DE1275235B - Process for the production of middle distillates by the hydrogenative cleavage of hydrocarbon oils - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Clog

German class: 23 b -1/04

Number: 1 275 235

File number: P 12 75 235.1-44 (S 103 132)

Filing date: April 12, 1966

Opening day: August 14, 1968

The invention relates to a process for the production of middle oil distillates by hydrogenative cleavage of hydrocarbon oils at a temperature of 370 to 430 ⁰ C and a hydrogen partial pressure of 75 to 150 atmospheres and in the presence of a tungsten, nickel and fluorine-containing catalyst which contains aluminum oxide in the support material.

A number of processes are known in which hydrocarbon oils are decomposed by hydrogenation converted to hydrocarbons of lower molecular weight or lower boiling point will. Usually the goal is to use gasoline or middle distillates, such as luminous oils and To produce gas oils that are more valuable than the starting material, ζ. B. higher boiling hydrocarbon oil distillates and residual hydrocarbon oil fractions.

The hydrogenative cleavage takes place at relatively high temperatures under hydrogen pressure and in the presence carried out a catalyst, which exerts both a hydrogenating and splitting effect. The metals of V., VI., Among others, are suitable for the hydrogenating effect. and / or VIII. group of the periodic table of the elements or compounds of these metals. For the splitting effect are in general Solid substances with an acidic character are used, which at the same time serve as carrier materials for the metal component (s) to serve. In particular, silica-alumina is a suitable material for the Manufacture of hydrocracking catalysts. Such catalysts and processes are, for. B. off British patent specification 928 762; Belgian patent specifications 637 762 and 639 291, patent specification of the Office for Invention and Patents in East Berlin, 13 369 and the French patent specification 1,388,593 known.

Furthermore, a process is known from French patent specification 1,355,210 in which a ^{hydrocarbon oil boiling above 149 °} C. is split by hydrogenation. The catalyst used contains 3 to 25 percent by weight tungsten and 0.5 to 10 percent by weight nickel and optionally 0.1 to 10 percent by weight. Fluorine or 1 to 15 weight percent silica. Both gasoline and jet fuel can be produced using this process.

As a rule, good results are achieved with the known catalysts when hydrocarbon oils of relatively low boiling point, e.g. B. gas oil fractions, to hydrocarbons boiling within the gasoline boiling range. Process for the production of middle distillates
by hydrogenative cleavage of
Hydrocarbon oils

Applicant:

Shell Internationale Research Maatschappij N.V., The Hague

Representative:

Dr. E. Jung and Dr. V. Vossius, patent attorneys,

8000 Munich 23, Siegesstr. 26th

Named as inventor:
Hendrikus de Ruiter,
Willem Cornell's Jan Quik,
Pieter Aldert van Weeren,
Amsterdam, Netherlands)

Claimed priority:

Netherlands of April 13, 1965 (6 504 682) - -

should be. In this case, the process takes place under comparatively mild temperature conditions, and the life of the catalyst is economically favorable.

However, if higher boiling hydrocarbon oil distillates, e.g. B. so-called flash distillates or Residual hydrocarbon oils, by hydrogenative cleavage into middle distillates, e.g. B. gas oil and luminous oil, are to be converted, it has been found that with the silica-alumina containing Catalysts produce less good results. The conversion takes place at a fairly low rate Selectivity, d. that is, a relatively large portion of the feed to undesirable low molecular weight Hydrocarbons is decomposed. Furthermore, the catalyst shows up after a comparatively short time a decrease in activity. These phenomena are probably due to the fact that these higher boiling oils contain certain components that under the temperature conditions of the hydrogenating Cleavage forms tar and coke-like products which are deposited on the surface of the catalyst.

It has now been established that higher-boiling hydrocarbons - among them hydrocarbon oils here with, a juice area completely

m »0/41«

or essentially above 35O ⁰ C - can be selectively converted into middle distillates in good yield if they are brought into contact under the conditions of the hydrogenative cleavage with a catalyst which contains two components as main constituents, namely one of tungsten and nickel, _{hydrogenation component} in the form of their sulfides and a carrier material consisting of aluminum oxide, which may be contaminated with a maximum of 1 percent by weight of silicon dioxide, and by one or more fluorine compounds in an amount of 6.5 to 12 percent by weight of fluorine, based on the total Catalyst, is activated.

These catalysts are particularly effective and have a performance compared to the known catalysts a surprisingly long lifespan. In addition, they are easy to regenerate and also show After several regeneration treatments, an activity that differs little from that of the fresh Catalyst differs.

The invention thus relates to a process for the production of middle oil distillates by hydrogenative cleavage of hydrocarbon oils at a temperature of 370 to 430 ⁰ C and a hydrogen partial pressure of 75 to 150 atmospheres and in the presence of a tungsten, nickel and fluorine-containing catalyst which contains aluminum oxide in the support material , which is characterized in that a hydrocarbon oil boiling entirely or substantially above 35O ° C is passed under such conditions over a sulfidic catalyst which, based on the total weight of the catalyst, 8 to 12 percent by weight of nickel and tungsten, 6.5 to 12 contains by weight percent fluorine, and as carrier material alumina, which may be contaminated with no more than 1 weight percent silica, that per pass at least 40 percent by weight of the starting material are converted in a below the final boiling point of a middle distillate boiling-point product having an initial boiling point of 160 ⁰ C whose boiling point is so high that the cloud point of the middle distillate is -15 ° C.

Higher-boiling hydrocarbon oils and / or their fractions which have been obtained by direct distillation, catalytic cleavage or in some other way are generally used as feed with a boiling range completely or essentially above 350 ^{° C.} Both the so-called flash distillates and residual oils or fractions of these are particularly suitable as starting materials. At the refinery, they fall oils in large quantities and at low prices and are according to the invention in wesentliehen in hydrocarbons having a boiling range between 160 and about 350 ⁰ C, so-called middle distillates, converted containing Leuchtöl- and gas oil components.

The hydrogenating cleavage reaction is expediently carried out at a relatively high hydrogen pressure, ie at partial hydrogen pressures of 50 to 250 atmospheres and preferably 75 to 150 atmospheres. Taking into account the high molecular weight character of the starting materials, the temperatures used can be chosen to be comparatively low as a result of the high activity of the catalysts used in the process according to the invention. The temperatures are preferably between 390 and 430 ⁰ C.

The temperature has a significant influence on the results of the process. At higher temperatures the conversion increases. However, no sharp temperature limits can be specified as the reaction temperature also depends on the type of starting material. In general are z. B. used, the higher the boiling range of the feed, the higher the temperatures.

The yield is given below as the yield of "middle distillate" obtained from the reaction product by distillation. Such middle distillate has been more or less arbitrarily defined as a hydrocarbon oil fraction having an initial boiling point of 16O ⁰ C and an end boiling point, which corresponds to a constant cloud point of -15 ⁰ C in about.

In this context, the conversion is expressed as a weight percent of the total below the Final boiling point of this middle distillate boiling product, based on the starting material.

The temperature in the reactor is adjusted so that the conversion per pass, i.e. H. Per Passage over or through the catalyst is at least 40%. Working conditions are preferably chosen to achieve a conversion of at least 55%.

The catalysts used according to the invention have a high activity, which means that with compared to the known catalysts, a high one even at relatively low temperatures Conversion can be achieved. This is of particular advantage in terms of service life of the catalyst. Despite the gradual decrease in catalyst activity, which with prolonged Use in a continuous process is inevitable, the conversion can take place on the desired level can be maintained when the reaction temperature gradually increases in a known manner is increased. Because in practice the final temperature is limited by technological and other considerations the lower the initial temperature, the longer the catalyst can be used is chosen.

Another surprising fact is that the inventive selective hydrogenating Cleavage of hydrocarbon oils on catalysts that have a high fluorine content have with an alumina support, so proceeds that in high yield middle distillates and only a small proportion of lower-boiling hydrocarbons can be obtained.

The catalyst contains a combination of tungsten and nickel in the form of their sulphides. In the The amount of tungsten and nickel present in the catalyst is 8.0 to 12.0 percent by weight based on weight on the entire catalyst.

The best results are obtained with a weight ratio or atomic ratio of nickel to Tungsten, preferably from about 0.25 to 0.75. This is shown in a number of experiments (see Example 1) with Ni / W / AkOg / F catalysts, in which the nickel content is changed while the content of tungsten remains constant. The best selectivity will be with achieved with these catalysts at a Ni / W atomic ratio of about 0.5 (see Table A).

The selectivity of the hydrogenative cleavage is given as follows:

Yield of middle distillate *) in percent by weight

S =

Yield of middle distillate *) (percent by weight) + fraction <160 ° C (percent by weight)

100%

*) Middle distillate with an initial boiling point of 160 ° C and an end boiling point that is determined by the conditions for a cloud point of -15 "C.

If the selectivity is plotted against the yield of middle distillate, the result is a straight line (for conversions of <75%) from which the selectivity index (SI) can be calculated using the following equation:

SI

Yield of middle distillate

100 - selectivity

Table A.

Effect of the Ni-W atomic ratio in
Ni / W / Al ₂ O ₃ / F catalysts

Ni / W atomic ratio S / 0 1.7 0.25 2.2 0.50 3.1 0.75 2.2

The influence exerted by the total amount of nickel + tungsten in the catalyst goes out three experiments (see example 1) which are carried out under the same reaction conditions, as they prevailed in the experiments given in Table A. The composition of the catalysts, whose Ni / W atomic ratio is 0.5 and their selectivity indices are given in Table B.

Table B.

Effect of the Ni + W content in
Ni / W / AkOa / F catalysts

Ni (parts by weight) W (parts by weight) 4.4 or to 100 parts by weight of aluminum oxide 8.8 0.7 13.2 2.4 1.4 3.1 2.1 2.3

The preferred use according to the invention of a relatively low content of nickel + tungsten in Catalyst is unusual for hydrogen cleavage. It is generally assumed that a hydrocracking catalyst with a higher hydrogenation efficiency, d. H. a higher content Metals that have a hydrogenating effect, have better activity and stability. The fact, that an increase in the metal content actually leads to a higher hydrogenation activity, is evident from Example 7, where the reaction rate constants measured in a series of experiments are given, in the experiments naphthalene in the presence of nickel and tungsten-containing catalysts with a Metal content of 23.4, 18.7, 13.2, 10.2 and 8.6 percent by weight, respectively, was hydrogenated.

Surprising is the fact that the invention catalysts used in relation to the hydrogenative cleavage of high-boiling hydrocarbon oils have high activity and excellent stability with low metal content. "Stability" is used here to denote the property of the catalyst during a longer period of time Time to keep practically the same activity, thereby reducing the transformations by hydrogenating Cleavage will remain at a comparatively constant level.

If the activity decreases over time, the degree of conversion can be restored to the previous level if the reaction temperature is increased gradually or gradually. With regard to the final temperature that can be used, the practical limit of approximately 430 ^° C. has already been pointed out above. The fluorine content is essential for the catalyst composition. It is relatively high and is more than 6.5 to 12.0 percent by weight, based on the total catalyst. The particularly high fluorine content is evident, especially when it is related to the total amount of nickel and tungsten contained in the catalyst. The weight ratio of fluorine to nickel + tungsten is generally between 0.2 and 2 and preferably between 0.4 and 1.2. This means that in some cases the catalyst contains significantly more fluorine than Ni + W.

Aluminum oxide is used as the carrier material, with a maximum of 1 percent by weight silicon dioxide may be contaminated, d. H. a material with relatively weakly acidic properties.

In order to achieve good catalyst properties, the type of starting material used is also important Alumina of importance. Although with practically all types of aluminum oxide available on the market If good results can be obtained, preference is given to alumina, which is in the pseudoboehmite form has been received.

A particularly suitable method for producing an aluminum oxide with excellent properties consists in continuously mixing an aqueous solution of an aluminum salt, preferably aluminum nitrate, with aqueous ammonia by introducing both simultaneously into a reactor with stirring. The amounts of the two reactants are adjusted so that the pH in the reactor is about 8.5 to 9.5. The continuously withdrawn as overflow alumina, for example, passed through a vacuum filter, is calcined and the filter cake at 110 to 130 ⁰ C dried and then at 300 to 1200 ⁰ C.

The catalysts used according to the invention have been prepared by the usual methods, generally preferably the alumina support material impregnated with an aqueous solution of a nickel and tungsten salt, then

7 8

dried and calcined at 300 to 1200 ⁰ C. Distillation is the use of hydrogen is appropriate. - Moderately between 20 and 200 normal liters / liter Be-The sulfidation of the catalyst is carried out. B. a mixture of hydrogen special from a catalytic cracking plant and hydrogen sulfide, the z. B. 10 volume percent 5 originating, can be much higher.
Contains hydrogen sulfide, under the usual conditions. Sufficient sulphidation is usually worked up by distillation, the different ones being indicated by the fact that the hydrogen _/ water sulphide fractions escaping from the catalytic hydrocarbon compounds into the desired sator bed are separated. The residue that contained the substance. According to another customary process from unconverted starting material and start-up, the catalyst to be summed is composed of one of its constituents; B. a hydrocarbon oil can be recycled.

which itself contained sulfur 15 One advantage of the catalysts used according to the invention or the 2 to 3 volume percent carbon disulfide catalysts is that they have been added over the or dimethyl sulfide. In this poisoning by nitrogen compounds, which is often the case, the temperature has been gradually increased to the level of the reaction temperature that occurs in the charge. are. Both nitrogen and sulfur compounds. The fluorine has been introduced in various ways in the fertilizers, completely or almost completely decatalyst, e.g. B. by hand. This means an important advantage of counteraction of the carrier with an aqueous solution of one of the for the production of gasoline by • fluoride, z. Ammonium fluoride, prior to the metal hydrotreating cleavage of hydrocarbon oil distile being deposited on the support. The Behänd- laten used known catalysts, with treatment with the fluorine compounds, if desired, a pretreatment, z. B. a catalysis tables at the same time or after the impregnation with hydrogenation is required.
the metal salt solution or on the finished catalyst. In general, the versator according to the invention can be carried out. The regeneration of the catalyst can be carried out by using a flash distillate as the starting material, an oxidizing treatment at an elevated temperature. Residual oils containing asphalt should be carried out with a mixture of nitrogen and air. After regeneration, which are completely free transit at most 500 ⁰ C of asphaltenes must of course completely or virtually before. When carried out, the catalyst has in many cases, this removal of the asphaltenes usually takes place on an activity that differs somewhat from the initial one, including a substantial reduction in the ash activity. There can be more than one salary. In those cases where the residue generation treatments are carried out without inherently free or substantially free of asphalt that the activity drops to an unsuitable level. In the process according to the invention for the service life of the heater, it is important to reduce the ash content, the catalyst will give preference to cleavage with a view to a long catalyst. This can be done in a known manner, e.g. B. applied wisely in the form of a fixed bed. The 40 percolation of the oil is done by a natural or charging that is below the set temperature- synthetic clay. Since, under these treatment conditions, some of the resinous substances and some of the resinous substances are initially present in liquid form and some in vapor form preferably continuously and in a downward flow, 45 reducing the nitrogen content,
passed over the fixed catalyst bed. The ash content can also be very expediently reduced, in which the starting material is reduced to a greater extent, in that the oil is severely split with water, the liquid is washed and then the aqueous phase is reduced, and finally the reactor becomes a product. is separated, e.g. B. by centrifugation. These ducts withdrawn, which completely or substantially 50 treatment, hardly sets the nitrogen content when present as steam. The space velocity decreases at all. Washing out with water expediently carries 0.2 to 51 oil / hour / liter of catalyst, but has the advantage that there is hardly any loss of analyzer and the amount of hydrogen from 100 to 3000 normal charge, as is the case with clay treatment gallons / liter of oil. ment is the case.

A preferred embodiment consists in 55 The method according to the invention is carried out by the

that the hydrocarbon oil is continuously explained in more detail in one of the following examples:
Temperature from 390 to 430 ⁰ C with a space velocity of 0.5 to 31 oil / hour / liter

Catalyst and an amount of hydrogen from 250 to B is ρ ie 1 1
2500 normal liters / liter of oil over a catalyst 60

is conducted, the nickel and tungsten in one atom- To the influence of the amounts of nickel and tungsten ratio from 0.25 to 0.75 and ram as a carrier material and / or the ratio of this metal composite aluminum oxide with a content of at most nenten to show each other, comparison-0.5 Contains percent by weight silica, tests carried out with six catalysts that the catalyst has a fluorine content of 6.5 to 10 parts by weight of each 8 parts by weight of fluorine per 100 parts by weight has weight percent. Contain aluminum oxide.

The hydrogen consumption is expediently 20 All catalysts are previously with a

up to 250 normal liters / liter load. With a flash mixture of hydrogen and hydrogen sulphide

sulfided at an overpressure of 10 atm, while the sulfidation temperature is gradually increased from 25 to ⁰ C.

A raw material obtained by direct distillation of a North African petroleum is used Residue used.

The reaction conditions are as follows: pressure 100 atmospheres, reaction ^{temperature 0} ° C., space velocity 11 residue / liter

10

Catalyst / hour, hydrogen consumption 2000 normal liters / liter residue.

Table I gives the compositions of the catalysts on as well as the results for conversion, selectivity, product fractions in weight percent, based on the liquid product yields of middle distillate having an initial boiling point of 160 ⁰ C and a cloud point of -15 ° C and diesel index of the fraction of 160 up to 340 ⁰ C.

Table I.

Catalyst composition, parts by weight

W.

Ni

Al ₂ O ₃

F.

Product fractions, based on the liquid product, percent by weight fraction

<100 ° C

100 to 160 ° C

160 to 250 ° C

250 to 32O ⁰ C

320 to 340 ° C

340 to 36O ⁰ C

360 to 375 ° C

> 375 ° C

Middle distillate

Initial boiling point 16O ⁰ C, '(cloud point -15 ° C)

Final boiling point ⁰ C

Yield calculated on the liquid product, percent by weight

Selectivity *),%

conversion

Diesel index of the fraction 160 to 340 ° C

*) "Selectivity" means in this and the following tables:

Yield of middle distillate oday, weight percent

2 try 3 4th 5 1 Q β
O, O 8.8 8.8 4.4 8.8 0.7 1.4 2.1 0.7 - 100 100 100 100 100 8th 8th 8th 8th 8th 6.4 4.9 6.3 5.3 6.9 8.7 9.1 9.3 6.7 7.8 36.8 { - 23.6
16.8 } 37.4 33.9 } 32.6 7.5 7.5 6.6 8.7 8.0 9.0 7.1 7.1 7.8 8.0 6.0 4.6 4.0 6.2 5.7 25.6 26.4 29.3 31.4 31.0 355 370 ' 360 355 345 51 58 51 48 43 " 77 81 77 80 74 66 72 67 60 58 61 61 63 61 59

13.2 2.1 100 8

34.7

32.7

365

51 78 65

64

Yield of middle distillate, percent by weight + fraction 160 ° C, percent by weight

100%

A comparison of the test results shows that 8.8 parts by weight of tungsten and 1.4 parts by weight Nickel containing catalyst (Experiment 3) the highest conversion, selectivity and Yield of middle distillate can be achieved. Excellent results are also obtained with catalysts the same amount of tungsten, but more or less nickel than the catalyst according to Trial 3 included (Trials 2 and 4). It is a surprising fact that with the catalyst according to experiment 2 with a low metal content practically the same results can be obtained as with the catalyst according to experiment 6, which has one-and-a-half times the amount of tungsten and three times the amount Contains nickel.

Example 2

Comparative experiments (experiments 7 and 8) are carried out under the same reaction conditions and with the same residue, with two catalysts are used, the 4 or 2 parts by weight of fluorine to 100 parts by weight of aluminum oxide contain. Otherwise, these two catalysts have the same composition as the catalyst 3 of Example 1 and are prepared in the same way.

H * 590/416

11 12

Table II gives the results of Trials 7 and 8 together with those of Trial 3.

Table II

Attempts 7

Catalyst composition, parts by weight

W.

Ni

Al ₂ O ₃

F.

Product fractions, based on the liquid product, weight percent fraction

<100 ° C

100 to 160 ⁰ C

160 to 250 ⁰ C

250-320 ° C

320 to 340 ⁰ C

340 to 360 ° C

360 to 375 ° C

> 375 ° C

Middle distillate
Initial boiling point 160 ⁰ C,
(Cloud point -15 ° C)
Final boiling point, ⁰ C

Yield calculated on the liquid product, percent by weight.

Selectivity,%

conversion

Diesel index of the fraction

160 to 340 ° C

A comparison of these test results shows that with decreasing fluorine content of the catalyst Selectivity increases somewhat, while the conversion-1.4 100

4.9 9.1 23.6 16.8 7.5 7.1 4.6 26.4

370

58
81
72

61

1.4 100

2.8 4.8

34.3

7.7

9.9

5.5

35.0

350

47 86 55

60

8.8 1.4 100

1.7 3.1

29.2

7.4

9.4

5.6

43.6

340

37 88 42

59

lung degree and the yield of middle distillate having a cloud point of -15 ⁰ C, based on the liquid product, significantly decreases.

Example 3

Experiments are carried out with the same residue as in the previous examples, with the exception of the temperature, which is now 440 ^° C., the same reaction conditions prevail and the catalysts according to example 2 are used which contain 4 or 2 parts by weight of fluorine.

Table III shows the results of tests 10 and 10, and also the results for comparison of experiments 3, 7 and 8 are given.

Table III

3 7th try
9 8th 10 Catalyst composition,
Parts by weight
W. 8.8
1.4
100
8th
425 8.8
1.4
100
4th
425 8.8
1.4
100
4th
440 8.8
1.4
100
2
425 8.8
1.4
100
2
440 Ni AK) ₃ F. Reaction temperature, C

continuation

14th

try
9

10

Product fractions, calculated on the liquid product, percent by weight fraction

<100 ° C

100 to 160 ⁰ C

160 to 250 ⁰ C Λ

250 to 320 ⁰ C

320 to 340 ° C

340 to 360 ⁰ C

360 to 375 ° C

> 375 ° C

Middle distillate
Initial ^{boiling point 160 0} C, (cloud point -15 ⁰ C) end boiling point, ⁰ C

Yield calculated on the liquid product, percent by weight

Selectivity,%

conversion

Diesel index of the fraction 160-340 ° C

4.9

23.6

16.8

26.4

370

58 81

72

61

2.8 4.8

34.3

7.7

9.9

5.5

35.0

350

47
86
55

60

5.7
8.3

39.6

8.4

8.1

5.1

24.9

1.7
3.1

29.2

7.4

9.4

5.6

43.6

340

37
88
42

59

2.8 5.9

37.3

9.1

9.1

7.6

28.3

340

46 84 55

60

From the table it can be seen that the conversion does not depend on the degree of conversion of the catalyst

increases significantly when reaching the temperature of 425 with 8 parts by weight of fluorine. Also at

to 440 ⁰ C is increased. For the catalyst with a content of 4 parts by weight of fluorine is used

2 parts by weight of fluorine is sufficient, however, the increase has not yet reached this level.

Example 4

At 400 and 425 ° C, two experiments with flash distillate with a boiling range of 308 to the same catalyst (fluorine content 8 weight 40 522 ° C used, which is made by direct distillation parts) as has been obtained in Experiment 3 of Example 1 and under an African petroleum. otherwise the same reaction conditions and with the In Table IV are the results of the comparisons Space velocity carried out. Instead of looking for 11 and 12 and to compare experiment 3 a residue is compiled from Example 1 as the starting material.

Table IV

try
H

12th

Catalyst composition, parts by weight

W.

Ni

AI2O3

F.

feed

Temperature, ⁰ C

Product fractions, based on the liquid product, weight percent fraction

<100 ° C

100 to 160 C

160 to 250'C

250 to 320 ° C

320 to 340 C

1.4 100 8 residue

425

4.9 9.1

23.6 16.8

7.5

8.8
1.4
100
8th

»Flash« distillate
400

2.1
4.4
9.1
18.6
8.8

8.8 1.4 100
8th

"Flash" distillate 425

8.5 10.5 20.2 17.8

7.5

continuation

try
11

12th

340 to 360 ⁰ C

360 to 375 ⁰ C

> 375 ° C

Middle distillate
Initial boiling point 160 ⁰ C,
(Cloud point -15 ⁰ C)
Final boiling point, ⁰ C

Yield calculated on the liquid product, percent by weight

Selectivity,%

Conversion, percent by weight

A comparison of experiments 3 and 12 shows that the conversion and the yield of middle distillate differ little if a flash distillate or a residue is used as the starting material. It is also clear from the experiments 11 and 12, that the catalyst with a content of 8 parts by weight of fluorine and at 400 ⁰ C has a sufficient conversion and a good selectivity.

7.1

4.6

26.4

370

58
81

72

9.7

5.5

41.8

345

39
86
45

9.5

4.2 21.8

365

56

75 75

Example 5

30th

Using the same residue as in Examples 1, 2 and 3, Experiment 13 is carried out with a sulfided catalyst which, apart from the type of aluminum oxide, has the same composition as the catalyst of Experiment 3 (8.8 parts by weight of tungsten, 1.4 parts by weight of nickel, 100 parts by weight of Al ₂ O ₃ and 8 parts by weight of fluorine).

The alumina in question has been prepared. by simultaneously introducing aqueous solutions of aluminum nitrate and ammonia into a reactor with stirring, the amount of the two solutions being adjusted so that the pH in the reactor was 9. The aluminum oxide gel formed was drawn off via the overflow and passed through a vacuum filter. The filter cake was then calcined at 120 ⁰ C and dried at 650 ⁰ C.

With the exception of the reaction temperature, which in this experiment is 400 ^° C., the experiment with the new catalyst is carried out under the same conditions as those given in Example 1.

The results of this Run 13 are in Table V along with the results of the run 3 given for comparison.

Table V

4.9 3.0 9.1 - 4.9 23.6 9.2 16.8 22.2 7.5 9.0 7.1 9.0 4.6 4.8 26.4 37.9

Catalyst composition,
Parts by weight

W.

Ni

Al ₂ O ₃

F.

try

1.4
100

13th

60

1.4
100
8 product fractions, based on the liquid product, weight percent fraction

<100 ° C

100 to 160 ° C

160 to 25O ⁰ C

250 to 320 ° C

320 to 340 ° C

340 to 360 ° C

360 to 375 ° C

> 375 ° C

Middle distillate,

Initial boiling point 160 ⁰ C,

(Cloud point -15 ° C)

Final boiling point, ⁰ C

Yield calculated on the liquid product, percent by weight

Selectivity,%

Conversion, percent by weight

From the table it can be seen that with this catalyst at the relatively low temperature of 400 ° C a comparatively very satisfactory conversion and a good yield of middle distillate be achieved.

Example 6

In order to show the stability of the catalyst used according to the invention, an experiment is carried out by carried out for a long time.

A flash distillate is used as the feed, in a yield of 87% by weight from a residue originating from a North African petroleum.

The reaction conditions are as follows: pressure 150 atmospheres, space velocity 1.0 l / liter of catalyst / hour, amount of aqueous Gas 2400 normal liters / kilogram charge.

The catalyst has the following composition: 8.8 parts by weight of tungsten, 1.4 parts by weight

try

370

58 81

72

345

44 86 51

18th

Nickel, 100 parts by weight of aluminum oxide and 8 parts by weight of fluorine. The catalyst lies in the sulfidic form and is made by adding 0.4 weight percent carbon disulfide to the feed kept in this form.

The conversion is kept at 60-70% with some loss of activity of the catalyst during of the experiment is compensated for by increasing the reaction temperature.

The results of this lengthy test, which is carried out continuously for 1588 hours of operation, are given in Table VI. During this time, the reaction ^{temperature must be increased from 418 to only 428 °} C. in order to maintain a conversion of 65%. At the beginning the selectivity is 78%, after 250 hours of operation it has automatically adjusted to 80 to 81%. At the end of the experiment, the total product has only a low nitrogen content, namely of about 0.001 percent by weight. The catalyst has thus proven to be very suitable for removing nitrogen.

Table VI

Trial time, hours - 96

Average reaction temperature, ⁰ C 420 Total liquid product

Yield, percent by weight of the

Charge 97.3

Specific gravity, 20/4 ⁰ C 0.778

Nitrogen content, ppm ~ 10

Chemical H2 consumption, percent by weight

of the feed 1,2

Product, weight percent of the charge

Gas ■ 3.9

Topdestillat <100 ⁰ C 4.5

Heavy naphtha 100 to 15O ⁰ C 6.4

Luminous oil 150 to 250 ⁰ C 20.3

150 ⁰ C *) gas oil (cloud point 15 ° C) .. 54.8

Residue> ucp *) of gas oil 31.6

Conversion,% 69.5

Selectivity,% 78.5

Product features

Pot fraction <100 ° C

F-I-O 68

F-l-1.5 83

Heavy gasoline, 100 to 150 ⁰ C

Paraffins, percent by weight (45)

Naphthenes, percent by weight (45)

Aromatics, weight percent (10)

Total nitrogen, ppm <0.2

Luminous oil

Aromatics, percent by volume (FI A) method 17

150 ⁰ C ⁺ gas oil

ucp, ⁰ C 350

Diesel index 67

Cloud point, ⁰ C -16

Total nitrogen, ppm 6.5

Specific gravity, 20/4 ⁰ C 0.821

Residue> ucp of gas oil

Specific gravity, 70/4 ⁰ C 0.801

Nitrogen, ppm ~ 15

*) ucp = upper intersection.

B e i s ρ i e 1 7

To show that the nickel-tungsten catalysts have greater hydrogenation activity, -728
420

97.4
0.788

<5

0.9

3.5

3.1

5.0
13.9
45.9
43.6
57.5
80

(68)
(83)

<0.2
24

341

62

-15

0.830

0.800

-767
423

96.3
0.780
<5

1.0

4.7

3.0

6.2
18.9
57.0
30.1
71
80

68.5
83

<0.2
21

350

65

-15

0.823

0.798

-1106 423

96.8 0.785

0.9

4.1 3.1 4.7 15.2 51.1 37.8 63 81

(68) (83)

<0.2 24.5

345

-15

0.828

0.800 15

the higher their metal content, the hydrogenation tests (14 to 18) are carried out. It will be five sulfided nickel-tungsten-alumina catalysts used, each containing 8 parts by weight of fluorine

"19 590/416

contain per 100 parts by weight of catalyst, but have different contents of nickel and tungsten.

A mixture of weight percent naphthalene, 78 weight percent benzene and 2 weight percent hydrogen sulfide is used as the starting material. The reaction conditions are as follows: temperature 300 ^° C., pressure ata, hydrogen / hydrocarbon molar ratio 10, space velocity 8 g of hydrocarbon mixture / g of catalyst / hour.

As can be seen in Table VII below, the reaction rate constants increase with decreasing nickel-tungsten content of the catalyst.

Table VII

Metal content * I. Ni W. Al ₂ O ₃ F. Composition of sulfidic W. , Weight percent F. total
metal content, Reaction speed Parts by weight 13th 20th 100 8th Nickel-tungsten catalysts ■. 14.2 Al ₂ O ₃ 5.7 Weight percent quality constant try Ni W. Al ₂ O ₃ F. W. 70.9 F. } 23.4 for hydrogenation T Vl ν MWÜW 9.8 15th 100 8th 11.3 Al ₂ O ₃ 6.0 I ι ο τ of naphthalene,
g naphthalene / Ni W. Al ₂ O ₃ F. Metal content W. 75.3 F. j 18.7 g catalyst / hour 14th per 100 parts by weight of carrier material 6.5 10 100 8th Ni 8.0 Al ₂ O ₃ 6.5 } 13.2 ■ f e Ni W. Al ₂ O ₃ F. 9.2 W. 80.3 F. } 10.2 1.5 15th 3.5 8.8 100 8th Ni 7.3 Al ₂ O ₃ 6.7 } 8.6 1 Λ Ni W. Al ₂ O ₃ F. 7.4 W. 83.1 F. 1.2 16 1.4 8.8 100 8th Ni 7.4 Al ₂ O ₃ 6.8 .5.2 84.6 0.9 17th Ni 2.9 0.5 18th Ni 1.2

Claims (4)

Patent claims: 1. Process for the production of middle oil distillates by the hydrogenative cleavage of hydrocarbon oils at a temperature of 370 to 430 ° C and a hydrogen partial pressure of 75 to 150 atü and in the presence of a tungsten, Nickel and fluorine-containing catalyst which contains aluminum oxide in the support material, characterized in that one Hydrocarbon oil boiling entirely or substantially above 350 ° C. under such conditions passes over a sulfidic catalyst, based on the total weight of the Catalyst, 8 to 12 weight percent nickel and tungsten, 6.5 to 12 weight percent fluorine and contains aluminum oxide as the carrier material, the silicon dioxide being at most 1 percent by weight may be contaminated that at least 40 percent by weight of the starting material per pass into a product boiling below the final boiling point of a middle distillate with a Initial boiling point of 160 C, whose boiling end is so high that the The cloud point of the middle distillate is -15 ° C. 2. The method according to claim 1, characterized in that a catalyst is used in which the atomic ratio of nickel to tungsten is about 0.25 to 0.75. 3. The method according to claim 1 and 2, characterized in that a catalyst is used where the weight ratio of fluorine to the total amount of nickel and tungsten is between 0.2 and 2. 4. The method according to claim 1 to 3, characterized in that the starting hydrocarbon oil a flash distillate or one freed or substantially freed from asphaltenes Residual oil used. Considered publications: Patent No. 13 369 of the Office for Invention and Patents in East Berlin; French Patent Nos. 1,355,210, 1388593; British Patent No. 928,762; Belgian published publications No. 637 762. 639 291.