DE2064195C3 - Process for the catalytic cracking of heavy gasoline - Google Patents

Description

keep known. In this patent specification will exist in minosilicates of the type X or Y, where

Examples 33 to 36 the catalytic activity both naturally occurring and syn-

so'.cher catalysts for the cracker, of n-decan thetic forms are used. Because of her

compared as a model substance. These comparisons show that zeolitic substances are having high activity

however, no technically feasible way of cracking 5 combines a substance whose catalytic activity

of heavy gasoline, because its individual inventory is much lower, namely with a synthetic

parts to which n-decane can belong, in terms of their table, semi-synthetic or natural silica

It is well known that there are strong differences in cracking behavior. tables matrix. For this purpose, SiO ₂ / Al, O ₃ , silica

The invention relates to the catalytic acid gel, SiO ₂ / beryllium, SiO, / magnesium.

Cracking heavy gasoline to count the octane number of the io SiO ₂ / thorium or SiO ₂ / zirconium oxide

To increase heavy fuel and substantial amounts have been used successfully in the past. in the

The compound crystalline contains lighter substances than starting materials for the general

position of petrochemical, polymerization and alky- zeolite catalysts 1 to 50 percent by weight

to win lat products. Zeolitic Krackkatal> sa- zeolite, 5 to 50 weight percent alumina, and the

gates with aluminosilicates of type X or Y have 15 and the remainder is SiO ₂ . The crystalline aluminosilicate fraction of the

Particularly useful in catalytic cracking Catalyst is a natural or synthetic,

such output currents arise. Crystalline aluminosilicate containing alkali ions

It has been found that by catalytic cracking of type X or Y, which has been pretreated in this way, of heavy boiling in the range from 37 to 232 ° C that the whole or at least a substantial portion petrol with zeolitic cracking catalysts, which are converted from 20 of the original alkali ions by other ions, Aluminosilicates of the type X or Y exist, both as z. B. hydrogen and / or a metal or a the octane number of the output stream as well as the combination of metal ions, e.g. B. Barium, wharf production substantial amounts of substances containing zium, magnesium, manganese ions or ions of the below the start of boiling of the starting heavy rare earth metals such as cerium, lanthanum, neodymium, pre-gas boil and are particularly good for making 25 odym, samarium and yttrium are replaced. The above petrochemical, Crystalline zeolites called polymerizate and alkyl products can be obtained by the are suitable, can be significantly improved. the following formula can be reproduced:

The invention relates to a method for catalyzing ". _n .. ^

table cracking of heavy gasoline, which is ^Μ Λ ^{υ: Al} * ° ^{3 : x blUi !: y} " ² ^ '

indicates that a heavy fuel in the 30 "

boils from 37 to 232 ° C, at a temperature in which M is hydrogen or a metal, η its valence-

371 to 871 ° C, with a catalyst heavy fuel, χ a value between 2 and 10 and γ a value

Ratio of 0.5 to 30 and a residence time of between 0 and 10, with γ at dehydrated

0.5 seconds to 15 minutes on a crystalline zeolite will be essentially zero. In the

Aluminum silicate of the type zeolite X or zeolite Y, 35 In accordance with the invention, the crystalline zeolites are either

which contains cations of the rare earth metals, catalytically natural or synthetic zeolites of type X

is cracked and from the cracked products products, or Y. In particularly preferred embodiments

whose boiling point is below the start of boiling of the starting point M is hydrogen, calcium, magnesium or

Heavy gasoline lies, as well as a heavy gasoline with rare earth metal ion.

higher octane number can be obtained. 40 The following working conditions are for the

The starting material for the process of invention - catalytic cracking of heavy gasoline is provided:

manure consists of heavy gasoline, which is in the range of reactor temperature from 371 to 871, preferably

Boils from 37 to 232 ° C. With the method of the invention 454 to 649 ^r C, reactor residence time of 0.5 seconds

many refinery streams can be adjusted to higher octane up to 15 minutes, preferably from 1 second to 10 minutes

set numbers. Appropriate starting materials are 45 slots, and a catalyst-oil ratio between

usually contains a lot of paraffin and contains a slight 0.5 to 30, preferably between 2 and 15.

Hydrocarbon fractions such as heavy gasoline with the use of a fluidized bed catalyst cracking plant

low octane number, Udex raffinate and heavy-duty implementation of the method of the invention and ins-

Gasoline with a low octane number, which is thermally special in a system for "riser cracking"

Cracking or hydrocracking were obtained. The 5 "are given the following additional conditions: Dwell

Difficulty, such starting heavy gasoline to time in the riser from 0.5 to 30, preferably 5 to

crack, did not expect catalytic cracking 20 seconds, residence time in the reactor bed from 0 to

in the presence of type 15 cracking catalysts, preferably from 0 to 10 minutes and one

Zeolite X or Zeolite Y to better quality this regenerator temperature of 538 to 816, preferably

Would feel currents. To the products of the invention 55 593 to 732 ⁰ C.

According to the procedure, heavy gasoline with

higher octane and hydrocarbons, which are subordinate to any of those currently in the petroleum

the beginning of the boiling point of the starting material boil and dustnc used catalyst cracking systems,

is particularly suitable as a starting material for the production of fixed bed, fluidized bed or fluidized bed catalysts

of petrochemical products, including polymer gasoline 60 sator crackers of various types

and alkylate petrol are suitable. those with whom the riser cracking

In which is used in the method according to the invention, to carry out the inventive

The catalyst is a cracking process that can be used. In case of

catalyst zeolitic type, for example in order to use a fixed bed reactor, this is in penosolche Catalysts in which the aluminosilicate is put out of operation at 65 dical intervals to avoid the

a silicate matrix is distributed. Appropriate catalyst to regenerate. With fluidized bed or

Catalysts for the process of the invention are fluidized bed catalyst systems, the catalyst is such zeolitic cracking catalysts that regenerate continuously from aluminum.

The starting heavy gasoline is fed to the catalyst reactor under the above-mentioned conditions in order to achieve the desired conversion; Bring starting material. After the heavy fuel has flowed through the reactor, the product flowing out of the reactor is fed into a conventional recovery plant which also contains a distillation ^device with which the product in heavy fuel and hydrocarbons is easier than heavy fuel, is broken down, whereby the high olefin and isobuian content of the lighter hydrocarbons specifically serve as the starting materials for alkylation «! and whose general properties make them particularly suitable as starting materials for petroleum chemistry and for polymer gasoline. In the following, using an example of the implementation of the method of the invention in FIG. ^4, its advantages over conventional and known methods are explained. All nine test runs were carried out in a Modeil test facility with fluidized r-estoeu. In this test system, between 400 and 1000 ml of heavy gasoline were applied to 400 g of catalyst, the dwell time being 15 minutes. The reactor temperature varied between 471 and 552 ° C. A heavy distillate gasoline (straight run) served as feed material in all test runs; its properties are listed in table ι.

Table I.
Analysis of the input material

description

Heavy distillate petrol (straight run)

54.5

0.011 1.5 50.3 50.6

74.8

115.6 / 120

121.1 / 123.3 125 / 126.7

129.4 / 133.8 138/142 149/153

166.5

13.6 48.2 37.8

C) Octane number with the addition of 3 ml of tetraethyl lead pm 3.785

The following catalysts were used in the comparative tests:

a) a conventional, high-alumina amorphous SiO ₂ / Al ₂ O ₃ catalyst.

b) an aluminosilicate catalyst, an acidic mordenite. In the experiments with this catalyst the acid mordcnite and the high-alumina catalyst were produced in a ratio of 50:50 and 11:89.

Density, ⁰ API

Sulfur, X-ray, in percent by weight

Bromine number

Aniline point, ⁰ C

Research octane number, of course

Research octane number,

plus 3 ml TAB ( ^l )

ASTM distillery, ⁰ C

Onset of boiling / 5%

10/20

30/40

50/60

70/80

90/95

End of boiling

FIA-MS, in percent by volume

Aromatics

Paraffins

Naphthenes

The SiO./Al ₂ Oj catalyst was used in experiments 6, while in experiments 4 and 8 a catalyst mixed _{from acidic mordenite and SiO / Al »O 3 was used.}

In the experiments with the invention. proceedings the following catalysts were used:

a) Zeolite # 1 contained about 3 percent by weight of one

ο zeolithsJvoinTypY.der in a SiOj / AljOa matrix

was distributed and contained rare earth metal cations;

No. 2 zeolite contained approximately 11 percent by weight

of a zeolite of type X, which in a SiO ₂ / Al., O ₃ -

Matrix was distributed and rare earth metal cations

contained; .

c) Zeolite No. 3 was a catalyst with a high zeolite content of about 40 percent by weight of a type X zeolite, distributed in a SiO / Al ₂ O ₃ matrix and containing rare earth metal cations. Zeolite no. 1 was used in experiments 2 and 7, zeolite no. 2 in experiments 3 and 9, and zeolite no. 3 in experiment 5.

Experiments 1 to 3 were carried out with a temperature of 5515 ° C. and a space velocity of 3.6. Experiment 1 shows the prior art, experiments 2 and 3 the method according to the invention. Experiments 4 and 5 were carried out at a temperature of 47Γ C and a space velocity of 7.2, where Experiment 4 of the prior art and test 5, the inventive method reflect Experiments 6 and 7 were with a temperature of about 479.5 ⁰ C and a space velocity of 36. Experiment 6 shows the prior art and experiment 7 shows the method according to the invention. Experiments 8 and 9 were carried out at a temperature of about 488 ° C. and a space velocity of 3.6. The former in turn represents the state of the art and the latter the method of the invention.

Each catalyst was subjected, before start of the experiment a seventeen hour activation treatment by heating at 804 ⁰ C

* c The process conditions and test results for all tests are summarized in Table II. The advantages of the method according to the invention emerge from the results of this series of tests. In all experiments with a zeolitic catalyst containing an aluminosilicate of type X or Y, the yield of C ₁ - and lighter hydrocarbons was higher than the total conversion of the substances boiling below 115.6 ° C. Furthermore, the research octane number of the heavy gasoline was significantly higher than in the comparison tests. In addition, the tests according to the method of the invention showed a high selectivity for the formation of isobutane. The heavy gasolines produced according to the process of the invention also contained 6c more aromatics and less naphthenes than the heavy gasoline obtained from the comparative tests using conventional or mordenite catalysts. In general, the test data of the tests according to the invention also showed a lower olefin content. Finally, the favorable results of the method according to the invention were also achieved within a wide temperature range.

Table II

Cracking catalyst

Approximate zcolith content in percent by weight

Reactor temperature, in ^{0 C}

Space velocity, part by weight / part by weight

Catalyst · hours

Yields, in percent by weight

coke

Propylene

Butylene

Isobutane

Conversion of C ₄ and lighter HC, into

Weight percent

Conversion O) ₁ in percent by volume

Selectivity ( ² )

37.8 / 221 'C heavy gasoline octane number, RON ( ³ ) FlA-MS, in percent by volume
37.8 / 115.6 "C heavy gasoline

Olefins

Aromatics

Paraffins

Naphthenes

115.6 / 22 Γ C heavy fuel η

Olefins

Aromatics

Paraffins

Naphthenes

SiO ₁ / Al ₂ O ₃

551.5 3.6

1.8 4.7 1.5 2.8

14.9 39.2 0.188 79.6

9.1 14.7 45.9 30.3

1.4 23.0 44.5 31.1

Zcolith No. 1

3
551.5

3.6

0.6

3.7

2.2
4.7

19.1
46.3
0.246
84.4

7.3
18.8
49.2
24.7

1.1
31.7
42.8
24.4

Attempt no.
3

Zeolite
No. 2

Mordenite H

plus
SiO ₂ ZAI ₂ O ₃ («)

11th
551.5

3.6

0.9
4.0
1.6
8.6

23.8
49.8
0.361
87.5

6.8
21.9
48.8

22.5

1.2
37.8
39.1
21.9

50
471

7.2

1.2
1.1
0.6
3.4

8.4
30.7

0.404
79.3

4.6
12.3
46.4
36.7

0.8
17.1
43.5
38.6

Table 11 (continued)

Cracking catalyst

Approximate weight percent zeolite content

Reactor temperature ^{in 0 C}

Space velocity, part by weight / part by weight

Catalyst · hours

Yields, in percent by weight

coke

Propylene

Butylene

Isobutane

Conversion of C ₄ and lighter HC, into

Weight percent

Conversion C ¹ ), in percent by volume

Selectivity ( ² )

37.8 / 221 ^ C heavy gasoline octane number RON ( ³ ) FIA-MS, in percent by volume
37.8 / 115.6 ° C heavy gasoline

Olefins

Aromatics

Paraffins

Naphthenes

115.6 / 221 ° C heavy gasoline

Olefins

Aromatics

Paraffins

Naphthenes

(·) Conversion = (100 - volume percent of the 115.6 / 221 ° C heavy gasoline yield).

(·) Selectivity = isobutene (percent by weight) butane and lighter hydrocarbons (percent by weight).

Attempt no.

Zeolite
number 1

Mordenite H

plus
SiO ₂ / Al ₂ Oa ( ⁵ )

481 3.6

3
479.5

3.6

0.6
1.6

1.1
5.3

12.4
39.2
0.426
83.3

3.6
13.0
55.4
28.0

0.5
27.4
46.1
26.0

11th
486.8

3.6

0.4
2.2
1.2
3.1

7.0
29.0

0.328
79.2

4.7
1.1.4
49.0
34.9

0.5
17.7
45.5
36.3

Zeolite No. 3

40

471

7.2

1.4 0.9 0.8 8.2

19.3 53.2 0.413 93.9

1.8 22.5 56.0 19.7

0.4 57.4 29.9 12.3

Zeolite No. 2

11 488

3.6

0.4 1.7 1.0

5.5

14.9 43.2 0.369 85.5

1.7 13.2 57.2 27.9

0.9 31.9 44.2 22.5

Research octane number, 3 ml tetraethyl lead per 3.785 liters 50:50 weight ratio. 11:89 weight ratio.

611

Claims (3)

ρ - k · hydrogen significantly lower than with conventional i-aientansprucne. functional catalytic cracking. So in future 1. Process for the catalytic cracking of the future of isobutane, propylene and butenes heavy gasoline, characterized gekennzeich- for the production of alkylates or the net mentioned that a heavy gasoline, -das in the range of 5 and other lighter hydrocarbons for the 37 to 232 ⁰ C boils, at a temperature of polymerisation and petrochemical processing steadily 371 to 871 ⁰ C, with a catalyst heavy going back. A method for increasing the octane gasoline ratio from 0.5 to 30 and a dwell number in heavy gasoline streams for use in time from 0.5 seconds to 15 minutes on a vehicle gasoline and for the simultaneous delivery of too crystalline aluminum silicate of the type zeolite X io additional amounts \ on C ₄ - and lighter carbon or zeolite Y, the cation of the rare earth metals hydrogen, is therefore very desirable. contains, is catalytically cracked and the heavy gasoline cannot be cracked as easily as cracked products like products whose boiling point is below gas oil, and until now heavy gasoline has only been catalytically cracked with limited success with the initial heavy gasoline boiling point. A conventional, as well as a heavy gasoline with a higher octane 15 Licher cracking catalyst such as SiO ₂ / Ai ₂ O ₃ showed at number to be obtained. its use to crack heavy fuel 2. The method according to claim 1, characterized in that the selectivity and activity are relatively low and that aluminosilicate catalysts lead to the formation of relatively large gas and coke walls which are in an amorphous matrix and only small amounts of the desired Al ₂ O ₃ and SiO _{2 are} distributed and hydrogen, 20 olefins and aromatics. The USA patent specification barium, calcium, magnesium or manganese 3,284,341 describes a method for containing catalytic cations. Cracking heavy gasoline with a SiO-Al ₂ O ₃ - 3. The method according to any one of claims 1 or 2, catalyst for producing substantial amounts of oil thereby characterized that it is at a tempe- fine and aromatics, where the space velocity rature from 454 to. 649 ° C, a catalyst 25 at about 4.5, the pressure between 0 and 1.41 atü and Heavy berizine ratio from 2 to 15 and with the reaction temperature between 538 and 649 ° C a residence time of 1 second to 10 minutes. is carried out. The new zeolitic cracking catalysts will be used on a large scale for cracking gas oil 30 sets, but their usability in the conversion of light heavy gasoline has yet to be concluded to be explored. From the USA patent The invention relates to catalytic cracking 3 247 098 it is found that acidic mordenite, a of heavy gasoline with a low octane number and a crystalline aluminosilicate, as a catalyst for the Boiling range between 37 and 232 ° C. 35 Conversion of light heavy fuel to still Light petrol is obtained by blending lighter components and increasing them at the same time »Naphtha sticks«, the octane number of which is often determined by the octane number of the heavy gasoline produced catalytic reforming can be increased. Both primal is extremely active. The usability of the mordenite initial As well as cracked stocks, aluminosilicate can act as a cracking catalyst for heavy reforming processes Petrol fueled with higher octane numbers was surprising in that it brought magnesium will. The catalytic reformers, faujasite catalyst will not have a satisfactory effect usually operated in such a way that the desired consumption had shown in the cracking of heavy gasoline. the Improving the octane number with the lowest possible magnesium faujasite was considered to be a highly effective cracking conversion known from light gasoline in butane and lighter catalyst for gas oil. The development Goes hand in hand with substances. 45 other catalysts used in The operation of the light gasoline blending plant ba- cracking heavy gasoline is useful and which is selective based on various processes, the feed for the production of light olefins and paraffins such as from isobutane and butenes to alkylation systems, which are also heavy fuels with higher octane numbers, Polymerization of light olefins to achieve this is therefore very desirable. high-octane mixed components, while the catalytic cracking of gas oil was known from the French patent specification of the use of heavy gas oil, a cracking process in which crystalline zeolites are used as gasoline and an additional starting catalyst, material for the alkylation - and polymerization systems which have an SiO ₂ -Al ₂ O ₃ molar ratio of 3 to 6 supplies. Although the hydrocracking adds and contains cations of the rare earth metals. As the additional amounts of heavy gasoline for the blend show 55 comparative tests of this patent specification are incurred for light gasoline, the heavy heavy gasoline obtained by hydro for cracking light gas oils only cracking the Mg and Zn salts often has one of these zeolites sufficiently active. Heavy gasoline with a relatively low octane number which can be increased by catalytic reforming as claimed for the process of the invention. Boiling ranges are in the French patent The introduction of zeolitic cracking catalysis has not been named as a suitable starting material, toren has led to significant improvements in the kata lytic cracking process. The use (col. 2, 3rd paragraph) teaches that in the frandieser highly active catalysts in existing Zeo catalyst cracking plants described in existing Zösische Patent 1,390,913 for cracking gas oil has lithe, such as Mg faujasite, for cracking such heavy loads increased throughput and improved product gasoline only low conversion rates (less than 10%). quality brought with it. Although this zeolitic also from US Pat. No. 3,210,267 was a Catalysts the accumulation of heavy gasoline of high process for cracking gas oils to zeolite quality increase is the yield of lighter carbon catalysts, the cations of the rare earth metals