DE1917883A1 - Process for converting a hydrocarbon feed - Google Patents

Description

PATENTAftWXitE

DR. E. WIEGAND DIPL-ING. W. NIEMANN 19178 8 3

DR. M. KÖHLER DIPL-ING. C. GERNHARDT MÖNCHEN HAMBURG TELEPHONE 55 54 7 «8000 MONKS 15, TELEGRAMS. KARPATENT NUSSBAUMSTRASSE 10

April 8, 1969 W. 14 111/69 13 / Loe

Mobil Oil Corporation New York, N.Y. (V.St.A.)

Process for converting a hydrocarbon feed

The invention relates to organic conversion reactions.

In general, zeolite catalysts have been particular useful in those classes of reactions that are endothermic, e.g. cracking to hydrocarbons Lower molecular weight products. Although the catalysts also have a certain ability in others Hydrocarbon conversion areas, namely those which include exothermic reactions or no heat of reaction, did not show particularly good behavior. The reason for this is based

essentially due to the fact that the catalysts usually unable to achieve sufficient hydrocarbon feed conversion at the desired levels To give selectivities to make the process sufficiently attractive for technical inclusion do. Moreover, in order to obtain a high yield, it was found necessary to add heat to the Increase response to one point at which secondary cracking will either be the reactant or products takes place, whereby the selectivity was reduced.

In accordance with the invention there is provided a method of carrying out the conversion of an organic feed in a reaction which does not involve heat consumption, in which the feed is heated at a temperature below 371 ° b (700 ^° P) but which is sufficiently high to be to effect the conversion brings into contact with a catalytically active zeolite which has an o-xylene selectivity factor of at least 2.5. The reactions which can be considered according to the invention are, as indicated above, those which are either exothermic or have no heat of reaction whatsoever (the latter type of reaction being referred to for the sake of brevity as a heat balanced reaction.) These reactions include aromatic alkylation, especially with olefins, isomerization of aromatic compounds, e.g. o-xylene, proportioning of aromatic compounds, for example of toluene to form benzene and xylene, polymerization of olefins and epoxides, alkylation of paraffins, e.g. B. of η-butane and isobutane, the disproportionation of paraffins, e.g. mproportionation of n-pentane

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with the formation of hexanes and butanes and the isomerization of n-pentane and n-hexane.

The zeolite catalysts which can be used according to the invention are those having an o-xylene selectivity factor of at least 2.5. The term "selectivity factor" as used herein refers to the weight ratio of isomerized o-xylene to disproportionated o-xylene using 2oo ml of o-xylene, which is activated by activated alumina at 2 volumes / volume / hour. at 22+ 3 ⁰ C and placed in a 1 liter steel shake bomb containing 3.0 g of zeolite, which was calcined, weighed and weighed after weighing at 482 ⁰ C (900 ° F) for 1/2 hour. dried, with the bomb flushed with nitrogen. The bomb is heated at 204 ¹ C (4oo ° F) using an induction furnace rapidly, it was shaken at 2oo U / min using an electrically driven single engine Lawson Haschine. After 20% of the o-xylene has been converted into conversion products, the bomb is quickly cooled or quenched with water, the shaking is stopped and the liquid sample is analyzed. A complete description is in determining the selectivity factor device to be used in the publication "A Hew Laboratory Tool for Studying Thermal Processes ⁿ JW Payne, CW Streed and ER .Kent in" Industrial and Engineering Chemistry ^{1, 1} Volume 5o, pages 47 -52 (1958).

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Catalysts with o-xylene selectivity factors above 2.5 include zeolite-β (described in US Pat. No. 3,3o8,069) and Zeplith ZSM-4 (described in British Pat. No. 1,117,568). Both ZSM-4 and Zeolite-ß can be converted into any number of a very wide variety of cationic forms, particularly forms comprising metals of Groups IB-YIII of the Periodic Table, particularly metals of Groups II and VIII of the Periodic Table and the Contains rare earth metals. In addition, ZSM-4 can be in the hydrogen form using either a suitable acid or converted by reacting initially ZSM-4 is converted into an ammonium form, and then heating the ammonium form at a temperature of at least about 204 ⁰ C (4oo ° F) and thereby brings about the evolution of ammonia and the conversion of the ammonium form into the hydrogen form. In addition, ZSM-4 can be converted to an alkylanmonium or arylammonium form using a suitable solution that provides these cations in a form suitable for base exchange.

ZSM-4 can conveniently be converted in a metal, hydrogen, ammonium, alkylammonium or arylammonium form into another form by heat treatment in which that form of ZSM-4 is at a temperature of at least 371 ⁰ C (700 ° F) for at least 1 minute and generally no longer than 20 hours. Although sub-atmospheric pressure can be used for this heat treatment, atmospheric pressure is desirable for convenience. Preferably in the conversion

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of ZSM-4 in this new heat treatment product, the heat treatment is carried out in the presence of moisture, although moisture is not absolutely necessary. The heat treatment may be carried out at a temperature up to about 871 ⁰ C (l6oo ° F) at which temperature the occurrence of some decomposition occurs. The thermally treated product is particularly useful in the catalysis of certain hydrocarbon conversion reactions, particularly those according to the invention which are generally low temperature reactions of the exothermic or thermal equilibrium type.

ZSM-4, expressed in molar ratios of the oxides, can be represented by the following formula:

0.9-0.2 M ₂ O ί W ₂ O ₅ : 3-20YO ₂ ι ζΗ ₂ 0 η

where M is a cation, η the valence of this cation, W aluminum or gallium, Y silicon or germanium and ζ is a number between 0 and 20. ZSM-4 has a characteristic X-ray diffraction pattern that Distinguishes members of the ZSM-4 class from other zeolites. The X-ray diffraction pattern of ZSM-4 is given in Table I below;

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Table I.

Interplanar distance d (£) Relative intensity I / I _Q

9.1 ± 0.2 very strong

7.94 ± o, l medium weak 6.9ο - ο, Ι 'medium

., 97 ± ο, o7 strong

5.5ο - ο, o5 medium weak

5.27 - ο, o5 moderately weak

4.71 ± 0.05 moderately weak

4.39 - o, o5 weak

3.96 ± 0.05 weak

3.8o - o, o5 strong *

3.71 ± o, o5 medium

3.63 ± o, o5 medium

• 3.52 ± 0.05 "thick

3.44 ± o, o5 medium

3.16 ± 0.05 strong

3, o9 ± o, o5 medium

3, o4 - o, o5 medium

2.98 ± o, o5 medium 2.92 - o, o5 strong.

These values were determined according to standard procedures. The radiation was the K- ° ^ doublet radiation from copper and a Geiger counter spectrometer with a Messkar tens honor ib facility was used. The peak heights I and their locations as a puncture of 2xö? Heta, where theta is the Bragg's angle _# - were read from the spectrometer measuring strip. This became the relative intensities, 100 I / I _Q , where I is the intensity of the strongest line or peak, and d (observed), the interplanar distance in I ₉ corresponding to the

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calculated lines. It can be seen that this X-ray diffraction pattern for all species of ZSM-4 compositions. at Ion exchange of the sodium ions for other cations will look essentially the same with some minor ones Shifts in interplanar distance and changes in relative intensity exhibited

Preferably the catalyst used in the process according to the invention has one of these Size that it is smaller than 0.5 microns in any dimension. In addition, the zeolite should preferably have a three-dimensional pore structure that allows the feed molecules to enter the zeolite and allowing the reaction products to escape. Generally, in the case of a porous zeolite catalyst Sators, it is preferred that the porosity of the catalyst is such that the pore volume is at least of the volume of the zeolite. However, it can be seen that for successful practical execution tion of the invention a porous catalyst is not essential.

The zeolites that are in a catalyst composition can be used according to the invention, can be composed with other masses, the act as matrices or binder materials. Such materials include active and inactive materials and synthetically or naturally occurring zeolites other than those described above as well inorganic materials such as clays, silica and other metal oxides. The latter can either be naturally occurring materials or in shape

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-S-

including a gelatinous precipitate or gel Mixtures of silicon dioxide and metal oxides are present · The use of a material in combination with these catalysts, i.e. with these connected that is active tends to improve conversion and / or the selectivity of the catalysts in the specific types of hydrocarbon conversion reactions, which are contemplated according to the invention. Inactive materials suitably serve as Diluents to control the degree of conversion in a given operation so that products in in an economical and orderly manner without the use of other means or regulation measures the extent of the reaction can be obtained. Usually zeolite materials were found in naturally occurring Clays, e.g. bentonite and kaolin, incorporated to the To improve the breaking or abrasion resistance of the catalyst under technical working conditions. These materials, i.e. clays, silica or other oxides act as binders for the catalysts. The creation a catalyst with good resistance to rupture or attrition is desirable in a petroleum refinery or another plant in which the conversion process according to the invention is carried out, the catalyst is often subjected to rough or rough handling, which leads to breakage of the catalyst down to powder-like materials, which can lead to problems in operational management and processing cause. Clay binders therefore became commonplace used only for the purpose of improving the breakage or abrasion resistance of the catalyst »

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Naturally occurring clays composed with the catalysts useful in accordance with the invention Include montmorillonite and the kaolin class, these classes or families being the sub-bentonites and the kaolins, commonly known as Dixie Maitfamee-Georgia- and Floridatone are known, or include others, wherein the main mineral component is halloysite, kaolinite, dickite, nacrite or anauxite. Such Clays can be used in the raw state in which they were originally extracted or after initial exposure to calcination, acid treatment, or chemical Modification can be used.

Aluminum oxide is used as a binder in combination with useful zeolites for the process according to Invention particularly preferred because it allows the formation of a hard compact or extrudate, which is sufficient is porous in order to prevent diffusion restrictions under normal reaction conditions the processes under consideration can be technically applied effortlessly, especially if the zeolite is in Compound with an alumina binder is present.

In addition to the materials specified above, the usable zeolites can also be used with porous matrix materials be composed, e.g. silicon dioxide-aluminum oxide, Silica-Magnesia, Silica-Zirconia, Silica-Thorium Oxide, Silica-Beryllium Oxide, Silicon dioxide-titanium oxide, as well as with ternary compounds, e.g. silicon dioxide-aluminum oxide-thorium oxide, Silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a mixed gel. The relative proportions of.

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- Io -

finely divided zeolite. and inorganic oxide gel matrix vary widely with a crystalline zeolite content ranging from about 1 "to 90 wt.% and more commonly in the range of about 2 to 50 wt the composition ο

The zeolites which can be used according to the invention can be used in a great variety of particle sizes can be produced and used. In general, the particles can be in the form of of a powder, of a granulate or of grains or in a particle form, for example an extrudate, or a pressed material with a particle size sufficient to pass through a sieve with a clear Mesh size of 8 mm (2 mesh Tyler) to go through and a sieve with a mesh size of about 0.05 mm (4oo mesh Tyler) retained to be grounded. In cases where the catalyst is in particulate form is prepared, for example by pressing, the zeolite material can be dried before drying State or in a partially dried state are pressed or extruded.

In the method according to the invention, paraffinic hydrocarbons can be used at a temperature between and 371 ⁰ C (35o to 7oo ° P), preferably between 2o4 and 288 ⁰ C (400 and 55o ° F) under a pressure between 0 and 141 atü (0 and 2ooo psig) and isoiaerized and / or disproportionated using an hourly fluid space velocity between 0.05 and Io. In the case of a rudimentary operational management, a corresponding duration of contact can be applied. Paraffinic hydrocarbons, the iso-

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Can be merized and / or disproportionated include η-butane, isobutane, n-pentane and η-hexane, as well Higher molecular weight compounds. Olefins can be isomerized by the process according to the invention will. Naphthenes can also be isomerized by the process according to the invention.

The Paraffinalkylierung is usually carried out at a temperature between about 177 and 371 ⁰ C (35o and 7oo ° F), preferably between about 2O4 and 26o ° C (4oo and 5oo ° F). In the case of continuous operation, an hourly liquid space flow rate between approximately 0.1 and 5, and in particular 1.0, is usually used. In the case of a rudimentary operational management, an equivalent duration of contact is used. In the case of paraffin alkylation, the hydrocarbon conversion conditions include the presence of a compound having an alkyl group available for alkylation. Preferred alkylating agents are olefins, for example ethylene, propylene, dodecylene, nonene and alkyl halides, alcohols or the like, the alkyl part of which usually has between 1 and 20 carbon atoms.

The aromatic alkylation is usually carried out at a temperature between about 177 and 371 ⁰ C (35o and 7oo ° F), preferably 177 and 232 ⁰ C (35o and 45O ⁰ F) under a pressure between about O and 7o, 3 atm (O and 3: ooo psig). In the case of continuous operation, an hourly liquid space flow velocity of between about 0.1 and 5 is generally used. In batch operations, an equivalent contact duration is used. The aromatic alkylation can be carried out using the same

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Alkylating agents such as those used for paraffin alkylation have been used. It works particularly well when using olefins or alkyl chlorides as a starting material for the alkyl group. Aromatic Compounds that can be alkylated to " contain benzene, naphthalene and their derivatives.

The aromatic isomerization, in particular of xylenes or other polyalkylated aromatic compounds, can generally take place at temperatures between about 177 and 371 ⁰ C (35o and 700 ° P), preferably between about 177 and 26o ° C (35o and 500 ° F) Applying a pressure between about 0 and 141 atmospheres (O and 2ooo psig) can be carried out. When the isomerization is carried out continuously, a liquid hourly space flow rate between about 0.1 and 5.0 is generally suitable. Equivalent contact times are used in the case of a rudimentary operational management. When carried out 4-way aromatic isomerization using the classes of catalysts described above, the selectivities achieved are far superior to those obtained in any other previous process. In particular, it was found that the o-xylene selectivity, measured according to the selectivity factor test described above, a selectivity when using a hydrogen form of zeolite β of 3.7 and when using ZSM-4 in a hydrogen form of above 4.0 and generally up to 15 results. In contrast, the selectivity of o-xylene isomerization using a rare earth exchanged Linde zeolite Γ catalyst, a rare earth exchanged Linde zeolite X catalyst, HY »SeI-

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clay earth HY and hydrogen mordenite always selectivities less than 2, ο and usually less than l, o,

According to the method according to the invention invention can be usually polymerized at temperatures within the. Range of 14-9 to 399 ⁰ C (3oo to 75o ° P) having a carbon-carbon multiple bond and epoxides. In the liquid phase, the polymerization charge can be passed continuously through a reactor at a liquid hourly space flow rate of up to 500o. A pressure between 0.25 atm and 10000 atm is suitable. An equivalent duration of contact for a batch management is used. If the monomer is gaseous under the polymerization conditions, its space flow rate through the catalyst in the reaction zone is between 50 and 200,000 volumes of gas per hour per volume of catalyst. The types of compounds with a carbon-carbon multiple bond and of epoxies include normal olefins, isoolefins, especially CU-CL, halogen-substituted oil / fin compounds, compounds containing polymerizable olefin groups and an oxygen-containing group, conjugated diolefins, non-conjugated diolefins, with Conjugated diolefins substituted by halogen or aromatic radicals, olefin compounds with terminal carboxyl groups or esters of the carboxyl groups, triolefins, cyoloolefins, e.g. cyolopentene, methylcyclohexene, cyclodiolefins, e.g. cyelooctadiene, vinyloyclohexene, acetylenes, allenes, styrene oxides, e.g. chlorohydrins, substituted epoxies Propylene oxide, isobutylene oxide and limonene diepoxide. Other compounds that can be polymerized according to the invention include polymerizable phenyl compounds and

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aromatic alkenyl compounds, polymerizable olefin compounds, containing silicon-carbon bonds, and generally compounds with. at least one polymerizable Carbon-carbon multiple bond, i.e. with an olefinic or acetylenic unsaturation.

The aromatic. Disproportionation can be carried out at temperatures between about 177 and 371 ⁰ C (35o and 700 ° F), preferably between about 288 and 343 ⁰ C (55o and 65o ° P) using pressures between about 0 and 141 atm (0 and 2ooo psig) are executed. An hourly liquid space flow velocity between about 0.1 and 5.0 is suitable if the operation is carried out continuously, and equivalent residence times are used in the case of batch operations. The disproportionation reaction of, for example, xylene tends to produce a mixture of methylbenzenes, mainly toluene and trimethylbenzenes. The selectivity of toluene or xylene disproportionation is conspicuous when carried out by the method according to the invention. Selectivities as high as 800 to 1,000 have been observed in the disproportionation of these types of aromatic compounds. In contrast, zeolite catalysts such as rare earth exchanged faujasite, hydrogen faujasite, V / ass er stoff mordenite and other selectivity levels of about 6. In this case, the selectivity is the ratio of disproportionate products to cracked products, since cracking is a competing side reaction in the Disproportionation of aromatic compounds is

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. It is considered particularly surprising that in accordance der.-invention ß in contemplated reactions with these catalysts · such as zeolite ~ and ZSM-4, examples of the according ^to: the invention provided catalysts represent extend so exceptionally well. These catalysts are not invariably usable ^cata-: reindeer in the catalytic cracking of gas oil, wherein the catalytically © cracking is an endothermic reaction, to useful compounds for the gasoline = to generate mixing. ZSM-4 and Zeolite-ß provide higher amounts of drying gas and coke than many other zeolite catalysts. Thus, they do not have the same cracking selectivity as these catalysts known in the art, particularly faujasite, synthetic zeolite X and synthetic zeolite Y, for Cc-C-.Q hydrocarbons, but rather have a greater selenium for dry gas synthesis. Thus, it is surprising and unexpected to find that these zeolites can be used effectively in this limited class of exothermic or heat balanced conversion reactions with selectivities never before obtained from any known zeolite catalyst. The hydrocarbon conversion processes proceed so extraordinarily well in the presence of these types of catalysts that these processes acquire technical significance with respect to uptake in a petroleum refinery. While zeolite catalysts have not generally been successful for these exothermic or thermal equilibrium reactions, the use of these catalysts according to the invention in particular enables them

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at the low reaction temperatures described above, these reactions can be carried out with these zeolite catalysts in an advantageous manner and therefore opens up a new technical field of selective exothermic Hydrocarbon conversion or hydrocarbon conversion with heat compensation at low temperature.

The invention is explained in more detail below with the aid of examples.

example 1

Zeolite ZSM-4 was prepared from four solutions, hereinafter referred to as Solutions A, 1, J2 and 3. Solution A was formed by mixing sodium hydroxide with sodium silicate. The respective components of the Solutions are given below.

Solution A:

Sodium silicate -47.6 kg (105 lbs.)

NaOH 6.08 kg (13.4 lbs.)

\ H ₂ O 16.84 kg (37.1 lt »s.)

Solution 1:

Al ₂ (SO ₄ J ₅ * 18H ₂ O 6, jj3 kg (14.95 lbs.)

H ₂ SO ₄ (98 wt %) 3.32 kg (7.32 lbs.)

H ₂ O 16.84 kg (37.1 lbs.)

Solution 2:

Sodium aluminate 0.64 kg (1.42 lbs.)

• H ₂ O 6 _t 66 kg (14.7 lbs.)

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Solution 3:

Tetramethylammonium chloride 1.20 kg (2.66 lbs.) H ₂ O, 1.20 kg (2.66 lbs.)

Solution 2 was added to solution 3 and the resulting solution (2 + 3) was added to solution 1, the resulting solution (1 + 2 + 3) being designated as solution B. Solution A was added to solution B with rapid stirring and the combined solutions were mixed in a Lightning mixer for 20 minutes. Solution A was added to solution B over a period of 13 minutes. The resulting solution (A + B) was heated at 101.6 ^{0 0} C to 103,30 C (215 to 2L8 ° F) for 90.5 hours, whereupon the crystallized product was removed by filtration. During the heating of the solutions, the liquid was covered with oil to keep evaporation to a minimum. The crystals thus filtered were washed with hot water. The product had a composition of the following molar ratios of oxides to aluminum oxide:

Tetramethylammonium oxide x 0.230

Sodium Oxide 0.808

Aluminum oxide 1.00

SiO ₂ . 6.86

The product was highly crystalline as determined by X-ray analysis. It sorbed 2.2 wt .- # cyclohexane at -6.67 ⁰ C (20 ⁰ F) under a pressure of 12 mm Hg,

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This product was base immersed at about 82.2 ° C (180 ° F) with four touches of an aqueous ammonium sulfate solution having a concentration between about 15 and 20% by weight ammonium sulfate. The replacement treatments took anywhere from half an hour to several hours. The exchanged ZSM-4 composition had a sodium content of about 0.43 wt .- ^, so that the finished product had a molar ratio of Na ₂ O / Al ₂ O, ^of ° * ^Qlv T. The exchanged product was filtered, washed and ^{dried at 110.0 °} C. (230 ^° F.) for 16 hours.

A portion of α-alumina monohydrate was peptized by treatment with 10% by weight acetic acid. This was mixed with the exchanged ZSM-4 catalyst prepared according to the procedure described above in a weight ratio of ZSM-4: α-alumina of 70 sec. The water content of the mixture was adjusted so that the blend contains about 65 wt -% solids contained.. At this concentration of water, the combined ZSM-4 / a-alumina monohydrate composition had a dough-like consistency. This was pressed through an extruder or an extruder and comminuted into compacts of 1.587 mm (1/16 in.). The product was dried for 17 hr. At 482 ° C (900 ⁰ F), said air through the catalyst at a level of. 3 volumes of air per 1 volume of catalyst was passed per min.

The ZSM-4 catalyst bound with the aluminum oxide has been made with respect to o-xylene isomerization in the course of 4 hours using 12 cnr of the catalyst at a

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A temperature of 204 ° C (400 ° F), a pressure of 14.1 atmospheres (200 psig), and a liquid hourly space flow rate of 2. The catalyst was found to convert 75 * 1 # of the feed o-xylene. The product contained 67.5 wt -.% Isomerization and 7 * 45 wt .- ^ disproportionation at a ratio of isomerization to disproportion! products of 9 * 0. The catalyst thus not only showed good conversion of o-xylene, but in particular a high selectivity, as can be seen from the ratio of isomerization products to disproportionation products.

Example 2

A ZSM- ¹ I catalyst was produced in a manner similar to that described in Example 1, with a silicon dioxide / aluminum oxide / Mo! Ratio of 7: 1 and a particle size corresponding to a sieve with a mesh size of 2.16 mm 1.168 mm (8 χ 14 Tyler mesh) and was evaluated for o-xylene isomerization under the conditions described in the previous example. When the o-xylene isomization catalysis was assessed for 5 hours, 77.7% by weight of o-xylene were converted and the weight ratio of isomer products to disproportionation products was 7 * 37.

Example J

A hydrogen form of ZSM-4, this material having been prepared as described in Example 1 and a silicon dioxide / aluminum oxide molar ratio of 7: exhibited was combined with kaolin clay. This material was

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- 2ο -

to a composition with a size corresponding to one • Sieve with a mesh size of around 2.36 χ 1.168 mm (8 χ 14 Tyler mesh) at a weight ratio of HZSM-4: kaolin clay of 80:20. This material was . similarly with respect to o-xylene isomerization evaluated under the conditions given in Example 1. A conversion of 34.8 wt .- ^ at a weight ratio of isomers to disproportionation products of Obtained 11.0.

Example 4

A ZSM-4 catalyst sample was prepared and converted to the active form by heating the NHH form for 2 hours at 593 ° C (1100 ⁰ F). Before use, this catalyst was ^{heated at 538 °} C. (1000 ^° F.) for 2 hours in air and for 1 hour in a stream of hydrogen. The particle size of the product corresponded approximately to a sieve with a mesh size of 0.853 to 0.37 mm (20 to 40 mesh). .... The chemical analysis of NHh-ZSM-4 before calcination was as follows: - -

Wt .- ^

Sodium 0.31

SiQ ₂ ° 86.5

Al ₂ O _3. '■■ .. "12.1

N (NH,) 2.06

Ash 86.4

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Physical properties:

HgO adsorption 12.1 %

Cyclohexane adsorption 3.9 wt .- #

Surface area 323 m / g

A HY catalyst was made by calcining the ammonium form of Y zeolite.

HY ¹ , an active and stable form of zeolite .Y, was made from NH ₁ -Y. NH ^ Y was added to a steam calcination at 538 ⁰ C (1000 ⁰ F) for 90 min, then exchanged with NH _2, Cl for 18 hours. Subjected. After filtering, washing with water and drying at> 105 ° C., the catalyst was treated with an (NHOpHp-ethylenediaminetetraacetate solution with a pH of 7 at reflux temperature for 90 minutes. # of the aluminum removed.

A zeolite X catalyst exchanged with rare earths was produced according to a known procedure and contained 27.5 # of rare earth oxides (Re ₂ O ₅ ).

These catalysts were compared with one another and with an amorphous SiO ₂ -ΑΙρΟ -, - standard cracking catalyst with regard to their polymerisation activity. The conversion of isobutene to oligomers and the conversion of propene and a refining butane-butene composition are given in Tables II, III and IV below.

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Table II into oligomers 1 2 -X- - Wt % conversion of isobutene atu (150 psig) 76.9 74.6 77.0 2.6 300 IHSV - 6O ⁰ C - 10.5 Operating time in hours 66.6 13.3 5.6 catalyst 1/4 1/2 It 7 0 li ^ L - 3.8 3, I ⁺ HZSM-4 86.2 82.0 HY ¹ 17.3 - REX 11.5 11.3 SiQ ₂ ZAl ₂ O ₃ ⁺ * Annotation: Φ 1.5 hours + Attempt at 37,

++ 50 wt .- $ silica. 10 % by weight of alurainium oxide, surface area 235 m ² / g.

Table III
Weight .- $ Conversion of 1-butene to oligomers 6.25 IHSV - 120 ° C - 25.3 atmospheres (360 psig)

Catalyst operating time in hours

JL 2__ 3 1/2 §_ 6 \ / ^r d. 7 1/2

HZSM-4 33.1 29.3 "28.5 28.5 26.9 25.8 HY 15.5 5.5 2.7 2.2

Table IV
Weight .- ^ Conversion of olefins to oligomers

Catalyst - HZSM-4 6.26-BISV - 52.0 atm (740 psig)

Temperature ⁰ C

Feeder IO5 I55 190

Propene 44.7 61.0 90.8

Butane-butene mass -37, I ⁺ 50.2 * 57, 4

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Note to Table IV:

⁺ % By weight of converted olefins * present in the refining butane-butene mass which had the following composition:

Propene 1.2 wt .- #

1-butene 10.8 wt .- ^

Isobutene 11.7 wt%, 41.6 wt% olefins

trans-2-butene 10.8 wt. - $>

cis-2-butene 7.1 wt -.%

Propane 3.4 wt .- ^

Isobutane 35.1 wt .- ^

n-butane 21.9 wt .- ^

From the results, in particular from the results shown in Tables II and III, it can be seen that the ZSM-4 catalyst maintains its activity over a long period of time (see e.g. HZSM-4 with each HY catalyst). Although the HY catalyst has an activity this activity decreases rapidly, whereas the activity of the ZSM-4 catalyst remains essentially constant. This is the same for the 1-butene polymerization as it is for the Isobutene polymerization is the case. It should be noted that after 5 hours a HY catalyst had a conversion of less than 10 5έ of that of a HZSM-4 catalyst during the 1-butene polymerization results. As from Table IV can be seen, the catalyst according to the invention is also in the propene polymerization and the polymerization of a Refinery streams containing both alkanes and olefins are useful.

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Example 5 ■ ..> ■■■. ■■.

In a shake bomb as described above, 23 g of ri-nonene and 90 g of naphthalene were placed. 3.0 g of HZSM-4 catalyst with a molar ratio of silicon dioxide: aluminum oxide of about 7 '> 1 were placed in the bomb. The temperature was raised to 232 ⁰ C (45O ⁰ F). After 5 hours, 90% by weight of the n-nonene had been consumed to form nonylnaphthalene.

n-nouns

G of this mixture was Another portion of 23 was added and shaken for a further period of 5 hr. At about 232 ⁰ C (450 ⁰ P). Analysis showed that 90 $ of n-nonene was consumed for the formation of nonylnaphthalene. No dialkylated products were found.

Example 6

A mixture of 65 wt -.% Benzene and 35 weight "- $ n-dodecene was charged to a reactor of 25 cm-HZSM-4 -Containing, of 25 wt ~% Aluminiumoxydbindemittel in the form of compacts or extrudates. a size corresponding to a sieve with a mesh size of about 0.76 χ 0.37 mm (22 40 mesh) extrudates. The HZSM-4 catalyst had a molar ratio of silicon = 'dioxide; aluminum oxide of about 7.7:. 1. The temperature (450 F ⁰⁾ is increased to 232 ⁰ C and a pressure of about 38, 7 atm was (■ 550 psig) is applied to keep the feed in-liquid phase "In a Ströraungsausmaß of- ^ 0 : 25 XHSV

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was about the theoretical amount of benzene for the formation of alkylbenzenes, of which about 80 wt .- # from Dodecylbenzene passed, consumed. After 91 hours of operation, the product showed the following analysis:

Table V *
1 % Lighter than benzene 3, 1 % Benzene 53 » 6 % Alkylbenzene 4}, Example 7 Styrene oxide Polymerization of

15 ml of styrene oxide was added to 1.0 g of HZSM-4 catalyst prepared by calcining an ammonium exchanged form of the sodium form of the catalyst. An instantaneous reaction took place, as indicated by an exothermic reaction which caused a rapid temperature increase from room temperature to 150 ^° C. The temperature then dropped, but was maintained at 110 to 115 ° C by the application of external heat. The samples taken at half, 1 and 2 hour intervals were increasingly viscous. The analysis of the withdrawn after half an hour sample showed a conversion of about 25 wt -.% In a dimer and 12.5 wt -.% In a trimer, which has been displayed a good selectivity. There was also a minor amount of phenoxyacetaldehyde produced.

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The sample taken after two hours was dissolved in ₂ J _- , filtered to remove the suspended catalyst and the solvent was removed by evaporation. The product was a gold colored viscous liquid. A conversion of over 65% in ^Q imeres, trimer and higher polymers had taken place. Infrared analysis of the product showed strong ether bands, indicating that polymerization was taking place with formation of a polyether of the type given below:

HH ₂ C-CHC ₆ H ₅ ^ I- 0-CH ₂ - CH - /

Examples 8-10

Using a 500 cm * stainless steel autoclave and magna drive stirring (2,000 rpm), several different hydrocarbon samples were isomerized or disproportionated using a HZSM - ^ catalyst . The normal operation was that one which introduced a weighed sample of the catalyst which had been freshly calcined for 2 hrs. At 516Έ (960 ⁰ F) in the open Autoldaven. A measured volume of hydrocarbon was poured into the autoclave and the unit was sealed and flushed with helium or hydrogen through a valve system (valving) to remove air. The catalyst and reactants were adjusted to the desired with stirring

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Reaction temperatures in such a closed System heated. The reactions were obtained by taking of vapor phase samples checked at regular intervals. This was done by draining samples in executed a small volume evacuated system. Since small samples are taken, the pressure drops were minimal in the reaction system. Chromatographic analyzes of the samples were made using a 6 m χ 6.35 mm (20 ft. χ 1/4 in.) n-propyl sulfone / dimethyl sulfoxide column (Weight ratio 73/27) at room temperature using hydrogen executed as a carrier gas at 70 cm / min.

Example e

Into the above-described apparatus 235 cnr n-ifesfean and 1o g HZSM-4'-catalyst introduced which prepared by Anmoniumaustausch of sodium ZSM-4-aluminosilicate and then initially for 72 hrs. At 538 ⁰ C (1ooo ° F) and then calcined for 2 hours at 516 ^° C. (960 ^° F.). The autoclave was closed and so under autogenous pressure; heats up so that the heat continued to rise. At a temperature below 232 ⁰ C (45 ° F ©) 3o% of n-pentane isomerized. Disproportionation products were observed to a very small extent. In particular, the n-Peiitan weight amount, in percent, decreased to 8-1.3% after heating the reaction mixture to a temperature τοη 231 ⁰ C (448 ° F.) For a period of . 2355 StA ,, The balance of Kohleiirasserstoff-component B contained 18 ₉ 1% isopentanes "No measurable · JieBge butanes or. Hexaaen was abandoned until this conversion. observed «- -. ....- ..; ..

903S45

Example 9

Using an ammonium-exchanged sodium-ZSM-4 aluminosilicate then calcined for 64 hrs. At 521 ⁰ C (9To ⁰ F), cooled, stored, and at 521 ⁰ C (97o ° F) also further 2 hours before After calcining after use, an n-pentane charge was disproportionated. The catalyst for 2 hrs. At 521 ⁰ C (97o ° F) was freshly before use

• κ calcined. 50 cnr of n-pentane and 2 g of the HZSM-4 catalyst were introduced into the autoclave, a hydrocarbon density of about 0.1 g / cm- ^{5 being} obtained. The product disproportionated to form both normal and isobutane along with normal hexane and isohexanes. The selectivity for disproportionation was highest when the normal pentane conversion was 69.3%. At 69.3% the hydrocarbon constituents contained 19.0% of disproportionation products, 53.0 % isomerization products and 28.0 % of products of a secondary reaction.

Example 1o

Using the same catalyst as in the disproportionation experiment described in Example 9, isopentane was disproportionated. The hydrocarbon density in the reaction zone was about 0.5 g / cm. The maximum selectivity for dispropportionation took place at the conversion rate of 48.8 % by weight, 3o.1% of disproportionation products, 35.4% of isomerization products and 27.5 % of secondary reaction products being obtained.

909-845 / 177

Was when an exchanged with rare earths, Linde X zeolite, the n-pentane as described above in an autoclave, introduced occurred at temperatures of about 238 ⁰ C (46o ° F) during heating up to 23 h. 2o min does not exhibit a measurable amount of disproportionation. When a rare earth chelated exchanged Linde zeolite Y (chelated rare earth Exchanged Linde zeolite Y) in an autoclave together with n-pentane and a small amount of o, 2 wt -.% Of pentane-2, to activate or catalyze the isomerization or disproportionation was introduced, found in the course of a period of heating at 235-241 ⁰ C (455-465 ⁰ F) in 24 hours. was statt.Desgleichen a negligible reaction with the use of a dealuminated (dealuminized) hydrogen mordenite for the n-Pentanisomerisierung or disproportionation in the presence of 0.2% by weight of pentene-2, only a negligible conversion was observed. It can thus be seen that using an HZSM-4 catalyst, good conversion and selectivities for paraffin isomerization and disproportionation were obtained at low temperatures.

Example 11

The ZSM-4 catalyst prepared as described in Example 1 was evaluated for the disproportionation of various feed weights. In one case, 100 % o-xylene was disproportionated with the formation of valuable tri- and tetramethylbenzenes, for example dur oil (1,2,4,5-tetramethylbenzene). In the other case, a mixture of toluene and tri-

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- 3ο -

methylbenzene disproportionates to form xylenes, the reaction was carried out in the liquid phase at a temperature of 316 ⁰ C (600 ⁰ F), a pressure of 35.2 atmospheres (5oo psig) and a liquid hourly space velocity (LHSV) of 1/1. The results are compiled in Table VI below.

Table VI

feed o-xylene - 2.5 o, 2 Toluene - 8o % ₉ o, 4 100 % 21.5 Example 12 Trimethylbenzene - 13.8 '47.8 2o % 4o, 7th Product ^ weight! o, o4 31.8 Light products (according to Ends) 0.8 Tri- and tetramethylbenzene 27.9 o, 5 benzene Ethyl toluene 12.3 toluene o, 7 Xylenes Ethylbenzene

A solution with a content of 68.8 g sodium silicate, 4.8 g sodium aluminate (approximate composition: 3o, 2 % Na ₂ O, 44, 5% Al ₃ O ₅ , remainder gliver loss), 38.6 g of 98 # Sodium hydroxide pellets and 153.0 g of water were prepared. It was formed by dissolving sodium aluminate in water and then adding to this mixture of sodium hydroxide "The solution was at a temperature from 60.0 to 65.6 C ⁰

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(14o "to 15o ⁰ F), the sodium silicate being incorporated into the solution. The resulting solution was aged for 15 minutes. The resulting solution was added to 27o, og sodium silicate. 47.5 g Al ₂ (SO ^), "14H ₂ O were dissolved in 150 grams of water along with 25.0 g of a 96.5% H ₂ SCK. The resulting aluminum sulfate / sulfuric acid water solution was

*) incorporated into the solution of sodium silicate and CDA.

36.0 g of 24% strength tetramethylammonium hydroxide in methanol were mixed into this solution. The resulting solution was maintained for 16 hrs. At 1oo ° C (212 ⁰ F) in a loosely capped container to evaporate the methanol. The Bäälter was sealed and heated at 11o ° C (212 ⁰ F) up to the formation of crystals. It has been found that the end product is a MolveÄältnis of Tetramethylammoniumoxyd to aluminum oxide of O, 16 to 1, a Molveäiältnis of Na ₂ O: Al ₂ O * O, 83: 1 and a molar ratio _o of SiO _2: Al ₂ O, of 5.78. The product crystals were ZSM-4 crystals with a rod-like habit. The crystals sorbed 3.9 wt .-% cyclohexane, measured at 2O ° C and 2o mmHg and 12.3 wt .-% of water, determined at 2O ⁰ C and 12 mmHg. The main part of the sodium content was a base exchange with; aqueous ammonium chloride and subjected to the ammonium-exchanged form wucLe then calcined at 538 ⁰ C (1ooo ° F) for 3 hrs., to obtain the hydrogen form of ZSM-4. The HZSM-4 composition showed the X-ray diffraction pattern essentially as shown in Table 1.

Example 13

A solution was made by dissolving 173.7o g of 97% sodium hydroxide in 688.8o g of water

*.) Crystallization directors (crystallization directing agent)

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And adding 21.60 g of sodium aluminate and 309.60 g of sodium silicate to this *. A 3.78 liter (1 gallon) capacity Waring blender was charged with an aqueous sodium silicate solution containing 1215.00 grams of sodium silicate. The power controller (powerstat) on the Wariiig mixer was switched on at a low speed of about 65 % capacity and the CDA solution was added to the sodium silicate solution * After the addition of the CDA solution, an alum solution (aluminum sulfate solution), which contained 213, 78 g Al ^ SO ^ · 14H ₂ O, 248.4o g of 96.5% igeni H «SO ^ and 1080.00 g H« 0 contained, was added. This caused the mixture to thicken in the Wariqg mixer. Mixing was continued with the help of a spatula. When the mixture was thoroughly mixed, 325.80 grams of a 25% aqueous solution of tetramethylammonium hydroxide was added until a smooth paste was formed. The product was poured into two i, 8o 1 containers (two-quart jars), sealed and placed in a steam box at 100 ° C. After 34 days a product crystallized out which had a ZSM-4 composition with a molar ratio of silicon dioxide to aluminum oxide of 13: 1. It showed the characteristic X-ray diffraction pattern of ZSM-4 as shown in Table I above.

The crystals were subjected to a base exchange with a 2ο weight, - subjected% ammonium sulfate solution, washed free of sulfate ions and Ho ⁰ C (25o ^o F) dried and then calcined to the ammonium form to the hydrogen form of ZSM-4, convert · Analysis the product had a sodium content of 0.34 wt. -96

0OQ84S / 1772

Example 14

A solution was prepared by dissolving 169.8 g of 97.3% sodium hydroxide in 673.2 g of water and adding 21.1 g of sodium aluminate and 30.2.7 g of sodium silicate thereto. A 37.3% aqueous sodium silicate solution containing 1,188 grams of sodium silicate was charged to the 3.78 liter (1 gallon) Waring mixer. The power regulator on the Waring mixer was turned on at a low speed of about 65 % capacity and the CDA solution was added to the sodium silicate solution. After the addition of the CDA solution, an alum solution (aluminum sulfate solution) containing 2o9, og Al ₂ (SO ^) ₃ * 14H ₂ O, 176, o g of 96.5% H ₂ SO ^ and 96o g H ₂ O contained, admitted. This caused thickening of the mixture in the Waring mixer. Mixing was continued with the help of a spatula or spatula. When the mixture was thoroughly mixed, 665.5 grams of a 24% aqueous solution of tetramethylammonium hydroxide was added until a smooth paste was formed. The contents were placed in a flask or bottle and heated to 100 ° C. After 30 hours a product crystallized out which consisted of a ZSM-4 composition with a molar ratio of silica: alumina of 7.7: 1 (7.7 to 1) and the characteristic X-ray diffraction pattern of ZSM-4, as in the above Table I indicated.

The crystals were subjected to a base exchange with ammonium chloride, washed free from Chirid,

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dried at 11ο, ο ⁰ C (23o ° F) and then ^{calcined at 538 0} C (100 ° F) to convert the ammonium form of ZSM-4 to the hydrogen form. On analysis of the product, a sodium content of 0.21% by weight was found.

The catalysts of Examples 12 to 14 were with respect to the o-xylene isomerization according to selectivity factor test described above. As shown in Table VII below, the crystalline aluminosilicate ZSM-4 zeolite gave high selectivity factors well above 4 layers. Other zeolites, which found particular application in endothermic processes, gave selectivities, which were usually below 1, o.

catalyst Table VII Total-
umwand-
• lung
1o hour Isomeri
sation Dispro
portio
renation at
game HZSM-4
HZSM-4
HZSM-4 Selective
vitality
factor 62.3
28.4
3o, 6 51.2
25.3
28.6 11.1
3.1
2, o 12th
13th
14th 4.6
8, ο
14.2

From the above it can be seen that the use of such catalysts does not without exception in catalytic cracking processes with the production of substantial amounts of materials that are within the eenzine boiling range, these are useful in an advantageous manner for the creation of high selectivities in these exothermic reactions

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and heat exchange type reactions according to the method can be used according to the invention. To this These reactions are of considerable technical importance. It can also be seen that the Particle size and the dimensions of the zeolite material play an important role in the process according to the invention can play.

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Claims (1)

1) Procedure for the application of an o ^ g ^ hisehefi Se sohiekung by a conversion, which k creases _t thereby gekerinzei ^ hnitijidal man maintenance 371 ^ (TQP ⁰ F) over einp y implements, <iejp iinpipsXylQl « L. self-efficacy factor of at least part S ₁ 5, 2) procedure. according to claim 1, characterized in that the zeolite the In Table $ 5) Method according to Ansgf * ueh 1 ojl§r 1 ₁ characterized in that the Z _e olith made of a · »ZSM-4 material with a MQl- ¥ erhj | ^ 1> nis ψοη ISiQ ^? - ^ 2 ¹³ J 5 and Ij? There are other metals except for the country or ORIQIMAL INSPECTED