DE1770904C - Process for the hydrogenation and hydrocracking of crude oils - Google Patents

Description

characterized in that the gaseous and the liquid phase are ^{fractionated before branching off a recycle stream to separate the fractions boiling above about 360 0} C, after which one of these fractions is returned to the reaction zone in an amount that corresponds to at least 25 percent by volume of the charge.

2. The method according to claim 1, characterized in that the temperature in the reaction ^{zone is about 454 ° C, the pressure between 140 and 175 kp / cm 2} and the hydrogen throughput is at least 90Nm ³ / hl, that the recirculation amount is at least 50 percent by volume of the charge , the space velocity is at least 0.25 vol. of the fresh charge / hour to the volume of the reaction vessel and the total conversion of the ^{constituents boiling above 525 G} C is greater than 90%.

3. The method according to claim 1, characterized in that the temperature in the reaction zone is in the range of 426 to 483 ° C and the pressure in the range of 105 to 210 kp / cm ² , and that the space velocity is a conversion of more than 50% and allows less than 75% of the constituents boiling above 525 ° C per operation, and the total conversion of the constituents boiling above 525 ° C is more than 90%.

4. The method according to any one of claims 1 to 3, characterized in that the returned Fraction boils at over 525 ° C.

5. The method according to claim 4, characterized in that the recycle ratio recirculated fraction / feed is at least 1.0, whereby a maximum amount of between 360 and 525 ^D C boiling heavy gas oil is obtained.

6. The method according to claim 4, characterized in that the return ratio stirred back Fraction / feed is at least 0.5 and the temperature in the reaction zone is lower than a process with the same conversion but less recycle.

7. The method according to claim 4, characterized in that that the recycle ratio of recycled fraction / feed is at least 0.5 and the pressure in the reaction zone is lower than in a process with the same conversion, but less repatriation.

8. The method according to any one of claims J to 3, characterized in that the recycled fraction boils ^{in the range from 360 to 525 C C.}

9. The method according to claim 8, characterized in that that no part of the fraction boiling from 360 to 525 C is removed from the system.

The invention relates to a process for the hydrogenation and hydrocracking of crude oil with at least 25 volume percent above 525 ⁰ C boiling components to substantially convert these ingredients in lower-boiling substances.

When converting crude oil through destructive hydrogenation, the main goal is to have such a high degree of conversion to achieve as it is possible due to the work system. The ultimate goal is conversion all feed material boiling above 525 ° C into a lower boiling material, such as B. in gasoline, kerosene, jet fuel, diesel oil and heavy gas oil, with complete exclusion lower-quality, higher-boiling liquids.

During the conversion of the crude oil by destructive hydrogenation under the necessary high temperature and high pressure conditions, many reactions take place, such as saturation, polymerization, cracking, desulfurization, denitration and hydrogenation, all of which occur simultaneously, albeit at different rates. The obtained result He ·: £ are therefore generally be recognized empirically and depend on the feedstock properties, temperature, pressure, speed ratios in the reaction vessel, the Wasserstoffdurchflußmenge, the type of catalyst and the catalyst efficiency.

A method for the catalytic hydrogenation of crude oil or residues is e.g. B. from the USA patent 2,987,465 known. This process is carried out at high temperature and high pressure conditions Crude oil passed upstream through a catalyst layer in the reaction zone of a reaction vessel together with hydrogen gas. The speed of the upward flow through the catalyst layer is such that the catalyst particles in a Vortex movement get and the catalyst layer by at least 10% of its volume in the settled State of stretching. The feed is after flowing through the catalyst layer in a

gaseous and liquid phases are separated, and parts of these products become re-flowed the catalyst layer returned to the bouen of the reaction vessel.

The working conditions inside the reaction vessel can be controlled so that no transfer of catalyst particles from the reaction zone is prevented. As a result of the vortex movement of the catalyst particles in the reaction zone can this essentially under isothermal conditions keeper, be. It is therefore possible to use a higher average temperature since By avoiding high local temperatures, the catalyst can be kept clean for a longer period of time. In addition, any coke that forms goes with the thanks to the expansion of the catalyst layer The reaction participants flow upwards without difficulty through the catalyst bed and the total pressure drop across the bed remains essentially constant.

The invention is based on the object of a method for the hydrogenation and hydrocracking of crude oil with at least 25 percent by volume above 525 ° C of boiling constituents of the type known from US Pat. No. 2,987,465 in such a way that at high throughput in a given reaction vessel, an increased rate of conversion than above 525 'C boiling components is obtained, with a deposit of contained in the feed Asphaltenes in the reaction vessel and thus contamination of the catalyst are largely avoided becomes what a further extension of the Roman Age, d. H. the time until the renewal of the catalytic converter, has the consequence.

This object is inventively achieved in that the gaseous and liquid phases before the branching a recycle stream can be fractionated, according to which one of these fractions is recycled to the reaction zone in an amount to boiling above about 36O ⁰ C fractions to separate, at least 25 volume percent corresponds to the load.

In the case of a return of the above 525 ° C boiling fractions would have a higher space velocity, i.e. H. Volume of fresh load / hour to the volume of the reaction vessel required to achieve the same residue conversion be as if no regression is being performed. The product yield shifts more in the range of between 360 and 525 ° C boiling heavy gas oil. Is the repatriate fraction the heavy one Gas oil with a boiling range of 360 to 525 ° C may have a lower space velocity for charging Fresh material can be used, with a lower yield of heavy gas oil with a boiling point from 360 to 525 ° C, but an increased yield of heavy gasoline and furnace oil is obtained. One A significant improvement in the procedure is also achieved in that a precipitate of asphaltenes is avoided in the loading.

To further explain the invention, an apparatus for carrying out the method is described below described in more detail according to the invention with reference to the drawing, in which this device is shown schematically is shown. It is then shown on the basis of four tables which advantages the inventive Process compared to known processes.

As shown in more detail in the drawing, a feed 10 can contain a residue with a catalyst 12, which may be in the form of a slurry, and together is introduced into a reaction vessel 18 with hydrogen from line 16 through line 14. As in the teaching of the aforementioned U.S. Patent 2,987,465, the reaction vessel may be a Have support surface 20 for the liquid distributor and the catalyst, so that the liquid and the Gases flowing up through the reaction vessel 18 tend to carry the catalyst into a To displace vortex movement.

The catalyst particle size range is usually narrow for uniform expansion under controlled liquid and gas flow conditions. While the total range is usually between 3.2 and 0.044 mm, according to the invention a so-called forced-flow mode of operation using a catalyst in the sieve size range 100 to 200 (= 0.149 to 0.075 mm) with a liquid velocity of the order of 200 to 40U l / min / m ² of the horizontal reaction space taken into account. Alternatively, a catalyst with larger particles - usually 0.8 mm in size - can be used with appropriate recirculation of the heavy oil or hydrocarbon gas from the upper part to the lower part through the grate to obtain about 1600 to 24501 total liquid / min / m ^{2 of} the horizontal reaction space. It is of course also possible to use a catalyst with a sieve size range of 40 to 80 (= 0.42 to 0.177 mm) by appropriately selecting the liquid velocity and the other relative control variables or work variables. If larger catalyst particles are used, it may be necessary to use pressure regulating chambers (not shown) with the catalyst being introduced through valve 48 and discharged through valve 50.

By controlling the catalyst particle size and density as well as the liquid and gas velocities and taking into account the viscosity of the liquid and the buoyancy of the hydrogen under the working conditions, the catalyst layer can be expanded so that it has a certain height or interface, which is indicated at 22, in who ingests liquid. It can be seen that the height of the catalyst in the static state - if z. B. the liquid flow rate falls below a value supporting the catalyst - much lower than the height 22 will be. Normally the layer extension must be at least 10% and rarely more than 300% of the height in the static state, and the liquid flow rate or velocity is usually in the range 40 to 4000 l / min / m ^{2 of} the horizontal cross-section of the reaction vessel.

In a reaction vessel system of this type, a vapor space 23 is provided, from which an absolute total liquid-free vapor is removed overhead through line 24. This total steam can suitably cooled and partially condensed in a heat exchanger 26 and in one Separator 28 into a gaseous portion 30 discharged overhead through a line and one through the Line 32 discharged liquid portion are separated. The gaseous portion 30, which is mostly

consists of hydrogen, can be purified by conventional means 40 and, after being reheated, be returned to the reaction vessel 18 through the compressor 42 and the supply line 14.

An internal circulation of the liquid within the reaction vessel from above the interface 22 to below the distributor support surface 20 is usually also desirable in order to ensure the completeness of the To ensure implementation and to ensure sufficient speed of the upward flowing liquid to achieve and thus the maintenance of the catalyst in an arbitrary movement (vortex movement) to promote in the liquid. This is preferably done through the use of a center line S1 reached, which has an enlarged conical or funnel-like cap 52. This line extends up to a pump 21 below the distributor support surface 20, to a compulsory and regulated Ensure movement of the liquid down through line 51.

The recirculation of liquid through the inner line 51 has many mechanical advantages and that Tendency to make external high-pressure connections superfluous, which would otherwise be in a hydrogenation vessel would be required. Nonetheless, repatriation can - as in the one mentioned above United States patent described - be carried out by an external pump.

The liquid portion 32 from the separator 28 is in a heat exchanger 34 and then in a Distillation column 36 in fractions boiling within the gasoline range (overhead), kerosene and diesel oil (Side streams) and fractionated into heavy gas oil with a boiling point above 360 ° C in line 65. Heavy liquid flowing out of the reaction zone, which is free of a catalyst, becomes from the Liquid outflow quantity in the upper region of the reaction vessel 18 through a catching trough 43 recovered such leakage liquid in line 44 through a pressure reducing valve 53 flows through and is fractionated in the distillation column 60 without cooling. Preferably be light products such as B. light gas, removed overhead through line 61, while materials in Boiling range of kerosene and diesel oil are removed as side streams 62 and 63. A heating oil fraction is removed as soil fraction at 64.

The structure and mode of operation of the steam section 23 of the reaction vessel 18 is essential for the successful The functioning of the entire system is critical in that the steam flow must be free of droplets or mist must, since asphaltenes present in high concentrations in these liquid droplets are caused by the Paraffinic heavy gasoline to be completely precipitated ', which is present when all condensable Materials in this stream are in liquid form. This would of course lead to pollution all exchanger surfaces, pipe surfaces. Guide valve and vessel walls.

At the same time it is necessary to keep this vapor space or section (23) small in order to reduce the amount of thermal cracking tu : this cracking produces olefins which tend to polymerize. The removal of catalyst-free liquid through the line 44 is controlled by the valve 54, which is confirmed by a control instrument 55. The control instrument 55 is a differential pressure measuring device. based on the pressure difference between

(a) the vapor space 23 and (b) a location just above the interface 22, i.e.. H. a place in the lowest part of the catalyst-free liquid layer in the reactor 18 responds. This diflerential pressure is a direct function of the depth of the catalyst-free liquid layer above the interface 22 and is thus more or less inversely proportional to the volume of the vapor space 23. The control instrument 55 is for determining the depth of the

ίο catalyst-free liquid layer arranged, the corresponds to the desired volume of the vapor space 23. When the depth of the catalyst free If the liquid layer decreases, the differential pressure measured by the control instrument also decreases.

and at a predetermined value, the control instrument closes valve 54 to lower the liquid level 56 and consequently also the differential pressure can rise to the desired level. The rising Liquid level higher than desired, the control instrument 55 opens the valve 54, so that the Lower the liquid level in the reactor to the value specified by the control instrument can.

The mostly above 360 ^c C-boiling oil fraction 64 is fed to a Vakuumdestillierkolben 66 and fractionated into a heavy gas oil or hydrocarbon gas which boils and in the range 360-525 ^L C is removed through line 67 and into a residue material that is above 525 ^C C boils and is removed through line 72. A portion of the heavy gas oil or hydrocarbon gas in line 67 can be removed through line 71 and combined with the portion in line 65 and returned all or part of it through valve 70 and line 69 to reaction vessel 18! will. Optionally, all or a portion of the heavy gas oil material can be discharged through line 82.

All of the material in line 72 that above

boiling of 525 ^r C, valve 76 and line 69 can be returned to the reaction zone through line 68. The portion that is not recycled is removed through line 75.

The valve control means for an independent recirculation and removal of the fractions - as described above - are not shown, since their arrangement and use are obvious to the person skilled in the art.
This way of working, deposits of

Agglomerates of coke and catalyst avoided in the reaction vessel, a recirculation of above 360 ⁰ C whereas in Nichtdurchführune boiling fractions the coke catalyst precipitation irr reaction vessel, the process unworkable wheeler and would result in short Anströmzeiten.

The following examples illustrate the procedure according to the invention.

example 1

Two trials were carried out using a Kuwait vacuum residue feeder. Both tests were carried out in similar test facilities. Each plant had a reaction vessel with a volume of 400 cm ³ and an inner diameter of 15.6 mm. The catalyst used was a cobalt molybdate catalyst with catalyst particles with a diameter of 0.8 mm in the form of 0.8 mm structures. The first

Test (referred to as a case 1) a degree of conversion of 89.3% was (conversion of above 525 ° C boiling feed to lower boiling products) at a temperature of 453 ⁰ C. a Wassersloffdruck of 157.5 kg / cnr and a space velocity of Fresh charge of 0.54 parts by volume of oil per hour per volume of the reaction vessel and with a hydrogen flow rate of 108 Nm ³ / hl. A similar experiment was carried out, but in this case (case 2) the product fractions boiling higher than about 525 ° C. were recycled. At a temperature of 454 ° C, a pressure of 157.5 kp / cm ² were a space velocity of the fresh loading. Destiny of 1.01 volumes of oil per hour per volume of the reaction vessel and a return feed of 0.53 volume of material with a boiling point of 525 ^C C and above needed per hour per volume of fresh feed, as well as a Wasserstoffdurchflußmenge of 92 Nm ³ / hl . The degree of conversion in this case was 92.8%. so a little higher than that achieved in the first attempt.

There was a remarkable effect in that this degree of conversion was about twice as high high space velocity (1.01 volume per hour per volume of the reaction vessel compared 0.54 volume per hour per volume of the reaction vessel) than that used in the first attempt would. At approximately the same temperature, the oil throughput required to achieve the desired degree of conversion was higher, if one Return of the higher than 525 ° C boiling product fractions was carried out. Additional advantages which were achieved consisted in reducing the gas yields from 7.6% in the first case to 4.9% in the second case and in higher yields of heavier

, ₅ gas oil or hydrocarbon gas with a boiling point of 360 to 525 ° C, as well as in the reduced yield of C ₄ -204 ° C heavy gasoline compared to the obtained in the first experiment. In addition, in the case of return, the quality of the product fraction was with a

ίο Boiling point of 525 ° C and above and the product fraction with a boiling point between 360
525 ° C higher.

Details of this series of tests are shown in Table 1 below.

Table I.

Hydrogenation treatment of oil from Kuwait vacuum residues with a 90% conversion yield with recycling or in a single operation

No repatriation
Case

return
Case 2

Fresh loading

Temperature, ⁰ C

Pressure in kp / cm ²

Fresh charge, space velocity, volume of fresh charge / hour / volume of reaction vessel (V _f fh / V _r )

Return feed of material with a boiling point of 525 ° C and above, volume of return feed / volume of fresh feed (V _n JV ₁ )

H ₂ flow rate, Nm ³ / hl

H ₂ consumption, Nm ³ / hl

Converting 525 ° C Boiling Point and Above Charge to Charge,%

Catalyst age, hl / kp

Q, percent by weight, yield

C ₂ , weight percent, yield

C ₃ , weight percent, yield

C ₄ + liquid product

(Continued) Kuwait Vacuum Residues

453
157.5

0.54

454
157.5

1.01

0 0.53 108 92 24 21 89.3 92.8 4.34 4.97 2.0 1.6 2.2 1.5 3.4 1.8

Feeding No return

return

Volume percent, yield

Specific gravity, 15.5 ° C / 15.5 ° C

Sulfur, weight percent

(Ramsbattom coke residue) RCR,% ...

C ₄ - 204 ° C, percent by volume

Specific gravity, 15.5 ° C / 15.5 ° C

Sulfur, weight percent

Aniline point (initial boiling point -204 ⁰ C). C.

1.017 5.53 16.67 104.6
0.868
1.05

31.2
0.722
0.10

53.3

106.1
0.884
1.25

22.0

0.739

0.11
53.7

209647

continuation

feed

No repatriation

return

204 to 360 ⁰ C, percent by volume

Specific gravity, 15.5 ° C / 15.5 ° C

Sulfur, weight percent

Aniline point, ⁰ C

360 to 525 ° C, percent by volume

Specific gravity, 15.5 ° C / 15.5 ° C

Sulfur, weight percent

Aniline point, ⁰ C

525 ° C and above, percent by volume. Specific gravity, 15.5 ° C / 15.5 ° C

Sulfur, weight percent

RCR,%

catalyst

Example 2

Example 1 shows the possibility of achieving a degree of conversion at a higher space velocity. This result can be used to work at a lower temperature than that which is required if the product fraction boiling ^{at 525 ° C. is not recycled.} At the same space velocity, it is possible to work at a lower temperature if the product fraction boiling above about 525 ° C. is recycled. This effect is shown in Table II. When recycling the product fraction boiling above 525 ° C, a temperature of 445 ° C was required compared to a reaction vessel temperature of 454 ° C, the necessary

39.9
0.856
0.35
56.5
22.8
0.959
1.30
67.8
10.7
1.067
3.30
37.23

0.8 mm in size
Extrusions
from cobalt molybdate
on clay

34.9 0.856 0.63 57.2 37.4 0.940 1.8 70.6 11.8 1.068 3.5 30.0

0.8 mm extruded pieces of cobalt molybdate on alumina

was manoeuvrable when the product fraction boiling above 525 ° C. had not been recycled Same benefit in product distribution, i.e. H. a lower gas yield, a lower heavy gasoline yield and a higher yield of heavy gas oil can be seen again.

In the case in which the recirculation of the product fraction boiling above 525 ° C does not go through long flow times could not be achieved. Precipitation from agglomerates on: Coke and catalyst particles found in the reaction vessel as a result of the asphaltene residues in the reactor tion vessel instead. On the other hand, long flow times were achieved when the product was returned faction took place.

Table II

feed

With repatriation

In a single operation

Fresh loading

Temperature, ° C

Partial hydrogen pressure, kp / cm ²

Space velocity, volume of fresh charge / hour / volume of reaction vessel (V _f fti / V _r )

Return material

Recycle Ratio, Recycle Charge Volume / Fresh Charge Volume (V _{1 JVf)}

Total conversion of materials boiling at 525 ° C and above - yield

C ₄ + liquid

C ₁ to C ₃ , weight percent

C ₄ - 204 ° C, percent by volume

204 to 360 ° C

360 to 525 ⁰ C

Kuwait vacuum residues

445
105

0.75

Product with a
Boiling point of
525 ° C and above

0.42

82.6 83.4 105.5 103.1 3.3 5.1 16.8 21.1 27.0 34.7 42.3 30.9

454 105

0.78 none

■■ V

770 904

Continued 12

Feeding with return

In a single operation

525 ° C and above, volume percentage ..
Specific weights, 15.5 ° C / 15.5 ° C

C ₄ + liquid

C ₄ - 204 ⁰ C

204 to 360 ⁰ C

360 to 525 ° C

525 ⁰ C and above

Weight percent S

C ₄ + liquid

C ₄ - 204 ⁰ C

204 to 360 ° C

360 to 525 ° C

525 ° C and above

catalyst

100

1,018

5.4 19.4

0.920 0.731 0.860 0.950 1.075

2.09 0.15 0.98 2.11 3.83

Cobalt molybdate microspheres on clay with a screen size of 100 to 200 (= 0.149 to 0.074 mm)

16.4

0.900 0.726 0.857 0.953 1.103

1.56

0.15

0.41

1.86

3.68

Cobalt molybdate microspheres on clay with a screen size of 100 to 200

Table III

Hydrogenation treatment of oil from Kuwait vacuum residues with recycling of the at 360 to 525 ° C boiling heavy gas oil versus destructive treatment and treatment

in a single operation.

With repatriation

In a single operation

catalyst

Procedural conditions

Hydrogen pressure in kp / cm ²

Space velocity, volume of the feed / hour / volume of the reaction vessel (V _f / h / V _r )

Temperature, ⁰ C

Recycle ratio, volume of material boiling at 360 to 525 ° C / volume of fresh feed (V _R / V _f ) ....

Hydrogen flow rate, Nm ³ / hl charging of vacuum residues

Amount of catalyst added in kp / hl

Yield in percent by volume based on the charge

H ₂ S, percent by weight

Q to C ₃ , weight percent

C ₄ - 166 ° C, percent by volume

166 to 360 ⁰ C

360 to 525 ° C

525 ° C and above

C ₄ + liquid, percent by volume

Specific weights, 15.5 ° C / 15.5 ° C

C ₄ +

166 to 360 ⁰ C

360 to 525 ° C

535 ° C +

Cobalt molybdate microspheres on clay, mesh size 100 to (= 0.149 to 0.074 mm)

105

105

0.38 0.96 463 463 1 0 216 112 0.032 0.026 5.0 4.5 7.7 4.6 25.0 14.8 65.2 40.2 - 32.0 15.9 16.8 106.1 103.8 0.862 0.901 0.864 0.847 - 0.957 1.152 1.131

continuation

With backward emotion In a single
Operation Sulfur content
C ₄ + 1.09
0.52
3.91 1.74 166 to 360 ⁰ C 0.78 360 to 525 ° C 2.01 525 ° C and above 4.02

It has been found that for separate distillation of the effluent from the reaction vessel liquid 15 and vapor portions for separating the heavy gas oil fraction (360-525 ^C C) from the two streams, and by combining the heavy gas oil streams and by Rückrührung the combined stream into the reaction vessel, the heavy gas oil product completely from - 20 could be switched. The test results for the comparison of this procedure with the procedure comprising only a single operation are given in Table III.

It should be noted that more than 90% heavy gasoline and heating oil (C ₄ -360 ° C.) were obtained from vacuum residues in a single reaction vessel with this procedure.

The use of a single reaction vessel to accomplish this conversion is special important in those cases where the total charge introduced into the plant is small. It's economical not justifiable, the amount flowing out of the first reaction vessel into an even smaller one Transfer system for the high-pressure hydraulic ackverfahrcn.

Another important benefit of treating residues using this process is: that due to the high concentration of heavy gas oil in the feed, the breakdown of the Asphaltene prevents undesired products and thus their deposition in the reaction vessel or is avoided in the downstream facilities.

Table IV

Hydrogenation Treatment of Kuwait Vacuum Residues with Recycle of the heavy gas oil condensed by the reaction vessel vapor versus the treatment

Mil return in a single operation

In a single operation

catalyst

Cobalt molybdate microspheres on clay with a screen size of 100 to 200 (= 0.149 to 0.074 mm)

Procedural conditions

Hydrogen pressure, in kp / cm ²

Space velocity, volume of fresh batch /

Hour / volume of the reaction vessel (V _f / h / V _r )

Temperature, ° C

Recycle ratio, volume of the fraction boiling at 360 to 525 ° C. / volume of fresh feed (V _R / V _f ) .... hydrogen flow rate in Nm ³ / hl feed of

Vacuum residue

Amount of catalyst added in kp / hl

Yield,% based on feed

H ₂ S, percent by weight

Ci to C ₃ , weight percent

C ₄ - 166 ⁰ C, percent by volume.

166 to 204 ° C, percent by volume

204 to 360 ° C, percent by volume

360 to 525 ° C, percent by volume

525 ° C, percent by volume

C ₄ + liquid, percent by volume

105

0.62
454

0.27

130
0.04

4.6

4.9

16.2

7.8

41.0

18.7

19.9

103.6

105

0.87 454

no

111 0.029

4.5

4.1 12.4

5.9

32.3

33.2

20.0

103.8

continuation

In a single operation

Specific weights 15.5 ° C / 15.5 ° C

C ₄ +

166 to 204 ⁰ C

204 to 360 ⁰ C

360 to 525 ° C

525 ° C

Sulfur content

C ₄ +

166 to 204 ° C

204 to 360 ⁰ C

360 to 525 ° C

525 ° C and above

0.900
0.785
0.860
0.950
1.0175

1.45
0.21
0.67
1.76
3.68

0.905 0.785 0.855 0.995 1.079

1.26 0.20 0.41 1.57 3.0

It has been found that by condensation and fractionation of the flowing out of the reaction vessel Steam to obtain a heavy gas oil product and by recycling this stream in the reaction vessel decreases the amount of the heavy gas oil product and the amount of the heavy gasoline Fuel oil product could be increased. This procedure is very useful if desired is to gain a certain amount of usable heavy gas oil. It is possible to use the vacuum fractionation to switch off the liquid flowing out of the reaction vessel in order to obtain a heavy gas oil recirculation stream.

In the simplest version of this system, the flow leaving the reaction vessel can be over Head partially condensed and the heavy liquid returned from the condensation without fractionation will. Certain differences will of course be made in the structure of the product yield. Unless there is a return in the range of 360

Stirred product fraction boiling up to 525 ° C long flow times could not be achieved. With the same high degree of conversion precipitates of coke catalyst agglomerates formed in the reaction vessel as a result of the

put asphaltenes in the reaction vessel. When carrying out the return of this product fraction on the other hand, long flow times were achieved. It is believed that the high percentage of heavy gas oil in the reaction vessel liquid, the asphaltenes in solution

strives to keep sung. When working with a single pass, these asphaltenes tend to to be precipitated.

The following areas of working conditions are particularly beneficial (depending on the nature of the

different feed materials).

Temperature, ⁰ C

Pressure, kp / cm ²

Hydrogen throughput, Nm ³ / hl

Space velocity, volume of fresh batch /

Hour / volume of the reaction vessel (V _f / h / V _r )

Return [V ₁ JVj)

catalyst

0.25 to 5.0

at least 25% fresh loading 3.2 mm up to sieve size 325 (USA standard) = 0.044 mm

Type of catalyst ι cobalt molybdate, nickel molybdate on clay

'earth base or alumina base containing the same amounts of silica

It has been found that by changing the recycle ratio that boiling at 525 ° C and above Product fraction the yield of the heavy gas oil could be changed. If the ratio is higher than 1.0 a higher yield of the heavy gas oil boiling between 360 and 525 ° C than with a ratio of 0.5 receive.

1 sheet of drawings

Area

399 to 483
70 to 350
at least 45

Preferred

454

140 to 175 90

0.5 to 1.0

Claims (1)

Patent claims: 1. Process for hydrogenating and hydrocracking crude oil at least 25 percent by volume above of 525 ° C boiling components according to the following process steps: a) The crude oil is passed at a temperature in the range from 399 to 483 ° C. and at a pressure in the range from 70 to 350 kp / cm ² together with at least 45 Nm ³ hydrogen / hl in an upward flow through a catalyst layer in the reaction zone of a reaction vessel , the grain size of the catalyst being within a size range between 0.044 and 3.2 mm. b) The speed of the upward flow through the catalyst layer is adjusted so that the catalyst particles get into a vortex movement and the catalyst layer expands by at least 10% of its volume in the separated state, with the space velocity, ie volume of fresh charge / hour increasing Volume of the reaction vessel is so high that more than 50% of the constituents boiling above 525 ° C are converted and sulfur is partially removed. c) The charge is after flowing through the catalyst layer in a gaseous and separated into a liquid phase, and parts of these products are used again Flow back through the catalyst layer,