DE1207034B - Process for the conversion of hydrocarbons - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Clog

German class: 23 b -1/04

Number: 1 207 034

File number: U 7684IV d / 23 b

Filing date: December 28, 1960

Opening day: December 16, 1965

The conversion of hydrocarbons in general and the isomerization of hydrocarbons in particular is of particular importance to the petroleum industry. With the appearance of gasoline engines with high horsepower in recent years there has been a need for gasoline with higher Octane number. Natural straight-run gasolines, i. H. Heavy gasoline, mainly contains normal paraffins, z. B. n-pentane and η-hexane, whose octane numbers are relatively low and for the modern Requirements are too low. It has therefore become important to use these low octane components to convert into their corresponding higher octane compounds. The transformation of this Hydrocarbon components is achieved by isomerization, since the isomers formed one have a much higher octane rating. The ease with which isomerization is achieved is thus extraordinary Gained importance.

In the past, straight-run, low-octane gasoline was used directly as motor gasoline. However, when the need for higher octane gasoline arose, attempts were made to remove the heavy gasoline molecules to thermally relocate or reform to improve the octane number. "Reforming" is used in the oil industry the treatment of gasoline fractions with a boiling range above 90 ° C, which is applied to through Formation of aromatic and branched hydrocarbons, higher octane numbers and improved To get "anti-knock properties". The thermal reforming of gasoline was found to be insufficient and has been largely replaced by catalytic reforming in a hydrogen-rich atmosphere.

In order to make full use of the tetraethyl lead (which is less effective with aromatics than with paraffins) To make this possible, high-octane paraffins must be added to the gasoline mixtures. These high octane Paraffins can only be obtained by alkylation (which may require the isomerization of butane) or by isomerizing the pentanes, hexanes or other light straight-chain hydrocarbons can be obtained.

According to the latest known isomerization processes, the normal paraffins, such as pentane and hexane, are converted into the corresponding branched compounds by contacting the straight-chain hydrocarbons with a solid reforming catalyst in the presence of hydrogen at elevated temperature and pressure. Processes of this type are described in US Pat. No. 2,831,908 and in British Patent Process for Conversion of
Hydrocarbons

Applicant:

Union Carbide Corporation, New York, N.Y.

(V. St. A.)

Representative:

Dr. H. G. Eggert, patent attorney,

Cologne-Lindenthal, Peter-Kintgen-Str. 2

Named as inventor:

JuIe Antone Rabo, Buffalo, N.Y .;

Paul Eugene Pickert, North Tonawanda, N.Y .;

James Edward Boyle, Buffalo, N.Y. (V. St. A.)

Claimed priority:

V. St. v. America December 30, 1959
(862 990)

788 588. In each of these processes, however, a corrosive activator is used, ζ. B. a halide used in the catalyst. Furthermore, none of these processes can be used for isomerization a mixture of n-pentane and η-hexane can be used with high efficiency.

In the catalysts that serve to boiling for reforming above 9O ⁰ C gasoline fractions in higher octane products are also used as activators acid halides which are corrosive.

The invention relates to a process for converting hydrocarbons, which is characterized in that the hydrocarbons are in a hydrogen stream under the conditions required for their conversion with a molecular sieve "Υ" consisting of a crystalline zeolite metal aluminosilicate (hereinafter referred to as "zeolite Y") wherein at least 40% ^er d Aluminiumoxydtetraeder are satisfied by polyvalent metal cations, having a silica-alumina molar ratio of more than 3 and on which a metal of the VIII. group of the Periodic system is applied in an amount of at least 0.05 percent by weight, be brought into contact.

509 758/389

3 4

For the production of this conversion catalyst, preferably a noble metal such as platinum and palladium, sators, no protection is applied within the scope of the invention. In this context, was claimed. The term "hydrocarbon wall - established that the catalytic activity of the zeolization process" encompasses very generally processes for lithes which is highly dependent on firstly the pore size, Improvement of the octane number of gasoline or secondly the crystallinity, thirdly the silicic acid conversion of heavy hydrocarbons in alumina ratio and fourth of the kind of light, low-boiling hydrocarbons or cations in the structure.

Conversion of hydrocarbons into example The pore size is important for the catalytic

wise aromatics by hydrogenation or dehydrogenation. lytic activity than it must be greater than that

These processes therefore include isomerization, io molecules of the input and the product. the

Reforming, splitting, alkylation, dealkylation, molecules must have unimpeded access to the structure

Hydrogenation, dehydrogenation and splitting hydration have and can be desorbed from them,

tion. Therefore, in processes for the conversion of

The term "zeolite" generally includes a hydrocarbon only large-pored molecular sieves

Group of natural or synthetic hydrati- 15 can be used, which are able to adsorb benzene.

The pores must - in other words - be so large

have structure. They differ from each other in that they contain substantial amounts of branched C ₄ -C ₁₀ -

due to their composition, crystal structure and hydrocarbons and their

Adsorption properties. A suitable method of speaking is structurally rearranged connections

to identify the crystal structure, the X-ray or isomer is given.

ray interference method. A pore size between 3 and 10 Å is in

In terms of structure, crystalline zeolites consist of an open three-dimensional lattice molecule and other frequently occurring molecules, made up of SiO ₄ and AlO ₄ tetrahedra. The tetrahedron gases and liquids, the molecules of which are smaller than the pores of the molecular sieve through the mediation of oxygen atoms, are adsorbed so that the ratio of oxygen atoms to and in the internal structure is retained, while the sum of the aluminum and silicon atoms is 2 is, others, whose molecules are larger, have no access ie o / (Al + Si) = 2. The negative electrovalence to the inner pores. This ability to separate substances from aluminum-containing tetrahedra by according to their molecular size is called mole inclusion of cations, e.g. B. Alkali or Erd- 30 kularsiebffekt designated. This effect enables alkali ions to become saturated in the crystal. This not only the separation of molecules of different equilibrium can be expressed by the formula 2 Al / (2 Na, sizes, but also the determination of the crystal 2 K, 2 Li, Ca, Ba, Sr etc.) = 1 ± 0.15 pore size of the crystalline zeolites,
will. A cation can be replaced by another by suitable exchange methods. 35 porous crystalline zeolites can have large sym-

Furthermore, as is known, the crystal structures have metric molecules used, for example

many zeolites leave gaps of molecular (C ₄ H ₉ ) ₃ N and (C ₄ F ₉ ) ₃ N. adsorption values

Dimensions on. The gaps are in all- recognize that all forms of zeolite Y approximately

common occupied by water of hydration. Less than 20 percent by weight of the (C ₄ H ₉ ) ₃ N molecule, the one

suitable conditions, d. H. after at least partially 40 has a size of about 10 Ä, but not that something

Dehydration, these zeolites can effectively adsorb _{larger (C 4} F ₉ ) _{3 N.} All other smaller ones

Adsorbents are used that are in the molecules, such as benzene and η-paraffins, are in

Retain adsorbate molecules between spaces. The similarly large amounts are adsorbed.

Access to the channels is through openings in the. The crystallinity of the zeolites strongly influences the

Crystal lattice given. These openings limit the catalytic activity. Zeolite catalysts,

The size and shape of the molecules that are adsorbed and have the crystal structure are more active than non-

can. A separation of mixtures of foreign crystalline zeolites of the same chemical ingredients

molecules on the basis of the molecular composition. The catalytic implementation of the

measurements, whereby certain molecules of the zeolite hydrocarbons are found at high temperatures

adsorbed while others are rejected, 50 instead. The crystal structure of the catalyst must therefore

is therefore possible. This characteristic property to be stable at the reaction temperature. In this

many crystalline zeolites led to their designation respect, it was found that a higher silica

"Molecular Sieves". acid-aluminum oxide ratio that is heat-resistant

The chemical formula for zeolite Y, in terms of speed, has been improved. An SiO ₂ -Al ₂ O ₃ molar ratio of

in molar ratios of the oxides, as follows, above 3 proved essential to the process

be written: according to the invention.

The cation in the process according to the

0.9 ± 0.2 Na ₂ O: Al ₂ O ₃ : W SiO ₂ : ZH ₂ O. also has the molecular sieve used

a great influence on the catalytic activity. 60 The alkali metal cations poison just like others

Here W has a value from 3 to 6 and X has a monovalent metal cation the catalyst in such a way

Value up to 9th that it has no activity for ionic hydrocarbon

The identification and production of zeolite Y reactions, but some activity for radicals

is the subject of German patents 1,098,929 and has hydrocarbon reactions. Since the iso-

1 164 384. 65 merization of paraffinic hydrocarbons

As mentioned earlier, when a catalyst is an ionic reaction, a molecular sieve can be used in

zeolitic molecular sieve with polyvalent catheter essentially all cation sites are shown

ions used, to which a metal of Group VIII, through the entire aluminum atoms in the crystal

5 6

lattice, by alkali metal ions or other mono- It is most advantageous to set the temperature several

valent metal cations are occupied, not used to hold at 500 ° C for hours. You can then access the

will. It has been found that the catalytic temperature of the isomerization can be lowered. the

Processes in the method according to the invention at least space flow rate of the hydrogen 40% of the monovalent metal cations from the 5 during the activation should be about 2 l / cm ³ catalyst

Zeolite must be removed. It was found, however, to be sator per hour.

that in this process the replacement of the mono- The isomerization process according to the invention valent cations versus polyvalent cations which is not only different from that described above increases catalytic activity. This, surprisingly, is a catalyst, but also from factors such as first since up to now the presence of cations io the reaction temperature, secondly the room (monovalent or polyvalent) the flow rate for the conversion, thirdly the hydrogen of Hydrocarbons used catalysts hydrocarbon ratio and fourth the re-poisoned became. Depending on the polyvalent cations, action pressure.

which is found to be particularly effective in the process according to "The isomerization process is at a temperature

Proved according to the invention, calcium will perform most strongly between 300 and 425 ° C. at

preferred. however, the isomerization of a pentane fraction will

The degree of exchange of the alkali metal cations preferably at a temperature between 350 and

polyvalent cations is therefore critical. It worked at 38O ⁰ C. As a result of the fact that the

it was found that for the process according to the optimal isomerization temperatures for pentane

Invention, the equivalent amount of polyvalent Kat- 20 and hexane fractions are close together, resulted

ions contained in the zeolitic aluminosilicate are another surprising advantage of the invention,

must be at least 40%. In addition, namely the possibility of using a mixture of n-pentane

the activity of the catalyst increases to the extent that n-hexane fractions are isomerized. It was

in which monovalent metal cations are removed. found that 'a mixture of pentane and hexane

In other words, isomerization can be carried out effectively in the catalyst according to FIG. 25 if the catalyst

Invention are of the aluminum atoms less than sators at a temperature between 350 and 375 ° C

60% with monovalent metal cations and at least used. It should be noted, however, that on

40% associated with polyvalent cations. the upper limit of the specified temperature range

Additional alkali metal cations can be isomerized more effectively by the pentane fraction,

Ion exchange with ammonium or alkylsubsti- 30 but a higher proportion of the hexane to gaseous

tuted ammonium cations are removed. These products will be split. Conversely, the

can then during a later activation lower limit of the temperature range of the hexane

treatment are driven off and leave behind effectively isomerized, while the pentane fraction in

additional active sites in the aluminosilicate is converted to a lesser extent. By addition

structure. 35 of activators, e.g. B. of Lewis acid halides,

The decomposition of the metal compound is due to an effective isomerization of hydrocarbons

Heating to a temperature above 300 ° C, preferred materials at temperatures significantly below 300 ° C.

wise above 400 ° C. Possible when using temperatures.

of a metal of the iron group, this measure is evident from the fact that the temperature is a

preferably in a reducing atmosphere, such as an extremely critical factor in the method according to FIG

Hydrogen, methane or carbon oxide, is the invention. It is essential that the isomerization

while in the case of precious metals, the used air temperature does not exceed 425 ° C, otherwise an un-

can be. Preferably, the decomposition will take place after the desired cleavage. Even above

after pressing the powder. If it is above 400 ° C, the splitting will be considerable and reduced

carried out beforehand, the pure yield of liquid product must be achieved in a dry atmosphere. Butane, on the other hand

be tabletted to avoid too strong renewed water- can also be ^{isomerized effectively at 425 0} C,

avoid recording. As optimal for the isomerization of a pentane

The results obtained with catalysts obtained with a platinum catalyst turned out to be a fraction

that a metal of the VIII. Group in quantities temperature of 380 ° C. A hexane fraction becomes

from 0.05 to 2.0 percent by weight dispersed, 50 particularly effective at a temperature of 360 ° C

are good though. However, the best results are isomerized. For isomerization of a mixture

achieved when these metals, especially precious metals, from hexane and pentane fractions turned out to be a

such as platinum and palladium, in an amount from 0.2 to a temperature of 370 ° C as the most effective. Except

0.6 percent by weight are contained in the catalyst. n-pentane and η-hexane can also contain other paraffins

Since the catalysts to be used according to the invention are isomerized by the process according to the invention

The isomerization of the former is usually relatively high

Water content, it is necessary to use them before because of their importance in gasoline top-ups

Use carefully to activate, as they are facing the greatest technical interest.

The speed at which the water is desorbed. The reaction is

are very sensitive. The 60 speed for these catalysts used from 1 to 10 g, preferably

Recommended activation includes the following stages: from 2 to 5 grams of feed, per gram of catalyst per

1 TN ν * 1 * · * 1 JT ^ r hour. It was found that with

? mh finn ' ^a r ^Or vni, I ⁸ T "? wr increasing space flow velocity the exit

I ^ I nH 1; TTh ' ^beu * ^e ω isoparaffins at a given temperature

heat and then cool. ^ _gerfnger ^ _wifd ^s _{the room flow} .

2. The catalyst is then kept constant at a hydrogen rate that increases with increasing flow at normal pressure slowly from room temperature, the yield of isoparaffins steadily temperature to be heated to 500 ° C. higher until a maximum is reached. As already

mentioned, however, the splitting of the insert increases when the specified optimal temperatures be crossed, be exceeded, be passed. The selectivity of the isomerization reaction is up to the optimal temperature very high. Above this temperature, however, the selectivity steadily decreases.

The molar ratio of hydrogen to hydrocarbon is between 0.5: 1 and 10: 1, preferably between 2: 1 and 5: 1.

The pressure at which the isomerization reaction according to the invention is carried out is between 7.8 and 69 atmospheres, preferably between 21 and 41 atmospheres. With constant contact time the reaction seems to be favored by lower pressures. At low reaction temperatures the selectivity of the catalyst is not adversely affected by the overall reaction pressure. Will however, the reaction temperature increases to a point where some cleavage hydrogenation occurs As a result, the extent of the latter can be reduced by higher working pressures.

As already mentioned, the invention has several advantages over known methods. At first Place among the benefits is the quality of the product itself, the balance for the relationships of η-paraffin comes very close to isomeric paraffin. The amount of 2,2-dimethylbutane that contained in the hexane isomerizate formed according to the invention was found to be more than 12 mole percent established. This isomer, i.e. H. 2,2-Dimethylbutane, is one of the most important of all isomers, the Reforming straight-run gasoline fraction can be formed. Provide great yields of this isomer thus represents a real advance in technology.

Another advantage of the process is that the previously used in all known processes Corrosive activators are no longer required.

A third advantage of the process can be seen in the fact that the hydrocarbons used before Contact with the catalyst according to the invention need not be particularly dried.

As a further advantage, the fact is to be mentioned that the optimum isomerization temperatures are generally lower than in the known methods erforderlichenTemperaturen.Darüber addition, there are the optimal isomerization of pentane and hexane fractions only 10 to 15 ⁰ C apart. As mentioned earlier, this is how it is

ίο possible a mixture of the pentane and hexane fractions to isomerize at the same time.

It has already been mentioned that firstly the type of cation, secondly the crystallinity, thirdly that Silica-alumina ratio and fourthly the pore size the activity of metal-loaded affect zeolitic catalysts. To determine the extent of these influences, various Types of zeolites loaded with 0.5 weight percent platinum and after subsequent Activation investigated for its isomerization activity using η-hexane as an insert.

The zeolites produced and examined included an amorphous zeolite with a high molar ratio of silica to alumina and certain crystalline zeolites. One of the crystalline zeolites had a small pore size and the other, a metal loaded zeolite Y, had large pores and a high SiO ₂ : Al ₂ O ₃ molar ratio. All of the selected zeolites were made in two different forms of cations: one containing sodium, the other calcium. The characteristics of the metal-loaded zeolitic catalysts used and their activity values are shown in Table 1. The isohexane yield and the amount of 2,2-dimethylbutane present in the product are indicative of the isomerization activity. The amount of dimethylbutane is an indication of the high activity of the catalyst, because the formation of this compound is much more difficult than the formation of the monoethylpentane.

Table 1 Activity of platinum-loaded zeolites in the isomerization of n-hexane

Zeolite type Mole
relationship Cations
distribution
equivalent to
in ° / " salary
at Pt-
metal
Weight Fluid
product
extraction yield
to Iso-Q
Mole Mole percent
2,2-dimethyl
butane im
Fluid React
functional
tempe-
rature SiO ₂ : Al ₂ O ₃ percent % percent product ⁰ C Amorphous zeolite 5.3 100Na 0.50 96.7 1.4 0.5 450 Amorphous zeolite 5.3 40Na 0.42 98 5.0 0.2 400 (no molecular sieve) 60 Approx Erionite 6.6 100 (Na + K) 0.70 91.6 6.6 0.1 400 Erionite 6.6 21 (Na + K) 0.47 71.0 3.4 0.1 400 (Pore size 4.8 Å) 79 Approx Metal loaded zeolite XI
(Pore size 9 to 10 Å) 1 2.4
2.4 100Na
13Na
-87 Approx 0.49
0.46 99.0
91.0 <l, 0
9.6 0.0
0.2 450
400 Metal loaded zeolite YJ
(Pore size 10 Å) 1 4.7
4.7 100Na
20Na
-80 Approx 0.50
0.43 95.1
97.0 0.4
66.5 0.2
10.4 400
400

The reaction conditions in the above experiments were as follows:

Space flow rate: 2.0 g of hydrocarbon feed per gram of catalyst per hour.

Pressure: 31 atmospheres.

Molar ratio of hydrogen to hydrocarbon: 5: 1.

These experiments showed that platinum-loaded zeolites with alkali metal cations are not worth mentioning Have activity as isomerization catalysts. The erionite contained potassium and sodium cations and had a pore size of about 4.8 A. This zeolite only adsorbs the n-paraffin molecules while the larger isoparaffin molecules are rejected. From the relatively low yield it can be seen that perhaps a small percentage of the η-hexane adsorbed is converted to isoparaffins but these become trapped and decomposed. The other zeolites with sodium cations have no isomerization activity at all. As can be seen from Table 1, the calcium exchanged Zeolite Y has a much higher activity for isomerization than the other zeolites.

The catalytic properties of the zeolites loaded with noble metal indicate that zeolite Y as a catalyst for hydrocarbon reactions with ionic mechanism any other known Catalyst is superior.

A series of ion-exchanged Y-zeolites with polyvalent metal ions loaded with 0.5% platinum were made and tested. The degree of equivalent ion exchange for these zeolites Y was between 60 and 80%. Mono-, di-, tri- and tetravalent cations were exchanged for the original sodium cations. Each group contained cations of different electropositive character. All ion-exchanged zeolitic catalysts retained the original crystal structure of zeolite Y. The ion-exchanged and platinum-loaded samples were first activated at 350 ° C in air and then in hydrogen, before being tested for their activity in the isomerization of η-hexane and the reforming of gasoline have been tried.
The test results compiled in Table 2 show that zeolites with alkali metal cations have no or only very poor activity and that only the lithium cation has a low catalytic activity. All polyvalent cation catalysts have significant activity. The activity of all zeolites with divalent cations (Mg ⁺ +, Ca ⁺ +, Sr ⁺ +, Zn ⁺ + and Mn ⁺ +) in the isomerization was very high. The experiments show, however, that a higher activity is achieved with calcium than with the other polyvalent cations and that this activity is also maintained for a longer period of time.

The catalysts made from zeolite Y were also used to reform a light gasoline. According to Table 2, when using the zeolitic catalysts with alkaline earth metal cations obtain a product with a higher octane number than with zeolitic catalysts with divalent and higher cations. The former are therefore preferred.

Tabel

Influence of the cation in various cation-exchanged zeolite Y catalysts on the isomerization results * (insert: n-hexane)

catalyst

Cations

Pt

Weight percent

Liquid product extraction

Iso-Q yield

Mole percent

Dimethyl Tempe butane rature Mole percent ⁰ C 0.2 400 0.2 400 0.0 450 6.7 400 10.4 400 4.1 400 6.8 400 10.2 400 10.5 400 6.9 400 2.3 400

Octane number at
85 ° / o liquid products
yield

Reforming **

Li-Y

Na-Y

K-Y

Mg-Y

Ca-Y

Sr-Y

Zn-Y

Mn-Y

Ce ⁺³ - Y

Al-Y

fp + 4 γ

33Na
100Na
2Na
19Na
20Na
17Na
37Na
26Na
34Na
32Na
32Na

67Li

98 K

81Mg

80 Approx

83Sr

63 no

74Mn

66Ce

68Al

68Ce

0.28

0.5

0.45

0.39

0.43

0.43

0.48

0.47

0.45

0.43

0.34

91.6 95.1

100 94.2 97.0 78.6 97 92.6 99 87.7

100

9.2 0.4 0.0

55.4

66.5

32.1

60

62

66

50.3

42.5 81.0

87.5

70.5

77

77

79.5

85

* Reaction conditions:

Space flow rate: 2.0 g feed per gram of catalyst per hour. Pressure: 31 atmospheres.
Molar ratio of hydrogen to hydrocarbon = 5: 1.

· * A light gasoline was used in the reforming reaction. The experiments were carried out at 450 to 500 ^° C. and 31 atmospheres. Molar ratio of hydrogen to hydrocarbon in use = 5.

The ability of metal-loaded zeolitic catalysts to catalyze cleavage, reforming and other ionic hydrocarbon reactions is based in large part on the active alumina. In order to stabilize the aluminum oxide in its most active form, the SiO ₂ -Al _a O ₃ molar ratio of the catalyst must have a value such that essentially all of the available aluminum oxides are present in a highly active form. For this reason, the SiO ₂ -Al ₂ O ₃ ratio must be at least 3, preferably more than 4.5.

As a use can straight-run fractions, consisting essentially of pentanes and hexanes in practical pure form, or a mixture in the gasoline boiling range can be used. Mixtures of this type contain paraffinic fractions, which are rich in n-pentane and η-hexane, from the products the conversion process will be separated. Ge

509 758/389

12th

A suitable use is, for example, a light paraffinic fraction rich in n-pentane and η-hexane, which is obtained by the reformate from the reforming of heavy gasoline by distillation in a light and heavy fraction is separated.

Suitable paraffinic fractions can also be obtained from the reforming products by other separation methods, z. B. by solvent extraction and adsorption on molecular sieves. According to the method according to the invention, branched hydrocarbons can also be added to their branched isomers are isomerized. For example, monomethylpentane can be converted to dimethylbutane are isomerized.

In addition to its use for the petroleum industry, the isomerization of practically pure n-pentane and η-hexane is also of great value to the chemical industry.

IO The invention is explained in the examples in conjunction with the drawing. In

F i g. 1 is the influence of changing the amount of exchange of sodium cations for Calcium cations are graphed, while in

F i g. 2 the best temperature-yield relationships when using the polyvalent ^ cations exchanged catalyst according to the invention are shown graphically.

example 1

The calcium-exchanged and loaded with platinum zeolite Y was used to isomerize η-hexane. The results are shown in Table 3. The experiments were carried out at a pressure of 31 atmospheres and a molar ratio of H ₂ to n-hexane of 5: 1.

Table 3

1 2 3 4th Versu chNr.
6th 7th 8th 9 350 375 375 400 375 400 425 375 400 2.0
27 2.0
30th 2.0
57 2.0
59 2.0
6th 2.0
27 2.0
30th 2.0
25th 1.0
104 94.7 97.1 96.7 84.1 99.4 94.2 87.1 100 91.4 19.8
18.1 17.2
15.2 22.4
19.0 21.4
18.0 32.1
18.5 22.8
19.1 22.7
18.7 27.0
19.5 21.9
20.3 36.7
12.0
86.6
63.3 31.0
10.1
73.5
55.0 38.2
12.4
92.0
67.3 35.6
10.8
85.8
54.2 34.9
8.7
94.2
61.7 37.3
11.2
90.4
63.7 36.4
10.4
88.2
50.3 37.1
9.6
93.2
66.2 36.9
10.6
89.7
62.0

Reaction ^{temperature, 0} C ...
Gram stake per gram

Catalyst per hour

Running time, hours

Yield from liquid product,

Volume percentage

Analysis of the liquid product,
Volume percentage

n-hexane

3-methylpentane

2-methylpentane

2,3-dimethylbutane

2,2-dimethylbutane

Total hexanes

Yield of isohexanes

400

2.0 126

96.7

24.2 19.3

36.9

9.7 90.1

63.7

Example 2

As further proof of the excellent self-listed. In experiments 4 and 5, their results of the catalyst, three attempts have also been made in the table carried out, in which n-pentane was used as a feed. Mixture of hexane and pentane over the catalyst The results are shown in Table 4 as Runs 1 to 3 45.

Table 4

Reaction temperature, ° C

Pressure, atmospheres

Space flow rate, grams of input per gram of catalyst per hour

Ha / hydrocarbon molar ratio

Running time, hours

Liquid product yield, percent by volume

Analysis of the liquid product, percentage by volume

n-hexane

3-methylpentane

2-methylpentane

2,3-dimethylbutane

2,2-dimethylbutane

Isopentane

n-pentane

1 2 Attempt no
3 4th 350 400 450 400 31 31 31 31 2.0 2.0 2.0 2.0 5: 1 5: 1 5: 1 5: 1 131 149 152 174 - 97.6 95.2 95.5 - - 12.0
8.3 - - - 15.6 9.9
87.1 49.8
48.5 50.4
37.5 3.1
2.22
33.4

425 31

2.0 5: 1,177 91.3

10.9 8.3

15.8

3.7 26.4 30.4

14th

Example 3

In order to determine the effects of a change in the extent of exchange for polyvalent cations in a zeolite Y catalyst containing 0.5 weight percent platinum on the catalytic activity, a series of isomerization tests were carried out with η-hexane as the feed. The results of these tests are shown in Table 5. All experiments were carried out at 31 atmospheres with a space flow rate of 2 g of n-hexane per gram of catalyst per hour and a molar ratio of H ₂ / n-hexane of 5: 1.

Table 5 Catalyst: Sodium Zeolite Y (100%)

Attempt no. 450 5 6th 2 3 j 4 98.7 475 500 400 425 93.6 98.7 94.7 99.0 99.1 - 89.0. 71.3 97.0 95.7 2.4 - 7.1 - - - 5.2 9.5 0.1 1.0 2.4 - 0.2 - - 5.1 15.7 0.1 1.0

Reaction temperature ^{, 0 C}

Liquid product yield, percent by volume

Product analysis

n-hexane

3-methylpentane

2-methylpentane

2,3-dimethylbutane

2,2-dimethylbutane

Yield of iso-C _e, volume percent, based on the use

Propane, mole percent

375
98.7

96.8

0.0

No propane analysis in this series. Catalyst: calcium (45 ° / ₀ ) zeolite Y

7th 8th Versu
9 chNr.
10 11 370 385 410 425 440 100.0 100.0 100.0 100.0 95.5 100.0 91.0
mas
kiert 76.5
8.8 70.6
11.8 57.4
14.8 - 5.6 11.2 14.0 21.3 - 0.0 0.5 0.8 1.8 0.0 5.6 20.0 25.8 36.2 - - 0.2 0.3 1.2

Reaction temperature ^{, 0 C}

Liquid product yield, volume percent product analysis

n-hexane

3-methylpentane

2-methylpentane ..

2,3-dimethylbutane

2,2-dimethylbutane

Yield of iso-C _e, volume percent, based on the use

Propane, mole percent

450 96.9

54.0 15.9

23.5 2.3

40.4 1.1

catalyst
Ca (45%) Y chNr.
15th 16 13th Versu
14th 480 500 460 470 97.4 88.8 96.2 96.2 40.5
18.1 27.9
17.4 47.0
17.4 41.4
18.4 28.2 29.7 26.9 29.1 4.3 6.0 3.3 4.2 49.3 47.2 45.8 50.0 3.9 7.3 2.1 2.9

catalyst
Ca (65%) Y

Attempt no.
I 19

20th

21

catalyst
Ca (85%) Y

Attempt no.
23 I 24

Reaction temperature ^{, 0 C}

Yield of liquid product, percentage by volume ...

Product analysis

n-hexane

3-methylpentane

2-methylpentane ...

2,3-dimethylbutane

2,2-dimethylbutane

Yield of Iso-C _e , percent by volume, based on the
mission

Propane, mole percent

400 410 99.3 99.4 35.7
19.1 34.0
19.7 32.5
6.7 34.1
7.0 57.9
2.0 60.4
2.0

425
98.7

32.3
20.2

34.0
7.4

60.8
2.8

435
99.4

32.2
20.6

33.1
7.7

61.4
2.6

450

25.9
18.3

33.6
8.5

60.4

7.7

350
97.4

27.0
19.4

360
97.4

23.2
18.9

36.2 36.4
10.7 11.7

64.6
2.2

65.3
3.0

370 94.7

20.3 17.4

34.3 11.4

59.8 5.3

The results listed in Table 5 are shown in FIG. 1 shown graphically. Experiments 1 to 6 with a non-ion-exchanged catalyst are shown as curve A. Experiments 7 to 16 with a 45% calcium exchanged catalyst are shown as curve B. Tests 17 to 22 with a 65% calcium exchanged catalyst are shown as curve C and tests 23 to 25 with a zeolitic catalyst according to the invention which have been exchanged for 85% calcium are shown as curve D. The improvement associated with extensive ion exchange is evident.

In Fig. 2 shows the optimum isomerization temperature and the isohexane yield obtained at this optimum temperature in percent by volume as a function of the degree of exchange for calcium in zeolite Y, to which 0.5 percent by weight of platinum is applied. These curves show that as the degree of ion exchange increases above 65%, the optimum temperature ^{falls sharply below 410 °} C. and the yield of isohexane formed approaches a maximum. An exchange of 75% or more gives the most active catalyst, the optimum temperature is its use for the isomerization of hexane to 37o C and ⁰ with the maximum degree of isomerization is achieved.

Catalytic cracking

The aim of cracking processes including catalytic cracking and hydrocracking is the production of gasoline from hydrocarbon fractions that boil above the gasoline range. In a few cases the product is a certain gaseous hydrocarbon compound, such as ethylene or propylene, is desired.

The conventional catalytic cracking process are carried out at about atmospheric pressure (0.55 to 1.4 atm) and at 470-510 ⁰ C, wherein the catalyst is used as a fluidized bed or fluidized bed. When operated with a straight passage, only 55 to 60% petrol-containing product is formed. Therefore, the unreacted fraction boiling ^{above 200 ° C. must be circulated.}

The known cracking catalysts split the large hydrocarbon molecules and isomerize apart- ' that of the broken down small molecules. However, they do not isomerize the starting hydrocarbons. The lack of activity for the isomerization of the paraffinic hydrocarbons without cleavage of the C-C bond is characteristic of all known catalysts used for catalytic fission will. However, this property is disadvantageous because the isoparaffins can be broken down more easily. Due the lack of activity for isomerization of the starting materials makes use by dehydrogenation and thermal cracking during the cracking process. Since when operating with straight Passing only 55 to 60% of the high-boiling point will be used to increase the Spreading worked on gasoline with circulation. By breaking down the stake and enriching it However, aromatics cannot crack a substantial amount of the recycled oil any further and must be sold as a cheap by-product.

The influence of the amount of multivalent cation exchange on the catalytic activity of zeolite Y in catalytic cracking is shown in Table 6. Corresponding values are given for the behavior of a representative commercially available cracking catalyst with an SiO ₂ -Al ₂ O ₃ -MoI ratio of about 11. The experiments were carried out in a manner similar to that described by Conn and Connolly (Ind. Eng. Chem., 39, ίο S. 1138 [1947]). The reactor was designed in the usual way and ^{filled with 170 cm 3 of} the activated catalyst in a layer 2.54 cm in diameter and 30.5 cm in height. The temperatures in the catalyst bed were monitored throughout the experiment by thermocouples placed in a pocket axially in the center of the reactor at the top, 7.5 cm from the top and bottom of the bed. As use a product obtained in the distillation of crude oil heavy gas oil was used with a final boiling point ao of approximately 450 ⁰ C (specific gravity of 0.864 at 15.6 ° C / 15.6 ° C). It was introduced for 60.0 minutes at normal pressure and a space velocity of 2.0 (by weight). After completion of the experiment, the reactor was 10 minutes with nitrogen at a rate of 571 / hour. flushed. The gaseous hydrocarbons formed during purging were not captured. The liquid cracked product was drawn off at normal pressure and room temperature. All uncondensed gases were recovered by displacement with water and analyzed by gas chromatography. The weight and volume of the liquid product were measured and a portion was distilled using a modified ASTM (D-86) distillation method. The distillation was stopped when a steam temperature of 204 ° C was reached. Then, the weights and volumes were determined between the Siedeanfang and 82 ⁰ C, between 82 and 204 ⁰ C and above 204 ⁰ C (gas oil) boiling fractions. The fraction between the initial boiling point and 82 ° C. was analyzed by gas chromatography. Combined with the analysis of the non-condensed gases, the composition of the total product was determined from C ₁ to 82 ° C. The catalyst was removed from the reactor and the weight of product retained on the catalyst was calculated. For each experiment, material balances were drawn up, which were between 90 and 97 percent by weight.

The yields were calculated on a lossless basis.

Table 7 illustrates the influence of the SiO ₂ -Al ₂ O ₃ ratio of the crystalline zeolite on the activity in catalytic cracking. The experiments were carried out in the same manner as the experiments, the results of which are given in Table 7.

From the values in Table 6 it is seen that the used as the catalyst, Katio-NEN with polyvalent exchanged zeolite Y at 350 ⁰ C is significantly more active than the commercially available amorphous comparative catalyst. The values also show that a zeolite Y used as a catalyst, the cation sites of which are at least 40% saturated with polyvalent cations, is just as active at 375 ° C. as the commercially available comparative catalyst at its optimum operating temperature of 480 ° C.

17 18

Table 6

Influence of the extent of the exchange of polyvalent cations on the catalytic activity of zeolite Y

in catalytic cracking

375

375

375

Temperature, ⁰ C
I 350

350

350

350

Catalyst composition exchange of Mg ⁺² , ° / o · ·

Cation deficiency, ° / o

Unexchanged Na ⁺ , 0 /

/O

Al ₂ O

₂ O ₃

Molverh. SiO ₂ :

Gasoline yield ^a

Selectivity ⁰

D + L ^c

Yields, weight percent of input

H ₂

C ₁

C ₂

C ₃

C ₄

C ₅

C _{6 to} 82 ° C

82 to 204 ⁰ C

above 204 ⁰ C

Deposition on catalyst

iC ₄ in C ₄ , percent by weight

iC ₅ in C ₅ , percent by weight

Specific gravity of the fraction 204 ° C + 15.6 ° C / 15.6 ° C

15th

85 5.0

11.9 97.7 15.0

0.28

0.4

0.1

0.1

11.9

78.2

9.2

24 12

64 5.0

25.4 97.5 31.5

! I.

52 5.0

<0.01 0.01 0.02 0.11 0.07 0.5 0.5 2.6 1.2 5.0 1.4 4.0 2.1 4.5 21.9 27.6 64.2 42.3 8.7 13.6 77.2 79.1 82.5
η ocp. 91.5
η 8 <1

24
5.0

34.6
90.9
46.7

0.03

0.12

0.4

3.6

7.0

4.4

4.3

25.9

42.2

12.1

79.8
89.1

Amorphous
SiO _{2 -Al 2} O ₃ comparative catalyst

34.5
84.3
45.0

0.14
1.22
1.57
5.14
7.96
4.49
6.54
23.51
44.31
5.12

73.5
86.6

19.5
99+

24.0

2.1
17.4
73.3

7.2

0.862 0.855

40
8th

52
5.0

30.2
96.8
40.0

<0.01

0.04

0.10

1.0

2.8

3.0

3.9

23.2

54.4

11.6

83.0

52
0

48
5.0

29.1
96.5
39.5

<0.01

0.02

0.12

1.1

3.4

3.2

4.0

21.8

55.2

11.1

81.9

91.4! 91.7

0.854 0.856 ^! 0 855

64
8th

28
5.0

25.0
96.7
32.0

<0.01

0.01

0.09

0.8

2.5

2.2

2.8

19.9

60.8

10.8

82.4

<0.01 0.02 0.16 2.1 4.5 3.4 3.4 19.5 54.5 12.1

91.7 91.2

0.853 0.856

^a = weight percent gasoline from C ₅ to 204 ° C, based on the input.

⁶ = weight percent product from C ₄ to 204 ° C in product C ₁ to 204 ° C.

⁰ = volume percent of cracked liquid product passing over ^{below 204 0 C + gas losses.}

ο = 64% exchange of Mg ⁺² , 7% exchange of Ca ⁺² .

Table 7 Influence of the SiO ₂ -Al ₂ O ₃ ratio of the zeolite on the activity in catalytic cracking

Temperature, ⁰ C

480

415

380

350

375

400

425

Catalyst composition exchange of Mg ^{+ 2.} %

Cation deficiency,%

Not exchanged Na ⁺ ,

Molar ratio SiO ₂ : Al ₂ O ₃ zeolite

Gasoline yield ^a

Selectivity ⁰

D + L ^c

Yields, percent by weight of input

H ₂

C ₁

C ₂

Amorphous SiO _{2 -Al 2} O ₃ comparative catalyst

34.5 84.3 45.0

0.14

1.2 1.6

77
0 75
3 77
0 79
0 711
5 711
5 ₇₁ d
5 23
2.3 22nd
3.2 23
4.3 21
4.6 24
5.0 24
5.0 24
5.0 X Y Y Y Y Y Y 40.0 35.4 32.9 28.8 34.6 40.0 36.9 89.7 95.2 96.3 94.2 90.9 91.7 86.7 50.0 43.5 41.5 38.0 46.7 53.5 54.0 0.10
0.80
1.2 0.03
0.18
0.36 0.01
0.06
0.21 0.01
0.05
0.16 0.03
0.12
0.44 0.03
0.23
0.64 0.05
0.25
1.2

^a = percent by weight gasoline from C ₅ to 204 ⁰ C, based on the use. "Product = C ₄ 204 ⁰ C in the product is C ₁ to 204 ° C. ⁰ = Below 204 ° C for continuous liquid cleavage product. ^D = Mg ⁺² -exchange 64%, Ca ⁺² -exchange replaced 7%. ^E = calcium cations .

83 ^e 0

17th
5.0

23.4 88.6 27.0

758/389

Table 7 (continued)

Temperature, ⁰ C

480! 480 415! 380 I 350 I 375 I 400! 425! 375

480 415 380 350 375 400 425 3.3 1.4 1.1 1.8 3.6 3.4 5.9 6.2 3.1 2.6 4.6 7.0 7.3 11.2 4.0 2.6 2.1 3.5 4.4 6.7 6.7 3.8 3.4 3.1 3.9 4.3 6.4 6.0 32.1 29.4 27.6 21.4 25.9 27.9 24.2 43.5 52.9 53.5 53.1 42.2 38.2 33.0 4.9 6.5 9.6 11.5 12.1 10.2 11.4 52.2 76 79.8 81.9 79.8 79.0 76.3 57.2 86 90.4 91.8 89.1 90.6 88.5 0.864 0.858 0.853 0.855 0.862 0.869 0.874

Yields, percent by weight
from the use

C ₃

C ₄

C ₅

C _{6 to} 82 ° C

82 to 204 ⁰ C

above 204 ⁰ C

Deposition on the catalyst

iC ₄ in C ₄ , weight percent ..
iC ₅ in C ₅ , weight percent ..

Specific weight of the
Fraction 204 ° C, 15.6 ° C ..

5.1

8.0

4.5

6.5
23.5
44.3

5.1
73.5
86.6

0.885

2.3
18.5
53.4

11.9
79.2
68.8

The values in Table 7 show that the polyvalent Y zeolite with an SiO ₂ -Al ₂ O ₃ molar ratio of more than 3 is just as active at considerably lower temperatures as the commercially available comparative catalyst and zeolite X. At 350 ⁰ C, the magnesium-exchanged zeolite X showed no activity for catalytic cracking. In contrast, the exchanged for magnesium zeolite Y at 350 and 375 ° C is about the same activity and considerably higher selectivity (-PrOdUkI less of C ₁ -C ₃₎ had as the commercially available Comparative Catalyst at 480 ⁰ C. At 375 ⁰ C, the exchanged for magnesium zeolite Y (SiO ₈ Al ₂ O ₃ = 5) the same activity as the commercially available comparative catalyst at a higher temperature to 100 ⁰ C. Since high conversions are obtained at lower temperatures with the zeolite Y exchanged for polyvalent cations, products of higher quality than with the commercially available comparative catalyst or with zeolite X are achieved. With the zeolite Y used as a catalyst, C ₄ and C ₅ products are formed which contain significantly higher proportions of branched isomers of higher octane number.

The following conditions were in the cracking reaction using the against polyvalent Metal cations exchanged zeolite Y applied:

Temperature, ° C.,
Pressure, atü,

Space flow velocity
g / g / hr

More general
area

200 to 600
0 to 14

0.5 to 5

More preferred
area

250 to 450
0 to 1.4

Ibis 2

Hydrocracking

The main difference between catalytic cracking and hydrocracking is application a significantly higher hydrogen partial pressure in the hydrocracking process. Generally metals are with Hydrogenation activity is preferably added to the hydrocracking catalysts. These proportions reduce the inclination to coke formation on the catalyst and thus extend its service life.

The results obtained in the hydrocracking of η-hexane with polyvalent cations Zeolite Y as a catalyst are shown in Table 8. Corresponding values are also shown for a commercially available amorphous catalyst. The hydrocracking attempts were made in the same reactors used for catalytic cracking, where but at a total hydrogen plus hydrocarbon pressure of 31.5 atmospheres and a hydrogen to hydrocarbon molar ratio from 3 to 5: 1 was worked.

From the results is seen that with CAY and MgY zeolite as catalysts at a lower by 25 to 50 ⁰ C temperature of the same conversion is obtained on inserted η-hexane as with the amorphous cracking catalyst. With the same conversion, the formation of branched isomers of the feed was more than twice as high in the zeolites used as catalyst (even when working with twice the space flow rate) with a correspondingly lower formation of less desirable propane.

This isomerization of the feed leads to a product boiling in the gasoline range with a higher octane number.

A comparison of the hydrocracking activity of an amorphous aluminosilicate, a zeolitic molecular sieve with an SiO _{2 -Al 2} O ₃ ratio of less than 3 and a catalyst according to the invention, all of which contain polyvalent cations and are loaded with 1.0 percent by weight of palladium, is in FIG Table 9 made. A fuel oil No. 2 with an end boiling point of 310 ° C. was used for these experiments. The values clearly illustrate the better results that can be achieved with the catalyst according to the invention. Metal Loaded Zeolite Y which is inserted ₃ ratio at a lower temperature than 200 ⁰ C the amorphous zeolite and at a lower temperature than 100 ⁰ C, the molecular sieve having a low SiO ₂ -Al ₂ O, converts a substantially greater amount of the under 204 ° C of boiling C ₄ + product.

The hydrocracking is with the metal-loaded catalysts according to the invention, preferably at temperatures of 150 to 400 ⁰ C, in particular from 250 to 350 ° C, atm at pressures from 21 to 140, and in

in particular from 28 to 70atü, at room flow rates (based on weight) from 0.5 to 5.5, in particular from 1 to 3, and with hydrogen-hydrocarbon molar ratios from 5 to 40, in particular from 10 to 20. When using the non metal loaded catalyst according to the invention, the hydrocracking preferably at temperatures of 300 to 600 ⁰ C, in particular of 400 to 500 ⁰ C, at pressures of 21 to atmospheres, especially from 28 atm to 70, at room flow rates of 0 , 5 to 1 (based on weight) and at a hydrogen-hydrocarbon molar ratio of 1 to 5, in particular 3, carried out. Magnesium and calcium are preferred as polyvalent cations and palladium and platinum, very particularly magnesium and palladium, are preferred as metals for loading the zeolite for the hydrocracking process.

Table 8

Comparison of the activity of the zeolite catalyst with the activity of a commercially available amorphous SiO ₂ -

Al ₂ O ₃ catalyst in hydrocracking

Ca (82 ¹ V ₀ ) Y catalyst

Commercially available amorphous cracking catalyst SiO ₂ -Al ₂ O ₃

Mg (72%) ~

Reaction temperature ^{, 0 C.}
Pressure, kg / cm ²

Flow velocity,
Weight / weight / hour

^ / Hydrocarbon

Running time, hours

Input material

375 29

400 32.5

1.0 1.0

3: 1 I 3: 1 17.5 j 19.3

425
32.5

450
32.5

Conversion, mole percent

Analysis results, mole percent

n-hexane

3-methylpentane

2,3-dimethylbutane

2-methylpentane

2,2-dimethylbutane

n-pentane

Isopentane

η-butane

Isobutane

propane

Ethane

Total Iso-Cg

Used catalyst volume,

n-hexane 25.0 I 35.9 j 39.4 1.0! 1.0
3: 1 I 3: 1 6.0 j 8.5

n-hexane 36.6 I 45.5

75.0 7.8

9.9 0.2

1.6 2.3 0.1

17.9 80

64.1 9.8

11.8 0.4

3.3 5.7 0.3

22.0 80

63.4
4.7

6.3

0.1
0.7
2.8
2.2
5.6
13.2
0.5

11.1
80

54.5
3.1

4.7

0.1
0.8
3.3
3.0
7.9
21.2
1.0

7.9
80

475 32.5

1.0 3: 1 11.5

49.6

50.4 2.6

3.8

0.8 2.8 3.3 7.9 25.7 2.2

6.4 80

345 32.5

2.0 3: 1

390 32.5

2.0 3: 1

4.0 j 9.0 n-hexane

25.4

74.6 8.1

10.7 0.3

1.8 19.1 80

43.1

51.9 10.0

14.5 0.5

6.7 25.0 80

Tabel

Catalytic activity of supports loaded with 1.0 percent by weight of Pd and subject to exchange for polyvalent cations (Mg ⁺² ) during hydrocracking

MgX

catalyst

Amorphous magnesium aluminosilicate ¹

MgY

Degree of ion exchange, ° / o
_{SiO 2} : Al ₂ O ₃ molar ratio

85
2.3

75 10

75 4.9

Process conditions:

Temperature, ⁰ C

Pressure, atü

Ha / hydrocarbon molar ratio

Room flow velocity, w / w / h ...

Application of product C ₄ ⁺ , volume percent

Sales ²

Base exchange capacity.

¹ amorphous aluminosilicate with
SiOa-AlaOa molar ratio = io.

² percent by volume

of boiling below 204 ⁰ C Product C ₄ + minus volume present in the feedstock boils below 204 ⁰ C ingredients (20%).

500

31.5 31.5 31.5

I 20

2.0 2.0 2.0

100 0.5 5

Starting material for the above experiment: heating oil no.

Boiling range: 121 to 310 ⁰ C.

Petrol content: 20 percent by volume.

Specific gravity at 15.6 ° C / 15.6 ° C: 0.843.

Reforming

The activity of the metal-loaded catalysts according to the invention for reforming can be seen from the following test results. In this reaction, a light gasoline was used as a starting material. The tests were carried out at a temperature between 450 and 500 ^° C. and a pressure of 31.5 atmospheres. The molar ratio of hydrogen to hydrocarbon in the feed was 5.

24
Table 10

Comparison of the activity of platinum loaded with 0.5 percent by weight and exchanged for polyvalent cations Aluminosilicates in catalytic reforming

Ca + ² -X

pressure

preferably

Molar ratio

Hg / hydrocarbon

preferably

Gram stake per gram

Catalyst per hour

preferably

7 to 84 atm
21 to 42 atü

1: 1 to 20: 1,
2: 1 to 5: 1

0.1 to 7,
0.5 to 3

catalyst
Type distribution
of the cations
0 /
"> Platinum-
salary
Weight
percent Octane number
at a
Fluid
product
yield of
85 volume
percent Na-Y 100Na 0.5 81.0 Mg-Y 19 Na 81 mg 0.39 88 Ca-Y 20Na 80Ca 0.43 87.5 Zn-Y 37Na 63Zn 0.48 70.5 Mn-Y 26Na 74Mn 0.47 77 Ca- ³ -Y 34Na 66Ce 0.45 77 Al-Y 32Na 68Al 0.43 79.5 Ca + ⁴ -Y 32 Na 68 Ce 0.34 85

Degree of exchange,%
SiO ₂ : Al ₂ O ₃

Liquid product
Yield,
Volume percentage

Composition,
Volume percentage

Paraffins

Olefins

Aromatics

Research octane number

without lead

85
2.3

92.6

72
0.6

catalyst

Calcium Aus-

exchanged

amorphous

Alumino

silicate ¹

Ca + ² -Y

45
5.0

89.9

74

24

57

i 89.4

According to these test results, the zeolites containing alkaline earth cations also form a gasoline higher octane number than the other zeolite catalysts containing divalent and higher valent cations. The former are therefore preferred.

The following table compares the reforming activity of various platinum-loaded aluminosilicates. Table 10 shows the improved results of the combination of metal and zeolite Y in reforming. A comparison of the results with Ca ¹² -X and with Ca ⁺² -Y reveals the importance of the SiO ₂ -Al ₂ O ₃ ratio. A comparison of the amorphous aluminosilicate with Ca ^ ² -Y makes it clear how important the crystallinity is in the context of the invention.

The reforming process using zeolite Y as a catalyst promoting the exchange against polyvalent metal cations and in the pore system 0.01 to 5.0 percent by weight contains active platinum group metal (Group VIII) is carried out under the following conditions:

55

Temperature, ⁰ C 300 to 600

preferably 400 to 525

¹ amorphous aluminosilicate with base exchange capacity; SiO ₂ : Al ₂ O ₃ = 5. The same working conditions were used for each catalyst:

Equilibrium ^{temperature, 0} C 500

Pressure, atü 31.5

Grams of use per gram of catalyst per hour 2

Molar ratio! ^ / Hydrocarbon 5

Input material light heavy petrol,

End of boiling 35O ⁰ C.
Composition:
85 percent by volume paraffins 10 percent by volume olefins
5 percent by volume aromatics

Dealkylation

In the dealkylation in the presence of hydrogen, the catalysts of the invention are the superior to known catalysts. In the catalytic dealkylation, alkyl-substituted ones are usually used Aromatics, such as toluene, are used.

According to the invention, the dealkylation is carried out under the following conditions:

Temperature 400 to 600 ° C,

preferably 450 to 550 ° C

Pressure 3.5 to 70 atm

preferably 3.5 to 35 atm

Gram stake per gram

Catalyst per hour 0.5 to 5,

preferably 0.5 to 2

Molar ratio

Ha / hydrocarbon 3 to 20,

preferably 5 to 10

A comparison of the activities of various platinum-loaded aluminosilicates in hydrodeskylation Table 11 below shows the importance of crystallinity, pore size and of the cation for the dealkylation catalyst

6o

25th

is visible. The amorphous aluminosilicate is an amorphous zeolite having an SiO ₈ -Al ₈ O ₃ ratio of 5, and zeolite T is a crystalline zeolite having a pore size such that benzene cannot be adsorbed inside. The activity of these two catalysts in dealkylation is considerably lower than that of the metal-loaded catalyst according to the invention.

Tabel

Catalytic activity of aluminosilicates containing polyvalent cations in hydrodeskylation - Comparison of different aluminosilicates and different polyvalent cations

Amorphous
Aluminosilicate Zeolite T * catalyst
Zeolite Y Zeolite Y Zeolite Y Aluminosilicate ¹
cation Ca + ²
40
3.6
95.0
0.0
1.3
Well Ca + ²
80
4.2
93.2
0.0
2.7
pretty good Ca + ²
85
22.2
63.7
11.3
2.8
Well Mn + ²
75
58.2
34.3
4.1
3.4
pretty good Al + ³
70
33.3
51.3
10.2
5.1
bad Degree of exchange
Composition of the liquid
product, mole percent
benzene toluene Xylenes Fission products
Stability of the catalyst

¹ Each catalyst contained 0.5 percent by weight of platinum, applied by ion exchange for Pt (NH ₃ ) ₄ cations and decomposition

by heat in an oxygen-containing atmosphere prior to conditioning in H ₂ prior to the reaction. ¹ Described in U.S. Patent 2,950,952.

Process conditions: Each catalyst was prepared under the same conditions with toluene as the starting material used.

Temperature 55O ⁰ C

Pressure 31.5 atm

Gram stake per gram

Catalyst per hour 1.0

Hg / hydrocarbon molar ratio.

The activity of copper-loaded aluminosilicates according to the invention can be derived from the values in can be seen in the following table:

Dealkylation of toluene with 1.0 percent by weight of Cu-containing Mg + ² -Y (continued)

³⁵ selectivity:

Benzene, mole percent

Attempt 1

Xylenes, mole percent
Non-aromatics, mole percent

Claims (3)

Claims: 68.8 4.0 27.2 Experiment 2 52.6 12.4 38.0 Feedstock inlet temperature, 0C average temperature for the experiment, 0C pressure, atmospheric / hydrocarbon space flow rate, grams per gram of catalyst per hour of running time at termination of the test, hours Test duration, rounded up to the full hour Yield of liquid Percentage by volume Percentage by weight Conversion Test toluene 550 571 31.5 10: 1 1.0 5.0 71.8 72.1 76.5 45 Test toluene 550 573 31.5 10: 1 1.0 23.0 18 55 60 74.6 72.1 63.3 1. A method for converting hydrocarbons, characterized in that the hydrocarbons in a hydrogen stream with a molecular sieve Y, based on a crystalline zeolitic metal aluminum silicate, in which at least 40% of the aluminum oxide tetrahedra are saturated by polyvalent cations, the molar ratio of SiO ₂ : Al ₂ O ₃ in the molecular sieve is greater than 3 and the molecular sieve contains at least 0.05 percent by weight of a metal of Group VIII of the Periodic Table. 2. The method according to claim 1, characterized in that the hydrocarbon at 300 to 425 ° C with a space velocity of 1 to 10 g hydrocarbon per gram Contacted catalyst per hour and a molar ratio of hydrogen to hydrocarbon from 0.5: 1 to 10: 1 is adhered to. 3. The method according to claim 1 or 2, characterized in that it is carried out at an elevated pressure of 21 to 41 atmospheres. 1 sheet of drawings 509 758/389 12.65 © Bundesdruckerei Berlin