DE1102945B - Process for the treatment of catalytic reformates - Google Patents

Description

GERMAN

The invention relates to the treatment of at products obtained from catalytic reforming, hereinafter referred to as catalytic reformates will.

In catalytic reforming processes, a gasoline fraction is at elevated temperature and elevated Pressure brought into contact with a dehydrogenating catalyst in the presence of hydrogen, wherein a gasoline fraction with increased octane number is obtained. Molybdenum oxide is used as a catalyst on an industrial scale on aluminum oxide and catalysts, which essentially consist of platinum and optionally bound Halogen on aluminum oxide as a carrier is used. Using catalytic reforming processes a platinum catalyst on aluminum oxide as a support are hereinafter referred to as "platforming" and the Products referred to as »Platformate«.

By platforming products with research octane numbers from 90 to 100 (without lead) can be obtained, however, the procedure is subject to certain restrictions. First and foremost it is above a certain octane number an increase in the octane number can only be achieved at the expense of reduced volatility. This is undesirable because at the moment value is placed on petrol, which has both a high octane number and a high volatility. Adjusting the boiling range of the feed can improve the volatility of the product however, the treatment of lower boiling feedstocks requires harsh processing conditions and results in lower yields. Secondly there is a practical upper limit for the octane number, regardless of the volatility.

It has already been proposed to divide a catalytic reformate into a higher-boiling and a lower-boiling one Separate fraction and then separate both fractions to a thermal reforming subject. If these two products are then combined again, a mixture with an increased octane number should be obtained compared to the original reformate. This prior art method does not increase the volatility of the catalytic reformate, as is possible by the process according to the invention.

According to the invention, a catalytic reformate is divided into a higher-boiling and a lower-boiling fraction decomposed, at least the higher-boiling fraction at a temperature of 450 to 580 ° C with a dehydration and Contacted dehydrocyclization catalyst to form a product with increased volatility and the treated higher boiling fraction either with the untreated lower boiling fraction or with that by treating the lower boiling fraction at elevated temperatures in the presence of dehydration and Dehydrocyclisierungskatalysatoren accumulating product of increased octane number reunited.

Method of treatment
of catalytic reformates

Applicant:

The British Petroleum Company Limited, London

Representative: Dr.-Ing. A. v. Kreisler, patent attorney,
Cologne 1, Deichmannhaus

Claimed priority:
Great Britain 23 May 1958

John Arthur Edgar Moy
and Peter Thomas White,

Sunbury-on-Thames, Middlesex (Great Britain),
have been named as inventors

The higher-boiling fraction of a catalytic reformate is relatively rich in aromatics and as such is not a suitable material for further improvement by dehydration and dehydrocyclization. However, such treatment results in a product with increased volatility. The octane number can also be increased further. When this treated higher boiling fraction is combined again with the untreated lower boiling fraction, an end product is obtained which has an increased volatility and usually also an increased octane number. The product and preferably has a research octane number (unleaded) of at least 90 such volatility that the ⁰ to 100 C boiling fraction is at least 40 ° / ₀ and especially 40 to 60%.

The product can be used as a component of motor gasoline, but the process is suitable especially for the direct production of motor gasoline with high octane number and high volatility, which do not require the addition of further mixing components.

In a further special embodiment of the method according to the invention, both the higher-boiling as well as the lower-boiling fraction separated with a dehydrogenation and dehydrocyclization catalyst brought into contact and the factions reunited. The mixture obtained preferably has a research octane number of at least 100 (unleaded). It was found that way higher octane at a given reaction temperature

109 537/496

numbers are achievable as if the catalytic ^ reformate is subjected to a single treatment in total. Furthermore, although the treatment of the lower boiling point Fraction lowered their volatility, but this is at least partially due to the increase in the S Volatility of the higher-boiling fraction treated is balanced, and given the volatility is one higher octane number or with a given octane number a higher volatility achievable than if the whole catalytic reformate is treated.

The preferred catalysts used for the treatment of both the higher-boiling and the lower-boiling fraction consist essentially of chromium oxide on aluminum oxide as the carrier. The dehydrogenation and dehydrocyclization catalyst is \ ^r orzugsweise at a pressure up to 4.5 kg / cm ² (including atmospheric pressure or less) without circulating the hydrogen-rich gas or additive formed of any foreign hydrogen-rich gas or inserted foreign hydrogen. The space velocity of the liquid feed can be between 0.1 and 1.0 V / V / hour. lie. The chromium oxide on aluminum oxide catalyst may contain a small amount of one or more activators, e.g. B. a rare earth or a mixture of rare earths, bismuth, boron, germanium, nickel, manganese, iron or beryllium, preferably in combination with an alkali metal, e.g. B. Potassium. A small proportion of a spinel, e.g. B. cobalt chromite, copper chromite, zinc titanate or iron chromite either as such or in the form of the naturally occurring chrome iron stone.

The proportions of the catalyst constituents, based on the weight of the ^{total catalyst stable at 550 °} C., are preferably within the following ranges:

Chromium oxide 5 to 25 percent by weight

Total activators (with
Metals expressed as oxide) 0.1 to 10 percent by weight,

but less than the amount of chromium oxide

Alumina remainder

40

45

The dehydrogenation and dehydrocyclization can be carried out using the catalyst as a fixed bed, moving bed or fluidized bed. In the case of the catalyst which is preferably used, which is slightly after the conventional methods can be regenerated, the fluidized bed is preferred. The preferred feed material is a platform is used.

The platform is preferably produced by a platforming process, a heavy gasoline being used as the feedstock and the operating conditions being such that the catalyst does not need to be regenerated in situ (ie the catalyst ^{life corresponds to at least processing of 14 m 3 of} feed per kilogram of catalyst).

By "heavy naphtha", a gasoline with a final boiling point according to ASTM between 150 and 200 ⁰ C and is preferably to be understood a Siedeanfang according to ASTM in the range of 70 to 100 ⁰ C.

The platforming stage is preferably operated so that a reformate with a research octane number from 90 to 100 (excluding lead) is obtained. Any suitable platforming technique can be used. Working conditions are usually within the following ranges:

Catalyst 0.1 to 10 weight percent

Platinum on aluminum oxide, optionally with 0.1 to 8 percent by weight halogen, especially fluorine and / or chlorine

Temperature 315 to 650 ° C, preferably

482 to 538 ° C

Pressure 4.5 to 71 kg / cm ² , preferably 22 to 50 kg / cm ²

Space velocity .. 0.5 to 10 V / V / hour, preferably 1 to 3 V / V / hour.

Molar ratio

H ₂ : hydrocarbon 0.5 to 15, preferably 6 to 10

The platform is to be fractionated so that the higher-boiling fraction contains most of the alkyl aromatics in the reformate. To this end, the intersection point is preferably suitably set in the range between 80 and 130 ⁰ C, in the range between 100 and 12O ⁰ C. The separation can be done by simple distillation.

example 1

A gasoline obtained from Middle Eastern crude oil with a boiling range according to ASTM of 90 to 171 ° C was reformed with a catalyst on aluminum oxide containing 0.7 weight percent platinum, 0.45 weight percent fluorine and 0.34 weight percent chlorine as a carrier under such conditions that A Research Octane Rating of 93 was achieved. The reforming conditions were as follows: 496 ° C., 36 kg / cm ² , 1.0 V / V / hour, molar ratio of hydrogen to hydrocarbon = 10: 1. The platformate thus obtained was (unleaded) by fractionation at 100 ⁰ C in a lower boiling fraction having an ASTM boiling range of 43 to 97.5 ° C and a research octane number of 69.2 and a higher boiling fraction with a Siedeanfang of 115 ⁰ C and a research octane number of 101.9 (unleaded). The lower-boiling fraction made up 34.4 percent by weight and the higher-boiling fraction made up 65.6 percent by weight of the platformate.

The higher-boiling fraction was over a catalyst arranged as a fixed bed, which consists of 10 percent by weight Chromium oxide consisted of aluminum oxide and 1 percent by weight of cerium oxide and 1 percent by weight as activators Potassium oxide, treated under the following conditions:

Pressure atmospheric pressure

Space velocity 0.2 V / V / hour

Cycle gas -

Processing time 5 hours

The results of the tests carried out at two different temperatures are shown in Table 1 specified.

Table 1

Yield based on
Use, weight percent

Specific weight at
15.6 ° C

Part boiling up to 14O ⁰ C,
Volume percentage

Research octane number
(without lead)

mission

100
0.8405

48
101.9

Reaction temperature

500 ⁰ C j 55 ^{0 0} C

87.9

0.8700

47.5

75.2

0.8732

51.7

108.4 108.4

1 1Ü2

The treated higher boiling fractions were combined again with the lower boiling fraction. The mixtures had the properties given in Table 2.

Table 2

U.N- Heaviness Heaviness treated Fraction, Fraction, Reformate at 500 ° C at 550 ^° C be be acts acts Yield based on Total format, 100 Weight percent .... 92.0 83.7 Boiling up to 100 ^° C 34.5 Share, volume percentage 40.0 43.5 Research octane number 93.0 (unleaded) 95.9 95.8

From the table it can be seen that both the volatility and the octane number of the end product compared the original platform format.

Example 2

Gasoline obtained from Middle Eastern crude and having an ASTM boiling range of 100-175 ° C was reformed with a catalyst containing platinum, alumina and bound halogen under "conditions such that the product had a research octane number of 92.8 (unleaded) The reforming conditions were as follows: 504 ° C., 32.5 kg / cm ² , 1.8 V / V / h, hydrogen-hydrocarbon molar ratio = 9: 1. The platform was converted into a lower boiling point by fractionation at 115 ° C Fraction with an ASTM boiling range of 34 to 108 ° C and a research octane number of 76.1 (unleaded) and a higher boiling fraction with an ASTM boiling range of 128 to 216 ° C and a research octane number of 104.6 (unleaded The lower-boiling fraction made up 41.2 percent by weight and the higher-boiling fraction made up 58.8 percent by weight of the platformate.

The higher-boiling fraction was under the same conditions and with the same catalyst as in Example 1 treated. The results of the tests carried out at four different temperatures are listed in Table 3.

Tabel

Insert 475 ⁰ C

Reaction temperature
500 ° C! 525 ° C

550 ° C

Yield based on input, percent by weight

Specific weight at 15.6 ° C

Part boiling up to 140 ° C, percentage by volume

Research octane number (without lead)

0.8565
20.0
104.6

86.0
0.8700
33.0
111.0

84.0
0.8730
34.0
112.2

79.0
0.8755
33.0
112.2

77.0
0.8765 57.0
112.8

The treated higher boiling fractions were combined again with the lower boiling fraction. The mixtures, in turn, had increased volatility and a higher octane number. The values are in Table 4 listed.

Tabel

treated platform Treatment temperature of the heavy fraction
475 ° C 1,500 ° CI 525 ° C '550 ° C

Yield, based on total platform format,

Weight percent

Part boiling up to 100 ° C, percentage by volume
Research octane number (without lead)

93.2
51.8
95.5

92.1
52.4
96.3

90.0
53.8
95.8

89.0
54.5
95.9

Example 3

Comparative experiments were carried out in which the entire platform mentioned in Example 2 and the The higher-boiling fraction and the lower-boiling fraction (also in the experiments described in Example 2) obtained) under the same conditions and with the same catalyst as in Example 1 were treated. The higher boiling and lower boiling fractions were after treatment put back together. The reaction temperatures used and the results obtained are in Table 5 listed.

Tabel

Use 475 ° C

Reaction temperature
500 ° C! 525 ° C

550 ⁰ C

Treatment of the entire platform
Yield based on input, percent by weight ..

Part boiling up to 100 ° C, percentage by volume

Research octane number (unleaded)

100 39.5 92.8 86
32.5
100.4

83
33.5
102.3

79

27

103.5

Table 5 (Continuation) 475 ° C Reaction temperature 525 ° C 550 ⁰ C mission 500 ° C Treatment of the lower-boiling fraction (speci fish weight 0.69) Yield 53.6 percent by volume = 41.2 percent by weight, 83.1 61.5 57.0 based on total reformate 74 72.6 62.0 59.0 Yield based on input, percent by weight .. 0.7360 67.2 0.7900 0.7970 Part boiling up to 100 ° C, percentage by volume 94.3 0.7610 102.1 103.0 Specific weight at 15 6 ° C 99.0 Research octane number (without lead) Treatment of the higher boiling fraction (specific Weight 0.8565) Yield 46.5 percent by volume = 58.8 percent by weight, 86 79 77 based on total reformate 0.8700 84 0.8755 0.8765 Yield based on input, percent by weight .. 111.0 0.8730 112.2 112.8 Specific weight at 15 6 ° C 112.2 Research octane number (without lead) Mixture of the treated higher and lower boiling fractions Mixed in educational ratio, based on total reformat 84.6 70.5 67.4 Yield, based on total reformate, 38.1 78.5 27.6 25.4 Weight percent 101.8 32.2 107.7 108.6 Part boiling up to 100 ° C, percentage by volume 105.8 Research octane number (without lead)

From the table it can be seen that at a reaction temperature of 475 ° C, the mixed product is a little has a higher octane number and a considerably higher volatility than the overall reformate treated. With the higher ones At reaction temperatures, the two products have the same volatility, but the mixed product has one significantly higher octane number.

Claims (8)

Claims: 40 1. A method for increasing the volatility of catalytic reformates or increasing the octane number for a given volatility by treating fractions of these reformates at elevated temperatures, characterized in that the reformate is separated into a higher-boiling and a lower-boiling fraction and the higher-boiling fraction at temperatures in the range from 450 to 580 "'C in the presence of dehydrogenation and dehydrocyclization catalysts converted to a product of increased volatility and then either with the untreated lower-boiling fraction or with that obtained by treating the lower-boiling fraction also at temperatures in the range from 450 to 580 ° C in the presence of Dehydration and dehydrocyclization catalysts obtained product of increased octane number is mixed. 2. The method according to claim 1, characterized in that a volatility of at least 40 percent by volume, preferably 40 to 60 percent by volume, at 100 ° C. and a research octane number (unleaded) of at least 90 ° C in the recombined mixture of treated higher boiling point Fraction and untreated lower boiling fraction is worked. 3. The method according to claim 1, characterized in that a research octane number of at least 100 (unleaded) in the recombined mixture of treated higher boiling and treated lower boiling fraction is worked. 4. The method according to claims 1 to 3, characterized in that with substantially chromium oxide on a support of alumina-containing dehydrogenation and dehydrocyclization catalysts is being worked on. 5. The method according to claim 4, characterized in that with 5 to 25 weight percent chromium oxide and preferably 0.1 to 10 weight percent but less than the weight of the chromium oxide of one or more catalysts containing activators is used. 6. The method according to claims 1 to 5, characterized in that in the catalytic treatment stage with pressures up to 4.5 kg / cm ² and without recirculation of hydrogen-rich gas or addition of extraneous hydrogen and with room flow rates of in particular 0.1 to 1, 0 V / V / h is being worked on. 7. The method according to claims 1 to 6, characterized in that with Platformaten as an insert work is being carried out, which is particularly important in the platforming of heavy gasoline under conditions which make a regeneration of the catalyst in situ unnecessary, are incurred and preferably one Have research octane number (unleaded) from 90 to 100. 8. The method according to claims 1 to 7, characterized in that the catalytic reformate in the higher and lower boiling fraction with an intersection point in the range from 80 to 130 ° C, preferably 100 to 120 ° C, is separated. Considered publications:
German interpretative document No. 1026 461. Legacy Patents Considered:
German Patent No. 1060 076. © 109 537/496 3.61