> 5.7
<tb> 41 <SEP> Zn / H / ZSM-5
<tb> 1, <SEP> 21% <SEP> Zn <SEP> 41.8 <SEP> 14.0 <SEP> 4.5
<tb> 42 <SEP> Ni / H / ZSM-5
<tb> 0.31% <SEP> Ni <SEP> 98.0 <SEP> 55.7 <SEP> 15.5
<tb>
 
Example 43:

   To compare the performance of a ZSM-5 catalyst with previously known selective 5 Angstrom catalysts, a nickel-hydrogen erionite was brought into contact with the same synthetic reformate mixture that was used in Examples 37 to 43. The following results were achieved:
 EMI17.2
 
<tb>
<tb> catalyst <SEP>% by weight <SEP> conversion
<tb> n-hexane <SEP> 2-methylpentane <SEP> benzene <SEP>
<tb> Ni / H / Erionite <SEP> 85, <SEP> 4 <SEP> 3, <SEP> 1 <SEP> 2, <SEP> 6
<tb>
   ZSM-5 catalysts in the H, Zn / H and Ni / H forms are more active than Ni / H erionite in cracking n-hexane and, what is not the case with Ni / H / erionite, they allow a much greater conversion of 2-methylpentane and benzene.

   In the liquid product obtained from the ZSM-5 throughputs, large amounts of C7 + alkyl aromatic compounds were found, which are apparently the result of the alkylation of benzene with cracked fragments. A typical analysis of the liquid product obtained at room temperature is as follows:
Composition of the liquid product from Example 40
 EMI17.3
 
<tb>
<tb> wt. <SEP> -%
<tb> 2-methylpentane <SEP> 1, <SEP> 5
<tb> n-hexane <SEP> 0.8
<tb> Benzene <SEP> 12.2
<tb> Toluene <SEP> 1,2
<tb> C aromatics <SEP> 30.2
<tb> C <SEP> + aromatics <SEP> 54.1
<tb> 100, <SEP> 0
<tb>
 
Examples 44 to 47:

   To compare the performance of ZSM-5 against known forms of selective acidic cracking catalysts, a hydrogen T, produced by calcining an ammonium-exchanged zeolite T, was brought into contact with the synthetic reformate mixture used in Examples 37 to 42 and the reactor effluent on stream 15 analyzed min and 3 h later.

   The following results were obtained:

 <Desc / Clms Page number 18>

 
 EMI18.1
 
<tb>
<tb> Example <SEP> catalyst <SEP> wt .-% <SEP> conversion <SEP> (15 <SEP> min <SEP> on the <SEP> stream)
<tb> n-hexane <SEP> 2-methylpentane <SEP> benzene
<tb> 44 <SEP> H / T <SEP> 58.5 <SEP> 3.3 <SEP> 0.6
<tb> 45 <SEP> H / ZSM-5 <SEP> 97.9 <SEP> 43.3 <SEP> 12.5
<tb> wt .-% <SEP> conversion <SEP> (3 <SEP> h <SEP> on the <SEP> current)
<tb> 46 <SEP> H / T <SEP> 29, <SEP> 7 <SEP> 0, <SEP> 5 <SEP> 0, <SEP> 6 <SEP>
<tb> 47 <SEP> H / ZSM-5 <SEP> 97, <SEP> 8 <SEP> 24.5 <SEP> 12.1
<tb>
 
These results demonstrate the remarkable activity and non-aging property of H / ZSM-5 with no added hydrogenation / dehydrogenation component under hydrocracking conditions. In contrast, H / T showed considerable signs of aging after 3 hours.



  ) Example 48: This example shows the typical production method of the ZSM-5 used in Example 38
Zeolite.



   22.9 g of SiO were partially in 100 ml of 2, 18n-Tetrapropylammoniumhydroxyd by heating on a
Dissolved at a temperature of about 100 C. Then a mixture of 3.19 g NaAlO (add. 42.0 wt .-% ALO,
 EMI18.2
 
 EMI18.3
 
<tb>
<tb> 0.382 <SEP> mol <SEP> SiO2,
<tb> 0.0131 <SEP> mol <SEP> Al2O3,
<tb> 0, <SEP> 0159 <SEP> Mol <SEP> Na20,
<tb> 0, <SEP> 118 <SEP> Mol <SEP> [<SEP> (CH3CH2CH2) 4N] 2O,
<tb> 6.30 <SEP> moles <SEP> H20.
<tb>
 
 EMI18.4
 
 EMI18.5
 
<tb>
<tb> OOC% by weight) <SEP> SiO <SEP> 93, <SEP> 62 <SEP>% by weight <SEP> adsorbed <SEP> n-hexane <SEP> 10.87
<tb>% by weight <SEP> Al2O <SEP> 4.9 <SEP>% by weight <SEP> adsorbed <SEP> cyclohexane <SEP> 3.60
<tb> wt.

   <SEP> -% <SEP> Na2O <SEP> 1.48 <SEP>% by weight <SEP> adsorbed <SEP> H2O <SEP> 9.15
<tb> 100.00
<tb> SiO2 / Al2O3 <SEP> 32.5
<tb> NaO / A <SEP> 0, <SEP> 5
<tb>
 
 EMI18.6
 cher catalyst in Examples 37, 45 and 47 was used.



   The ZSM-5 zeolite was prepared according to the general procedure described in Example 48. It was then brought into contact with a saturated solution of ammonium chloride to replace the original attached cations, after which it was washed with water, dried and calcined in air at 5400C to convert it to the hydrogen form, i.e., H-ZSM- 5, convict.



   Example 50: A ZSM-5 catalyst was prepared according to the general procedure in Example 48. The reaction composition and the properties of the end product are given below:
 EMI18.7
 
<tb>
<tb> temperature, <SEP> C <SEP> 150
<tb> time, <SEP> days <SEP> 5 <SEP>
<tb> reaction composition
<tb> SiO3 / Al2O3 <SEP> 29.1
<tb> Na2O / A <SEP> 1, <SEP> 19 <SEP>
<tb> TPA2o / Al2o3 <SEP> 9
<tb> H20 / TPA20 <SEP> + <SEP> Na <SEP> 0 <SEP> 47 <SEP>
<tb>
 

 <Desc / Clms Page number 19>

 
 EMI19.1
 
<tb>
<tb> composition
<tb> NaO, <SEP>% by weight <SEP> 2.42
<tb> Na, <SEP>% by weight <SEP> 1.8
<tb> AO ,, <SEP>% by weight <SEP> 6, <SEP> 1 <SEP>
<tb> 3 <SEP> SiC2, <SEP> wt .- <SEP> 90.6
<tb> SiO2 / Al2O3 <SEP> 25.2
<tb> NaO / A <SEP> 0.65
<tb> Adsorption cyclohexane, <SEP>% by weight <SEP> 3.07
<tb> n-hexane, <SEP>% by weight <SEP> 9.88
<tb>) <SEP> H2O, <SEP> wt .-% <SEP> 7,

  51
<tb>
 
The above material was then calcined at about 540 ° C. for 16 hours and divided into 2 parts (A and B).



  Part A was exchanged with 100 ml of a 0.5N aqueous solution of ammonium chloride at room temperature for 1 hour in order to form the ammonium salt. This catalyst was called Catalyst Al-
 EMI19.2
 exchanged. The material was then washed with water and dried in air to give a catalyst having a zinc content of 0.9% by weight and a sodium content of 0.2% by weight. It was used in Example 39 after calcining at 5400C for 16 hours.



   Part B was treated with anhydrous ammonia (100 cm3 / min) at room temperature to reduce the NH-
Reconstitute seats. The catalyst was referred to as catalyst B1. 3 g of the catalyst B1 were exchanged with a 0.5N solution of zinc and ammonium chloride as above. The finished catalyst contained 1.2% by weight of zinc and 0.3% by weight of sodium. It was used in Example 41 after calcining at 540 ° C. for 16 hours.



   The catalysts used in Examples 40 and 42 were prepared in the same way, with the exception that a nickel salt was used instead of the zinc salt for the base exchange of the zeolite.
 EMI19.3
 



     Example 51: This example shows the effect of the absence of hydrogen, the results are given below:
One feed was cracked over Ni / H / ZSM-5 zeolite. The characteristics of the feed as well as the working conditions and results were as follows:
 EMI19.4
 
<tb>
<tb> Loading <SEP> Example <SEP> 51
<tb> pressure, <SEP> kg / cm2 <SEP> 35
<tb> H / HC molar ratio
<tb> LHSV <SEP> 1
<tb> temperature, <SEP> OC <SEP> 318
<tb> drying gas, <SEP>% by weight <SEP> 7.38
<tb> C4 <SEP>, <SEP>% by volume <SEP> 6.8 <SEP> 16.8
<tb> C5 +, <SEP>% by volume <SEP> 93.2 <SEP> 76.0
<tb> C5 +, <SEP> RON, <SEP> pure <SEP> 90.3 <SEP> 98.9
<tb>
   Example 52: In this experiment a synthetic C6 reformate was converted over an acid-exchanged ZSM-5 zeolite catalyst.

   The C6 reformate charge had the following composition:
 EMI19.5
 
<tb>
<tb> component <SEP> vol .-%
<tb> 2,2-dimethylbutane <SEP> 10.5
<tb> 2,3-dimethylbutane <SEP> 6.2
<tb> 2-methylpentane <SEP> 15.3
<tb> n-Hexen-1 <SEP> 5, <SEP> 8
<tb> Benzene <SEP> 40.4
<tb> n-hexane <SEP> 21.8
<tb>
 
The composition had an octane number (ON) of 77.1.



   In this experiment the aforementioned feed was converted by passing it over an acid exchanged ZSM-5 zeolite at 100-200 LHSV at 482-510 ° C. In particular, the reaction was carried out at 100 LHSV and 4820C, and the properties of the final product were given below.

 <Desc / Clms Page number 20>

 



   Improvement of the octane number:
The synthetic reformate had a calculated pure octane number (R + 0) of 77.1 [the measured micro-octane number is 77.6 (R + 0)]. At 100 LHSV and 4820C, the modified fuel had an initial clean
Octane number of 92.3, calculated from the composition of the products. Accordingly, a gain in octane numbers of 15.2 was achieved through the conversion over the zeolite.



   This octane gain was achieved as follows:
1. Cracking of 62.9% by weight of the n-hexane and 12.5% by weight of the 2-methylpentane and 2,3-dimethyl
 EMI20.1
    -OlefinenExample 53: In this experiment, a reformate from a platinum reforming plant with an octane number of 86.0 (R + 0) and a final boiling point of 204 C was converted over the acid-exchanged ZSM-5 zeolite catalyst mentioned. The catalyst had an a value of 13,000.

   The feed had the following analysis:
 EMI20.2
 
<tb>
<tb> Average <SEP> molecular weight <SEP> 96.5
<tb> Octane number <SEP> (lead-free) <SEP> Research method <SEP> 86.0
<tb> Paraffins <SEP> 57.3 <SEP>% by weight
<tb> Olefins <SEP> 1, <SEP> 1 <SEP> Motor method <SEP> 79.5
<tb> alkylbenzenes <SEP> 38, <SEP> 6
<tb> Other <SEP> (by <SEP> difference) <SEP> 3, <SEP> 0 <SEP>
<tb> 100, <SEP> 0
<tb>
 
 EMI20.3
 
 EMI20.4
 
<tb>
<tb> Average <SEP> molecular weight <SEP> 89.2
<tb> Paraffins <SEP> 68.3 <SEP> wt. <SEP> -0/0 <SEP>
<tb> Olefins <SEP> 1.5
<tb> alkylbenzenes <SEP> 29.4
<tb> Other <SEP> (through <SEP> difference) <SEP> 0, <SEP> 8 <SEP>
<tb> 100, <SEP> 0
<tb>
 
The octane rating of the liquid product and that of the modified fuel (liquid + gas) are given below:

   
 EMI20.5
 
<tb>
<tb> time <SEP> on <SEP> current <SEP> only <SEP> liquid <SEP> modified <SEP> fuel
<tb> 20 <SEP> min <SEP> 91, <SEP> 3 <SEP> 93.8
<tb> 3 <SEP> h <SEP> 40 <SEP> min <SEP> 88.7 <SEP> 90.8
<tb>
 Compared to the reformate, a gain of 12.6 and 9.6 octane numbers could be achieved.



    Example 55: The following example illustrates the nickel-H-ZSM-5 zeolite used in Example 51.



  The following solutions were prepared:
 EMI20.6
 
ALO, (c) 4.5 kg of tetrapropylammonium bromide and 22.5 liters of water; (d) 3.6 kg of sulfuric acid in 10.8 l of water.



   Solution (c) was added to solution (b). solution (a) was then added to the mixture of (c) and (b). The solution (d) was then added to the mixture of (a), (b) and (c) with vigorous stirring.

 <Desc / Clms Page number 21>

 



   A gel formed and the mixture was held at a temperature of about 90 to 99 ° C. for about 267.5 hours until crystallization was complete and ZSM-5 was formed. After filtration, the wet filter cake was mixed with water, washed and dried at 121.degree. After drying, the product was calcined at 3710C for 3 hours. The calcined ZSM-5 product was then subjected to exchange treatments for 4 hours with 1.0-on ammonium nitrate solution at room temperature.



   The ammonium-exchanged zeolite was then subjected to a 4-hour exchange with a 0.5N nickel nitrate solution at 87.degree.



   The exchanged material was then washed free of nickel solution, dried at 1210C, brought to a size of 30 to 60 meshes and then calcined at 540C for 10 hours.
 EMI21.1
 sulfided in hydrogen at 400C.



   The catalyst contained 0.11% by weight sulfur, 0.32% by weight nickel and 0.02% by weight sodium.



     Example 56: The following example illustrates the preparation of the hydrogen / ZSM-5 zeolite used in Examples 52, 53 and 54. The following solutions were prepared: (a) 0.25 kg of sodium aluminate, with a content of 44.71o aluminum oxide, 6.31 l of water;
 EMI21.2
 



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



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



   The ZSM-5 zeolite was calcined for 10 hours at 540 C after drying and then with an on-
 EMI21.3
 division as to whether a certain zeolite is effective in the process according to the invention.



   In these examples, equal parts by weight of benzene and n-heptane were passed over different catalysts to be evaluated, and the conversion of heptane and benzene was measured.



   The following conditions were used:
 EMI21.4
 
<tb>
<tb> temperature <SEP> 315-4820C
<tb> pressure <SEP> 0 <SEP> - <SEP> 28 <SEP> kg / cm2
<tb> LHSV <SEP> 0.4 <SEP> - <SEP> 62
<tb> H2 / HC <SEP> 0 <SEP> - <SEP> 7
<tb>
 
The reason for the large variation in process conditions was an attempt to achieve the best results for each catalyst tested. All the catalysts to be evaluated were first tested under the following conditions:
 EMI21.5
 
<tb>
<tb> 4000C
<tb> 28 <SEP> kg / cm2
<tb> 62 <SEP> LHSV
<tb> 7/1 <SEP> H / HC
<tb>
 
Those which failed the test were retested under other conditions within the above wide range in an attempt to improve their performance.



   The following table shows the best test results and the temperatures used.

 <Desc / Clms Page number 22>

 
 EMI22.1
 
<tb>
<tb> Example <SEP> Zeolite <SEP> Organic <SEP> SiO / ALO <SEP> cracked <SEP> Benzene <SEP> temperature
<tb> cation <SEP> n-heptane <SEP> converted <SEP> oc
<tb>% by weight <SEP>% by weight <SEP>
<tb> 57 <SEP> TMA-Offretit <SEP> yes <SEP> 8.0 <SEP> 15 <SEP> 1.5 <SEP> 425
<tb> 58 <SEP> ZSM-4 <SEP> yes <SEP> 6,7 <SEP> 8 <SEP> 0, <SEP> 1 <SEP> 400
<tb> 59 <SEP> Mordenite <SEP> no <SEP> 24 <SEP> 9 <SEP> 2 <SEP> 400
<tb> dealuminized
<tb> 60 <SEP> TEA <SEP> Mordenite <SEP> yes <SEP> 32 <SEP> 61 <SEP> 18.5 <SEP> 482
<tb> 61 <SEP> Beta <SEP> yes <SEP> 30 <SEP> 68 <SEP> 10,

  5 <SEP> 482
<tb> 62 <SEP> ZSM-5 <SEP> yes <SEP> 30-70 <SEP> 80 <SEP> 28 <SEP> 315
<tb> 63 <SEP> ZSM-8 <SEP> yes <SEP> 53 <SEP> 61 <SEP> 15 <SEP> 400
<tb> 64 <SEP> ZSM-11 <SEP> yes <SEP> 76 <SEP> 38 <SEP> 15.5 <SEP> 315
<tb> 65 <SEP> ZSM-12 <SEP> yes <SEP> 52 <SEP> 52 <SEP> 18 <SEP> 400
<tb>
 
The table above shows that there are large differences in the catalytic behavior among the tested zeolites. It should also be noted that all of the above tested zeolites have the ability
To adsorb monomethyl paraffins under the conversion conditions used. So the difference between zeolites is whether or not they were synthesized in such a way that they contain an organic cation, another difference is their ratio of silica to alumina.



   From the table above it can be seen that TMA-Offretit, ZSM-4 and Mordenit are not in the desired
Work wisely. With the TMA-Offretit it should be noted that the cracking of heptane and the conversion of
Benzene are too low even at temperatures of 4250C. TMA-Offretit therefore does not fall into the definition of preferred zeolites, as its silica to alumina ratio is below 15. In the same way, ZSM-4 is not a good catalyst for the conversion of heptane and benzene, although it contains an organic cation and has the ability to adsorb monomethyl paraffins, although it should be noted here that the ratio of silica to alumina is below 15 lies.



   Furthermore, the table above shows that it is not just the ratio of silica to alumina that gives the catalyst the improved properties. Reference is made to mordenite, which was synthesized in a conventional manner and then dealuminized in order to raise the ratio of silica to alumina to 24. The table shows that mordenite also has poor catalytic properties with regard to the conversion of heptane and benzene, which means that it cannot be used as a catalyst for upgrading a reformate according to the invention.



   All of the remaining zeolites gave good results by converting substantial amounts of heptane and benzene.



    PATENT CLAIMS:
1. Process for the preparation of reformates and products from reforming plants by
 EMI22.2
 (2) was crystallized from a solution containing organic cations, so that it contains organic cations in the synthesized state, and (3) has a pore size such that it adsorbs methyl paraffins under the aforementioned conversion conditions.



   2. The method according to claim l, characterized in that the crystalline aluminosilicate zeolite has a ratio of silica to alumina of more than 20.

 

Claims (1)

3. The method according to claim 1 or 2, characterized in that the crystalline aluminosilicate zeolite is assigned a hydrogenation / dehydrogenation component. 4. The method according to any one of claims 1 to 3, characterized in that the crystalline aluminosilicate has been base-exchanged with ammonium or hydrogen cations. 5. The method according to any one of claims 1 to 4, characterized in that the crystalline aluminosilicate is SS-zeolite. 6. The method according to any one of claims 1 to 4, characterized in that the crystalline aluminosilicate is TEA-mordenite. <Desc / Clms Page number 23> 7. The method according to any one of claims l to 4, characterized in that the crystalline aluminosilicate is zeolite ZSM-12. 8. The method according to any one of claims 1 to 4, characterized in that the crystalline aluminosilicate is zeolite ZSM-5. 9. The method according to any one of claims 1 to 4, characterized in that the crystalline aluminosilicate is zeolite ZSM-8. 10. The method according to any one of claims l to 4, characterized in that the crystalline aluminosilicate is zeolite ZSM-11. 11. The method according to any one of claims 1 to 10, characterized in that the reformate consists essentially of aromatic hydrocarbons and paraffin hydrocarbons.