DE1050477B - - Google Patents

Description

The invention relates to the catalytic reforming of petroleum hydrocarbons into products with increased octane number, which are suitable for use in motor gasoline.

In the known catalytic reforming process, gasoline fractions are processed at elevated temperatures and pressures in the presence of hydrogen treated with dehydrogenation catalysts and gasoline fractions obtained with increased octane number. Catalysts used for this purpose in the art are e.g. B. molybdenum oxide on aluminum oxide. It is also known to use petroleum straight trunks, i. H. so petroleum hydrocarbons, which have not yet been subjected to any finishing treatment, by reforming with catalysts, the oxides or sulphides of the metals of the VI. Group of the Periodic Table on a support included in to change their composition. Another widely used reforming process Catalysts, which mainly consist of platinum on aluminum oxide, optionally in combination with halogen. Catalytic reforming processes that use platinum on aluminum oxide catalysts are called platforming processes and the products are called Platformate.

The invention relates to the production of gasoline fractions with even further increased octane numbers from products of catalytic reforming processes.

According to the method according to the invention for increasing the octane number of catalytic reformates or proportions thereof, catalytic reformates or parts thereof are at temperatures in the range from 450 to 580 ° C, pressures of not more than 4.5 kg / cm ² and room flow rates of the liquid starting material of 0 , 1 to 1.0 V / V / hour brought into contact with dehydrogenation and dehydrocyclization catalysts containing essentially chromium oxide on aluminum oxide without hydrogen recycled into the reaction or added externally and optionally then combined with untreated portions of the catalytic reformates.

All of the catalytic reformate may be dehydrated or subjected to the dehydrogenative cyclization treatment will. But since the higher-boiling end fraction is relatively rich in aromatics, they are not further enriched can be used as starting material for the process according to the invention, preferably the lower-boiling, relatively aromatic-free fractions of catalytic reformates are used. These factions can be obtained by simply distilling catalytic reformates. Used preferably catalytic reformates obtained with platinum catalysts.

The dehydrogenation and dehydrocyclization catalysts consist essentially of chromium oxide

Procedure for increasing the octane number of catalytic reformates or parts thereof

Applicant:

The British Petroleum Company Limited, London

Representative:

Dr.-Ing. A. ν. Kreisler, Dr.-Ing. K. Schönwald, Dipl.-Chem. Dr. phil. H. Siebeneicher and Dr.-Ing. Th. Meyer, patent attorneys, Cologne 1, Deichmannhaus

Claimed priority: Great Britain April 16 and December 7, 1956

John Arthur Edgar Moy and Peter Duncan Bond, Sunbury-on-Thames, Middlesex (Great Britain), have been named as inventors

Aluminum oxide carriers. Activating agents, e.g. B. small amounts of alkali metals, especially potassium and / or rare earths, especially cerium or compounds of these elements, e.g. B. Oxyde, before. The relative ratio of the constituents, based on the total catalyst stable at 550 ° C, corresponds e.g. B.

Chromium oxide 5 to 25 percent by weight

Alkali metal (as oxide) .. 0.1 to 5 percent by weight Rare earths (as oxide) 0.1 to 5 percent by weight Alumina remainder

The expression »at pressures not exceeding 4.5 kg / cm ² * includes normal pressure and pressures below. It is preferred to work at essentially normal pressure.

The other important variable process conditions, such as temperature and space velocity, can depending on the desired increase in octane number and the octane number of the starting material within of the specified range. at

809 7W351

higher temperatures, the octane number of the product is increased, but the yield is reduced, while a Decreasing the space velocity increases the octane number for a given yield. Within In the temperature range from 450 to 580 ° C, temperatures around 525 ° C are preferred.

The process according to the invention can be carried out with fixed bed, fluidized bed or fluidized bed catalysts will. The process is particularly suitable for working with fluidized bed catalysts. The catalysts from chromium oxide on aluminum oxide carriers can easily be regenerated in the usual process.

In the process according to the invention, large amounts of hydrogen-rich gases fall as a valuable by-product at. If the starting material is low-boiling, relatively aromatic-free fractions of catalytic Reformats are used, one obtains gasoline mixtures with a high octane number and great volatility. The reformed product can optionally with the higher-boiling fraction of the catalytic reformate be mixed to a mixture with a higher octane number than the original reformate. When using the Process according to the invention on reformates obtained with platinum catalysts can use these mixtures be less volatile than the original disk format. In this case, the volatility may vary according to Procedure to be increased. For example, the starting material for the dehydrogenation or dehydrocyclization process Contain fractions whose boiling points are below the initial boiling point of the starting material for the platforming process, thereby reducing the proportion of low-boiling components in the product of the dehydration and dehydrocyclization is increased. Optionally, the Reformed lower-boiling fractions and the higher-boiling fractions of the platform in the required Proportions are mixed to have sufficient volatility and the octane number of the mixtures can be maintained by the addition of tetraethyl lead. Finally, the final boiling point of the low-boiling fraction are adjusted so that no toluene-forming constituents are present.

example 1

^y

A platform is separated into light and heavy components and the lighter component with a final boiling point of 108 ° C with a chromium oxide on aluminum oxide catalyst for those listed in Table 1 Conditions brought into contact.

Table 1

Procedural conditions

Catalyst IO ⁰ Zo Cr ₂ O ₃ on aluminum

nium oxide + 1% K ₂ O + 1 o / o Ce ₂ O ₃

Pressure atmospheres

Temperature 530 ° C

Room flow rate 0.2V / V / hour.

Recirculated gas -

Duration of the procedure 5 hours

yield

Stabilized product 68.6 percent by weight _fi

Gas 273 m ³ / m ³

Hydrogen content 85.7%

The characteristic values for starting material and product are given in Table 2 below.

Table 2

Source material Low
boiling Reformed
low- Platform format C1 H iiTl f \ ac
OLC KXKjLLKdtSs
Platform format Specific weight at 15 ° / 15 ° 0.6900 0.7748 A ^ TM distillation l ° C \ 34 40.0 2 ° / ₀ recovered at 41 50.0 5 ° / o recovered at 45 53.0 10 ° / o recovered at 49 57 ^ 0 20% recovered at 54 65.0 30 ° / o recovered at 59 75.0 40 ° / ₀ recovered at 65 84.0 50 ° / o recovered at 72 93.0 60 ° / o recovered at 79 100.5 70 ° / o recovered at 87 106.0 80 ° / ₀ recovered at 92.5 110.0 90 ° / ₀ recovered at 100 115.0 Final boiling point 108 126.0 Total distillate (volume 97 95.0 XvCll ^ lvo LCH IV_l IV »Ji Ulli LtL KJ £ j \ ^ LL L i · · 1 4.0 O
Δ Evaporates at 70 ° C (volume 47 25.0 Evaporates at 100 ⁰ C (volume 90 59.5 3.1 47.5 Hydrocarbon analysis Aromatics (volume percentage) 14.5 55.5 Olefins (volume percentage) .... 17.5 27.0 Research octane number 76.1 101.2

Example 2

A low-boiling platform fraction with a boiling range of 42 to 110 ° C (ASTM) is used with a fluidized bed catalyst from 10% chromium oxide on aluminum oxide, which is activated by 1% calcium oxide and 1% cerium oxide, brought into contact. It will be three Tests carried out at different temperatures, the results of which are given in the table below are.

Table 3

temperature
⁰ C Space-
fluidic
swiftly
speed
V / V / h catalyst
dwell time
hours Butai
and des
Per
Research
octane
number
(without
Additive) ifreies
tilled
duct
yield
Weight
percent 492
521
549 0.20
0.21
0.19 10.0
9.5
10.5 91.2
95.2
98.1 83.6
75.0
63.3

The three products obtained are converted into motor gasoline with a high-boiling plateau fraction a research octane number + 1.5 ecm tetraethyl lead = 4.551 of at least 100 mixed. As a high boiling point Platformat fraction was after distilling off the

above-mentioned low-boiling platform fraction obtained residue is used.

Specific gravity at 15 ° / 15 °

distillation

Initial boiling point ( ⁰ C)

2 ° I ₀ recovered at

5 ° / ₀ recovered at ....

IO ⁰ Z ₀ recovered at ....

20% recovered at ....

30 ° / o recovered at

40% recovered at ....

50% recovered at ....

60% recovered at

70 ° / ₀ recovered at ....

80 ° /, recovered at

90% recovered at ....

Final boiling point

Recovery (%)

Residue (%)

Loss (%)

Recovered at

70 ° C (%)

100 ° C (%)

HO ⁰ C (o / ₉ )

Research octane number (without addition)

The proportions in which the three products are mixed with the high-boiling platform, as well as the

The analysis values of the three products and the heavy platform content are given in the following table.

Table 4

attempt j /, ο weight- percent residue Reformed low boiling point from a Platform share Platform format Attempt 1 Attempt 2
Attempt 3 the octane number 93 U, / ώΟΟ U, / OtU 0.8540 45 47 46.5 125 50 51 51 129 53 ro c
53.5 54 132.5 54.5 56 56 134 57.5 59 59.5 137 62 63.5 64.5 140 67.5 68.5 70.5 144 73.5 75.5 78 148.5 80 83.5 87 1 5λ 87 91.5 96 158.5 96 100.5 103.5 165 105 108 110 174 115 124.5 124.5 214 98 97 97.5 98.5 1 1.2 1.2 1.4 1 1.8 1.3 0.1 43.5 42.5 39 85 79.5 75 30th 91.2 95.2 98.1 IC ₈ + 0.30 ecm Tetraethyl lead / 4.55 1 (103.5)

Analysis values of the motor gasolines obtained are contained in the table below.

Table 5

Composition of the mixture Volume percentage of product of product of product with OZ 91.2 with OZ 95.2 with OZ 98.1 60 65 70 Residue of a platform with an octane rating of 93 40 35 30th 0.7775 0.7810 0.7850 Distillation test 51 46 44 56 52 49 59 58 54 65 65 58 20% recovered at 73 72.5 66 30% recovered at 86 81 75 40% recovered at 94 92 86.5 108 106 99 122 116 111 134 128 121.5 80% recovered at 146 141 133.5 161.5 159 153 201 197 190 98.5 98.5 98.5 Residue (%) 1.0 1.0 1.0 Loss (%) 0.5 0.5 0.5

Table 5 continued

Composition of the mixture by volume

of product
with OZ 91.2 from. !Product
with OZ 95.2 VUU JT1 UU. Ll it L
with OZ 98.1 15.5 16.5 24.5 44 * 5 46 51.5 74.5 79 84 0.002 0.006 0.001 22nd 27 30.5 48.5 50 48.5 85.7 86.6 87.1 90.0 90.4 90.5 97.4 98.9 99.5 IC ₈ + 0.07 ecm IC ₈ + 0.16 ecm ICg + 0.23 ecm Tetraethyl lead / Tetraethyl lead / Tetraethyl lead / 3.785 1 (100.9) 3.785 1 (102.0) 3.785 1 (102.8)

Recovered at

70 ° C (%)

100 ° C (%)

140 ° C (%)

Total sulfur content (percent by weight)

Bromine number

Aromatics (volume percentage) Octane engine method, without addition Octane engine method, +1.5 cc tetraethyl lead / 4.551 Research octane number (without addition) Research octane number +1.5 ecm tetraethyl lead / 4.551 Example 3

The entire platform from a gasoline fraction with a boiling range of 92 to 177 ° C is with a Chromium oxide catalyst treated on aluminum oxide under the conditions given in the table below.

Table 6

Procedural conditions catalyst

10% Cr ₂ O ₃ on aluminum oxide + 1% K ₂ O + 1% Ce ₂ O ₃

Temperature 525 ° C

Room flow rate 0.2V / V / hour.

Recirculated gas - Duration of the procedure 5 hours

yield

Stabilized product ... 70 ° / ₀

Gas 272 m ³ / m ³

Hydrogen content 79%

The analysis values for the starting material and product are contained in Table 7 below.

Tabel

Source material Source platform format Reformed platform format

Specific gravity at 15.5 ° / 15.5 ° ASTM distillation Initial boiling point ( ⁰ C)

2% recovered at

5% recovered at

10 ° / ₀ recovered at

20 ° / ₀ recovered at

30% recovered at

40% recovered at

50% recovered at

60% recovered at

70% recovered at

80% recovered at

90% recovered at

Final boiling point Distillate (volume percentage) Residue (volume percent) Loss (volume percentage) Vaporizes at

70 ° C (volume percentage)

100 ° C (volume percentage)

140 ° C (volume percentage)

Total sulfur content (percent by weight)

Bromine number

Hydrocarbon analysis Aromatics (volume percentage) Olefins (volume percentage) Saturated hydrocarbons (volume percentage) Research octane number (without addition)

0.7450

44

62

72.5

83.5

97.5 107.5 115 122 128 135.5 144 157.5 184

98 0.8 1.2

4.5 22.5 76.5

0.0004 1.7

30.5 1

68.5 73.9

0.8270

60

68

77

85

95 104 111 117 120 123 126 136 155

98 1.5 0.5

3.5 25.5

15.4

76.5 5.5 18

101.3

Example 4

A high-boiling platform is treated under the process conditions of Example 3 and 81%

of a stabilized product and 157 m ³ / m ³ gas with a hydrogen content of 79%.

The analysis values for the starting material and product are contained in Table 8 below.

Tabel

material High boiling platform Reformed high boiling point Source material Platform format 0.8450 0.8740 ASTM distillation 114 90 10T
IUu 114 128 p 121 20% recovered at L <J £ i 12Q 40% recovered at Π9 X OO 60% recovered at 149 139 155 146 80% recovered at 162 153 90 ° / »znriickp won at 171.5 161 213 180 99 99 "Riir ^t IfiitaηH fVoliiTnTvrozPTit ^ 1 1 0 0 Vaporizes at 70 ° C (volume percentage) 0 IOO ⁰ C (volume percent) 0 140 ° C (volume percentage) 43 62 7.1 Hydrocarbon analysis Aromatics (volume percentage) 82.5 99.5 0 Saturated hydrocarbons (volume percentage) 17.5 0.5 102.3 111.3

As can be seen from the table, the percentage of aromatics was 99.5% and also the percentage of at 140 ° C evaporated substances increased.

Example 5

A number of experiments are carried out on a lightweight platform starting material to determine the effect the reaction pressure and the effect of the presence of added hydrogen on the reforming reaction to determine.

A fixed bed catalyst is used under the following process conditions:

Temperature 550 ° C

Room flow velocity 0.2 V / V / hour.

Duration of the procedure 20 hours

Catalyst 10% chromium oxide

on aluminum oxy d + 1% K ₂ O
+ 1% Ce ₂ O ₃

Starting material low boiling point

Platform format

Research octane number (without addition)
of starting material 76.1

Four attempts are made. The pressures used, the amount of hydrogen added and the results are contained in the table below.

Tabel

Trial no. 1 2 3 4th 0 4.5 0 4.5 Hydrogen feed rate (m ^s / m ³ ) 0 0 714 714 Carbon content of the spent catalyst (Ge 0.6 weight percentage of the starting material) 4.4 6.7 0.8 208 191 204 129 Hydrogen content of the outlet gas (volume percentage) ... 67 32 74 16

809 749/351

11 12

Continuation table

Trial no. 1 2 3 4th Butane-free, liquid product Total yield in percent by weight of the starting material 70 51 66 59 Research octane number (without addition) 1f) 1 Q 102.0 100.4 Ql Λ IUI, / 101.1 100.0 yo, D bi <? 3 hours of the ** trial 101.3 101.3 97.4 95.4 99.6 102.4 97.6 95.0 98.0 102.9 97.3 96.4 93.8 100.8 97.1 95.1 99.0 95.6 94.5 10 to 15 hours of trial 89.3 96.0 94.8 96.2 15 to 20 hours of trial 91.4 94.6 93.8

The results show that the greatest yield is obtained at atmospheric pressure with no additional hydrogen will. If the pressure is increased or hydrogen is added, or both, the yield is reduced. the Effect on octane number is more intricate. With increased pressure and the addition of hydrogen, the starting octane number falls in comparison to experiment 1 significantly; reduced when hydrogen is added at atmospheric pressure the starting octane number increases by 1.5. The starting octane numbers for Trials 1 and 2 are similar, but how already mentioned, the yield in experiment 2 is significantly lower than in experiment 1.

In all experiments, with the exception of experiment 4, the octane number drops in the course of the process. The speed however, the amount of waste does not appear to be solely a function of the amount of carbon on the catalyst.

Example 6

The starting material of Example 1 is used in a series of experiments under the process conditions of Example 1, except that a different alkali metal activator is used for the catalyst and each catalyst was tested at two different reaction temperatures. The results are included in Table 10 below.

Tabel

catalyst Butane-free product Exit gas Activator Research octane number
(without addition) Weight percent,
based on
Source material yield in m ³ / m ^: ' H ₂ content
Volume percentage at 475 ° C at 530 ° C at 475 ° C at 530 ° C at 475 ° C at 530 ° C at 475 ° C at 530 ° C Ce ₂ O ₃ , K ₂ O
Ce ₂ O ₃ , Li ₂ O
Ce ₂ O ₃ , Na ₂ O
Ce ₂ O ₃ , Cs ₂ O 89.1
89.4
85.2
88.9 100.7
99.3
98.0
99.5 85.8
81.2
89.5
87.4 66.9
68.0
72.7
68.9 117
109
89
108 270
264
262
258 82.9
80.5
75.6
80.4 81.6
77.6
83.5
78.5

Activator concentration: 1 percent by weight.

Example 7

In this example, (a) reforming the entire platform with (b) mixing a reformed compared low-boiling with the associated high-boiling platformer portion.

The total product from the platforming process is broken down as follows:

Entire platform

ASTM boiling range 38 to 200 ° C

Research octane number (without addition) 92.8

High-boiling platform content

Yield based on
total platform 51.8 percent by weight

ASTM boiling range 128 to 216 ° C

Research octane number (without addition) 104.6

Low-boiling platform content

Yield based on

total platform 48.2 percent by weight

ASTM boiling range 34 to 108 ° C

Research octane number (without addition) 76.1

When processing the overall platform and the low-boiling platform portion, each of them is similar Process conditions the results contained in Table 11 below are obtained.

13 14

Tabel

Process conditions common to both experiments:

Pressure atmospheric pressure

Duration of the procedure 5 hours

Room flow velocity 0.2 V / V / hour.

Catalyst 10% chromium oxide

on alumina, activated with 1% K ₂ O and l ° / ₀ Ce ₂ O ₃

Source material Total plate format Low boilers
Platform share Yield of butane-free product (percent by weight) ...
Yield of butane-free product based on the 550
70
103.6
70 475
86
100.4
86 531
62
102.2
29.9 474
83
94.0
40.0

The conditions were selected so that the mixture obtained as the end product of the high-boiling and the reformed, low-boiling platform has the same octane rating as the reformed overall platform Has.

The mixing proportions for the high and low boiling platform portions are in the following Table included.

Table 12

Yield, based on the total plate format (percent by weight)

Yield of the high-boiling platform portion (percent by weight)

Total yield, based on total platform format (percent by weight)

Concentration of the low-boiling platform component in the mixture (percent by weight)

Calculated research octane number of the mixture (without addition)

531

29.9
51.8
81.7

36.6
103.7

474

40.0 51.8 91.8

43.5 99.6 obtained while reforming the low boiling platform portion and mixing with the high boiling Proportion of a product with a research octane number of 99.6 (without addition) in a yield of 92 percent by weight is obtained.

35

Reforming temperature of the low-boiling platform portion in ⁰ C

45

50

55

The comparison of the yields and octane numbers obtained in each experiment shows:

1. If the process conditions are severe, a product is included when reforming the entire platform obtained a research octane number (without addition) of 103.6 in a yield of 70 percent by weight, while when reforming the low-boiling platform portion and mixing with the high-boiling portion, the yield 82 percent by weight of a product with a research octane number (without additive) of 103.7.

2. If the process conditions are less severe, reforming the entire platform will result in a product with a research octane number of 100.4 (without addition)

Patent claims:

1. A method for increasing the octane number of catalytic reformates or portions thereof, characterized in that catalytic reformates or parts thereof at temperatures in the range from 450 to 580 ° C, pressures of not more than 4.5 kg / cm ² and space flow rates of the liquid Starting material from 0.1 to 1.0 V / V / hr. without hydrogen recirculated to the reaction or added externally, are brought into contact with dehydrogenation and dehydiocyclization catalysts containing essentially chromium oxide on aluminum oxide and optionally then combined with untreated portions of the catalytic reformates.

2. The method according to claim 1, characterized in that catalysts with 5 to 25 percent by weight of chromium oxide, based on the total weight of the catalyst, are used.

3. The method according to claims 1 and 2, characterized in that a lower boiling, relatively aromatic-free fraction of a catalytic reformate is used.

4. Process according to claims 1 to 3, characterized in that catalysts having a low content, preferably from 0.1 to 5%, of compounds of rare earths, in particular cerium, and a low content, preferably 0.1 to 5 ° / ₀ , an alkali metal compound, especially potassium, can be used.

5. Process according to Claims 1 to 4, characterized in that the treatment in the fluidized bed process is carried out.

6. The method according to claims 1 to 5, characterized in that Platformate or parts thereof be used.

Claims (1)

7. Process according to Claims 1 to 6, characterized in that a low-boiling fraction a Platformates subjected to the treatment and then with a higher-boiling fraction of the Platformates being mixed up. 8. The method according to claims 1 to 7, characterized in that the platform or its proportions Material is added that is below the Boiling initial boiling point of the starting material for the Platformienmgsverfahren. Documents considered: French Patent Nos. 833 971, 862 421; U.S. Patent No. 2,198,545; Industrial Engineering Chemistry, 47, pp. 731-735. @ 809 749/351 2.59