DE1263209B - Process for lowering the sulfur content and pour point of heavy vacuum gas oil - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Clog

German KL: 23 b -1/04

Number: 1263 209

File number: G 39633 IV d / 23 b

Filing date: January 16, 1964

Opening day: March 14, 1968

Heavy petroleum distillates, such as heavy vacuum gas oils made from crude oils containing sulfur and wax are obtained are often because of their high sulfur content, their high pour point and their high viscosity unsatisfactory for various purposes, namely as technical heating oils or starting material for catalytic cleavage. The residue fractions of many crude oils are also made from the same Reasons as low-quality or technical heating oils or even as bunker heating oils are unsatisfactory.

The invention provides a method for producing heavy distillate fractions with satisfactory Sulfur content and pour point from heavy vacuum gas oil available, which itself has a relatively high sulfur content and high pour point. Furthermore, the invention provides a method for the production of residual heating oils with satisfactory Sulfur content, pour point and satisfactory viscosity from residual heating oils available, which leave something to be desired in this regard.

The inventive method for lowering the sulfur content and the pour point of heavy vacuum gas oil with a boiling range between about 343 and 577 ° C, which contains a substantial amount of ^{boiling in the range of about 399 to 577 0} C constituents, is characterized in that the heavy Vacuum gas oil by catalytic hydrogen desulfurization under known conditions at a temperature between about 343 and 427 ° C, a hydrogen partial pressure between about 36.7 and 105 kg / cm ² and a space velocity between about 0.2 and 10 at least 50% of the Removes sulfur compounds by converting them into hydrogen sulfide, the gas oil obtained in the hydrogenative desulfurization in a manner known per se at an overpressure between about 3.5 and 84 kg / cm ² , a temperature between about 427 and 538 ^° C. and a space velocity between about 2, 5 and 15.0 subjected to heat splitting with the formation of about 10 to 15% light gasoline, from the Pro In the product of the heat splitting, a distillate with a high pour point and wax content with a boiling range between about 343 and 538 ° C is distilled off, this is returned to the heat splitting stage in an amount of 1 to 3 parts by volume per part of the fresh charge fed to the heat splitting stage, and as a bottom fraction in the Distillation of the product of the heat dissociation separates a high-boiling hydrocarbon mixture of relatively low sulfur content and pour point, this product optionally with the distillation residue of the product of the viscosity process to lower the sulfur content and pour point of heavy ones
Vacuum gas oil

Applicant:

GuIf Research & Development Company,

Pittsburgh, Pa. (V. St. A.)

Representative:

Dr. K. Jacobsohn, patent attorney,

8042 Schleissheim, Freisinger Str. 38

Named as inventor:

James Albert Frayer, Pittsburgh, Pa .;

Theodore Rice, Beaumont, Tex .;

John Robert Strausser, Baytown, Tex .;

Eldon Marvin Sutphin, Pittsburgh, Pa. (V. St. A.)

Claimed priority:

V. St. v. America July 2, 1963 (292 281) - -

breaking treatment of a concentrated crude oil and possibly also with a part of the recovered from the distillation of the product of the viscosity breaking treatment of the concentrated crude oil Heating oil fraction and a part of the heating oil fraction obtained during the distillation of the product of the heat splitting mixed and optionally one in the distillation of the product of the viscosity-breaking Treatment of the concentrated crude oil recovered heavy gas oil fraction to the feed of the hydrogenating Desulfurization stage or the heat gap stage added.

By "space velocity" the throughput speed in space of feed is to be understood per hour to the separation system in each space portion of the heated in the cracking unit to a temperature above 399 ⁰ C fuel oil.

The catalytic hydrogenative desulphurization of petroleum fractions, in particular of gas oil or of products resulting from the coking of residual oils are known (cf. German Auslegeschriften 014 692, 1 050 946).

The heat splitting of hydrocarbon oils is also known per se. This is how the USA. Patent describes 2,687,986 a method of extraction

809 518/615

3 4

high gasoline yields thanks to two-stage viscosity-hydrogenating desulphurisation Treatment of heavy oil distilleries.

tion residues. The starting material in the For further explanation of the invention is on

Referring to the first stage of a sharp viscosifier, reference is made to the drawing, in which a pre-subjected to high gasoline yield treatment, Fig. 5 is shown the preferred embodiment. Sulfur and the tar obtained in this way is in a second high-melting wax containing crude oil, which process stage under mild conditions on heating oil in vacuum distillation processes a heavy vacuum, gas oil with unsatisfactory sulfur content and stock in the USA. Patent 2 662 845 is a process point would deliver , is fed through line 2 to the special heavy oils, such as crude oil or distillation plant 4, which work in the case of heat splitting of hydrocarbons, in particular atmospheric pressure and under vacuum. From the distillation-concentrated crude oil, at 232 to 288 ^° C. and 3.5 to system 4, the lighter fractions are described by 14 atmospheres, which is deducted from the extraction of high line 6, while line 8 aims at a yield of luminous oil and gas oil fractions. heavy vacuum gas oil or a wax distillate - but the 15 fraction with a boiling range between 343 and the process according to the invention was not suggested by these known processes. When 577 ° C is taken, which share an essential, obvious way to produce a heating oil share (at least 50% and preferably 60 to a sufficiently low pour point and sulfur 90%) of between 399 and 577 ° C boiling content of high-boiling, high-sulfur gas oil contains. Rather, the residue fraction of the crude oil would probably have been first that 20 flows off through line 10. The heavy vacuum gas oil fraction withdrawn through line 8 and subjected to heat splitting has distilled off a high-boiling fraction from the heat splitting products, the undesirably high sulfur content and pour point desired as heating oil, and only this fraction is desulphurised in the catalytic hydrogenation plant 12 because it has to be removed Subjected to desulfurization. The product of these sulphurizing amounts of material would then be much less 25 catalytic hydrogenating desulphurisation flows. There is also the fact that through the hydraulic line 14 to the heat splitting system 16. Low desulphurisation of the entire starting material amounts of low-boiling hydrocarbons, within the meaning of the invention, the paraffin content of the gas oil such as light gasoline, which increases in the hydrogenating process and thus the subsequent heat splitting Form sulphurisation, can possibly be made more difficult, so that the heat splitting in the previous 30 heat splitting are distilled off, the case under more stringent and therefore costly product must be carried out under more stringent conditions than it gets through line 18 into the distillation plant 20. Would be necessary if the same starting material, low-boiling substances, such as gas, light petrol and had not previously been desulphurized. Heating oil or the like, which are formed during the heat splitting The procedure according to the invention must therefore have formed 35, will appear at first glance to be unfavorable due to the lines 21 and 22. Over-deducted. The heating oil from line 22 can, surprisingly, but it has been shown that if it is used as a mixing component. A heavy wax distillate fraction with an unsatisfactory sequence of process stages in double the pouring point is returned from the distillation system 20 through the 4 ° line 24 in the circuit to the heat splitting system 16, which is more than balanced, due to the resulting increase in the cost of the process. The heaviest constituents are, if one makes use of the further measure Ge as soil residue from the distillation plant 20, the heaviest, during the distillation of the through line 26. This material represents the end product in the thermal splitting products, very wax-rich broader sense of the invention. Pour point and can be used for all purposes. In the process according to the invention, higher-boiling fractions with these are usually supplied as a direct process product with advantageous properties - heating oil with a lower sulfur and wax content than the. This soil residue represents z. B. is an excellent soil residue from the distillation of heat - 50 netes technical heating oil; it can also be obtained as product cleavage products, and this product component for the starting material of the catalytic can, if desired, be used with others in the cleavage.

Process obtained fractions are mixed, which are separated in the distillation plant 20 and

to change its properties. The recovery through line 24 in the recirculated fraction is such a product in high yield 55 is a wax distillate, which has about the same boiling point due to the special, on superficial examination, area as the charge of the hydrogenating, difficult to understand sequence of desulfurization plant 12. It contains A large number of steps in combination with the circulation amount of high-melting wax, which has been converted during the first run of the wax distillate fraction not obtained by products during the distillation of the heat gap passage through the heat gap system, and therefore has an unlight and is based on the unexpected fact that desired high pour point. In order to achieve the goals of the high-boiling, high-boiling discovery resulting from heat splitting, this waxy distillate fraction, which consists almost entirely of grain and medium boiling ranges and consists of circular components with undesirable properties, has to be fed back into the heat splitting system in the above-mentioned cycle at throughput 65 substances that contribute to the undesirable properties of the end product produced by the heat splitting system to be converted into substances with more favorable higher percentages in products with favorable properties. This recycled material is converted to boiling properties than the fresh one, which is usually in the range of about 343 to 538 ⁰ C.

5 6

According to a preferred embodiment of the Er line 8 introduced so that their sulfur content in the finding, the rehydrating desulphurisation plant 12 flowing through line 10 is reduced Stand fraction of a viscosity-breaking treatment. If the sulfur content of the fraction, however treatment in Annex 28. After this is satisfactory and only its pour point is too high,

Treatment, the material arrives through line 30 in FIG. 5, it is fed through line 44, so that through the

Distillation plant 32. One or more lower-subsequent treatments in the heat gap plant 16

boiling fractions, which are only improved in the viscosity- only the pour point. That through

Have formed refractive treatment, in line 42 can of course not only fed material

the distillation plant 32 are separated. In terms of its sulfur content, but also

For example, one can improve light gasoline and heating oil through io with regard to its pour point, since it

Pull off line 31 or 33. This heating oil can also flow through the heat gap system 16. if

if necessary, used as a mixing component are used by this measure of the introduction of the

the. Through line 34 a heavy gas oil hit fraction is passed through line 42 or 44

discharged. The non-distilling residue is made use of, it is beneficial through this

withdrawn through line 36 and with that through line 42 or 44 the liquid in one amount

Line 26 flowing off, the hydrating Ent- of about 4 to 15 percent by volume of the line 8

To allow sulphurization and the heat splitting subjected to the supplied liquid to flow.

Fraction to a heavy residue fraction with that of the hydrogenating desulfurization plant 12

Satisfactory sulfur content, satisfactory- supplied starting material contains components of the

the pour point and satisfactory viscosity 20 specified boiling range including significant

mixed, which turns out to be high-quality technical quantities of high-melting wax, which the

Fuel or the like. Suitable. The cause of the unsatisfactory pour point is.

The purpose of the addition carried out in the distillation plant 32 is that of the hydrogenating desulphurisation distillation and has the purpose of lowering the lower-boiling amounts of sulfur compounds that form in the excess breaking treatment of the starting material supplied to the viscosity plant 12. Separate the sulfur fractions, as they usually have a higher value content between about 1.0 and 4.0 than the residual heating oil fraction. This weight percentage. The starting material for the hydrogenating residue fraction is withdrawn through line 36, as well as for the desulphurisation system 12 and for the viscosity and although compared to the viscosity breaking cracking system 28, the feed flowing from the asphalt cracking system 28 usually has improved or mixed asphaltic-paraffinic acid properties, However, it turns out to be usually obtained from crude oils. In the preferred embodiment, unsatisfactory in terms of its sulfur content, form of the invention in which a mixed residue, its pour point and its viscosity. This post-heating oil is produced, the starting material for which part is removed by extracting the product which may flow off through line 26, hydrogenating desulphurisation system 12 (and possibly also the 35 from a completely different crude oil than from lines 22, 33 and 34 withdrawn pro - the starting material for the viscosity breaking fissure ducts) mixed with this residue fraction. The plant 28. The starting material for the viscosity bred products withdrawn through lines 26 and 22 have the corresponding cracking plant 28, any desired petroleum-related low sulfur content, stock residue fraction, the hydrocarbon points and viscosities can be used. By mixing these substances 40 containing asphalts, etc., and has a boiling range materials with the effluent through line 36 production above about 552 ° C, usually above 577 ⁰ C, the viscosity breaking treatment domestic product in comparable. Such residue fractions contain different proportions, one wins a comfortably considerable amount of asphalt, wax, number of different products, the different sulfur compounds, etc. and are often used as requirements for a high-boiling heating oil with low-quality heating oil, such as bunker heating oil, low sulfur content, low pour point and In general, however, heating oils are required which satisfy low viscosity. The fuel oil taken from line 33 with regard to its sulfur content, its pour point and the gas oil taken from line 34 and its viscosity meet strict requirements Residue fractions meet these requirements. However, the latter two do not have stakes. These residue fractions have a significantly higher sulfur content in product streams - usually a specific gravity of more than that drawn off through lines 22 and 26 - about 0.986.
genen fractions. In the hydrogenating desulphurisation plant 12

The heavy gas oil 55 removed through line 34 is subjected to catalytic hydrogenation desulfurization has the same or a similar boiling range of a known type instead. As a catalyst you can like the starting material flowing through line 8. a hydrating component on one If necessary, it can be porous support, such as aluminum oxide, with a neten lines 34,38,40 and 42 circulated small amount of silica activated aluminum and that of the hydrating desulphurisation system 60 oxide. The hydrating compo through Line 8 supplied starting material mixed component can be a metal, an oxide and / or a will. Likewise, this heavy gas oil fraction can sulfide of a metal of group VI and / or the also be that through line 14 from hydrogenating Group VIII of the Periodic Table. One Desulphurisation system discharging product in the case of a particularly advantageous combination is a mixture are mixed by being introduced into the line 14 by the dashed line 65 of an oxide and / or sulfide of an iron line 44, such as nickel and / or cobalt oxide and will. If this fraction has an undesirably high or or sulfide, with molybdenum oxide and / or Has sulfur content, it normally turns into the sulfide. The catalytic hydrogenative desulphurization

7 8

takes place under known conditions, ie usually device 8 in an amount of 483 m ³ / day of the catalytic at about 343 to 427 ⁰ C, a hydrogen partial see hydrogenating desulfurization system 12 added pressure between about 36.8 and 105 kg / cm ² and one leads. A distillation back throughput rate between about 0.2 and the 10 parts by volume of starting material indicated in column 4 of the table per part by volume of catalyst 5 characteristic values in an amount of 321 m ³ / day is deducted per hour through line 10. The ratio of hydrogen to exits and the material supplied to the viscosity breaking system 28 is usually between about 17.8 and leads.

89 Nm ^{3 of} hydrogen per 1001 starting material. Hydrogen desulphurization in plant 12

The heat dissipation in the system 16 also takes place at a hydrogen partial pressure (attack in a manner known per se, but must be relative ίο pressure) of 43.6kg / cm ^a at 361 ° C with an hourly mild, so that less as about 15 and the existing liquid space velocity of 1.92 in preferably between about 10 and 15% light gasoline in the presence of 46.3 Nm ^{3 of} hydrogen per 100 liters of Be. The starting material for the transfer of heat. The catalyst contains 2.5 weight cleavage usually consists of 1 to 3 parts of the percent nickel, 1.0 percent by weight cobalt and circulating material per 15-11.0 percent by weight molybdenum on activated aluminum part of the hydrogenated desulphurizing amine oxide . During the distillation of the material fed in through line 14 through hydrielage 12. The desulphurisation of the gas oil obtained is heat splitting takes place at about 427 to 538 ⁰ C, a 18.4 m ^{3 of} heating oil and lighter products per day excess pressure between about 3.5 and 84 kg / cm ² and leads; the distillation residue is obtained in an amount with a throughput rate between about 2.5 20 of 467 m ³ / day and has the characteristic values given in column 3 of the table and 15.0 parts by volume per part of space of the characteristic values given in. This bottoms fraction is the cracking unit at a temperature above 399 ⁰ C ER- 35.3 m ³ heavy gas oil per day from line 34, 38 overheated fuel oil per hour. and 44 mixed. This heavy gas oil has the in

The viscosity breaking treatment in the on column? the characteristic values given in the table. The location 28 is also mild, that is, it is mixed in such a way, which is carried out in an amount of 502.8 m ³ / day, that about 5 to 13% light petrol is formed; has the values given in column 9 of the table for most of the residue fractions. This mixture is proven to be the most advantageous oil circulated through line 24 ^{with 770 m 3 of light gasoline formation of 7 to 11% per day.} The viscous mixing is preferably carried out. The characteristic values of the cycle oil are given in the activity-breaking treatment with the greatest sharpness, column 12 of the table. The product obtained in this way, which still provides a stable product, ie a mixture is subjected to the heat splitting system 16 in accordance with the NBTL stability test.

US Federal Standard 3461.1 is sufficient. The heat splitting takes place at 477 ° C (outlet

Stability test is to be examined oil 20 STUN temperature), a gauge pressure of 14 kg / cm ^2, a to through a chamber rotate left in the 35 flow rate, corresponding to a Vosicheinauf 315 ⁰ C heated steel tube. If the lumen of 0.0006 m ³ of the oil located above 399 ° C is to meet the requirements, part of the reaction coil per 1001 throughput per the steel pipe must not or only insignificantly day, and a cycle ratio of 153 ⁰ J ₀ . This is allowed to discolour, and during the product of the heat splitting, no or at most a very weak 40 is distilled on the pipe. Here, 65.3 m ^{3 of} light petrol per day (brownish to bluish) carbon deposits are deducted. The characteristics of this light gasoline. If the visbreaking treatment in can be found in column 10 of the table. A heating oil system 28 is carried out too sharply, precipitate fraction is discharged through line 22 in an amount from the end product solids, which of course 231.3 m ³ / day. This fuel oil has that in is undesirable. The reaction conditions are given in column 11 of the table. By means of a viscosity-breaking system, the same as line 26, a residue tar fraction is withdrawn in an amount of 200.7 m ³ per day, usually for viscosity-breaking treatment. The identification of residue fractions are used, values of this residue tar fraction can be found in column 13 of the table, provided that a stable product is obtained.

will. The viscosity-breaking treatment can at 50 The through line 10 in an amount of 321 ³ / a temperature between about 427 and 538 ° C and Day m flowing, has by vacuum distillation eineinem pressure between about 3.5 and 21 kg / cm ² geengte crude oil in column 4 of the table. The throughput speed is a characteristic value. This concentrated crude oil is in is from 2.5 to 15.0 parts by volume of the feed system 28 the viscosity breaking treatment in each space portion of the ER in the reaction vessel over 399 ⁰ C subjected 55th This treatment is heated at 454 ° C per hour. (Outlet temperature), an overpressure of 14 kg / cm ²

. and a throughput rate, accordingly

^{3 e 1 s} P ^{1 e 1} a volume of 0.00075 m ^{3 of} the above 399 ° C

In the following, a combined process of heated oil per 100 liters of throughput per day is carried out, measured in the drawing using the 60 The viscosity-breaking treatment described therein with the reference numerals given. 1590 m ³ thrown product is distilled in the plant 32, crude oil per day with the ^{characteristic values given in column 1 of the table below with 18.3 m 3 of} light gasoline per day through line 31, the distillation will be removed, which the in column 5 of the lation at atmospheric pressure and the vacuum table has given characteristic values. Subjected by distillation, 38.2 m ^{3 of} heating oil per day with the ^{light fractions in m 3 being} removed per day through line 6 65 line 33. Column 6 of the table indicated characteristic values withdrawn A heavy gas oil fraction with the in column 2 of the withdrawn. A residual tar fraction is given by the characteristic values specified by the Lei table and is discharged through line 36 in an amount of 227.7 m ³ / day.

This residual tar fraction has the in column 8 of the Characteristic values given in the table. A heavy gas oil fraction is withdrawn through line and im Circuit returned to the heat gap system 16.

By mixing 132 m ^{3 of} the heating oils withdrawn through line and 33 (characteristic values see column or 11 of the table) per day with 169.5 m ^{3 of} the residual tar fraction withdrawn through line 26 (characteristic values, column 13 of the table) per day and with 227 , 7 m ^{3 of} the residual tar fraction withdrawn through line 36 (characteristic values column 8 of the table) per day, a heating oil with a Redwood viscosity of 3500 is produced, which has the characteristic values given in column 14 of the table.

By mixing 269.5 m ^{3 of} the heating oils withdrawn through lines 22 and 33 (characteristic values column 6 and 11 of the table) per day with 196 m ^{3 of} the

Residual tar fraction withdrawn through line 26 (characteristic values column 13 of the table) per day and with 147 m ^{3 of} the residual tar fraction withdrawn through line 36 (characteristic values column 8 of the table) per day, a heating oil with a Redwood viscosity of 350 is produced, which contains the in column 15 of the table has the characteristic values.

Of course, the various product streams can also be used in quantitative ratios other than those given above are mixed with each other, or certain product streams, such as the heating oil or that from Line 34 withdrawn heavy gas oil, can be omitted from the mixtures in order to make various To produce mixtures that meet the various requirements for heating oils, and / or or to balance the production of the petroleum refinery.

split

Yield, percentage by volume of the crude oil. Characteristic values

specific weight

Viscosity, SUS

at 38 ° C

at 54 ° C

at 99 ° C

at 149 ⁰ C

at 204 ⁰ C

Softening point, ⁰ C

Penetration, 25 ^° C., 100 g, 5 seconds

Flash point, ⁰ C

Pour point, ⁰ C ·.

Sulfur, weight percent

Nitrogen, weight percent

Sediment by extraction,

Weight percent

Coking residue,

Ramsbottom,%

Coking residue,

C 0 nr ad s ο n, ° / o

insoluble in n-pentane,

Weight percent

Aniline point, ⁰ C

Octane number, converted to
Reid vapor pressure of 0.7 kg / cm ²

Motor OZ, unleaded

Motor OZ + 0.528 ml BTÄ / 1 ....

Research-OZ, unleaded

Research-OZ + 0.528 ml BTÄ / 1 .. copper strip test, 50 ° C, 3 hours ... Copper strip test, 100 ° C, 3 hours ..

Upper calorific value, g-cal / g

Hydrogen, weight percent

Lower calorific value, g-cal / g

Heat resistance

Distillation, ⁰ C

Start of boiling

End of boiling

10%

30%

50%

70%

90%

100.0 0.8751

-12 1.98

52

130 239 337 367 30.4
0.9188

103

48.1

+32
2.85
0.082

0.50

367
408
443
483
532

29.4
0.8956

0.65
0.068

0.10

349
394
428
463
513

20.2
1.0344

20 597

47
57

357 (D92)
> +49

5.17

<0.01

21.7

18.6

1.15
0.7316

0.99

64.9

71.8

70.1

78.8

46
166

75

96
113
130
147

809 518/615

12th

split

10

Yield, percentage by volume of the crude oil. Characteristic values

specific weight

Viscosity, SUS

at 38 ° C

at 54 ⁰ C

at 99 ⁰ C

at 49 ° C

at 204 ° C

Softening point, ⁰ C

Penetration, 25 ° C, 100 g, 5 seconds

Flash point, ⁰ C

Pour point, ⁰ C

Sulfur, weight percent

Nitrogen, weight percent

Sediment by extraction,

Weight percent

Coking residue,

Ramsbottom, ° / ₀

Coking residue,

Conrad s on,%

insoluble in n-pentane,

Weight percent

Aniline point, ⁰ C

Octane number, converted to
Reid vapor pressure of 0.7 kg / cm ²

Motor OZ, unleaded

Motor OZ + 0.528 ml BTÄ / 1 ....

Research-OZ, unleaded

Research-OZ + 0.528 ml BTÄ / 1 .. copper strip test, 50 ⁰ C, 3 hours ... copper strip test, 100 ° C, 3 hours ..

Upper calorific value, g-cal / g

Hydrogen, weight percent

Lower calorific value, g-cal / g

Heat resistance

Distillation, ⁰ C

Start of boiling

End of boiling

10%

30%

50%

70%

90%

2.4

0.8633 36.3

72 (D 93) -26
2.52

182 384 350 410 220 432 248 454 278 477 307 333

2.2 0.9484

123 47.1

4.7

63

14.3
1.0647

4700

410

71

10

6.0
0.5

0.02

34.1

9542

8.7
9100

31.6 0.8996

101 45.8

(D 93) +32 1.08 0.094

0.11

87

354 396 427 463 506

4.1 0.7279

0.13

66.1 77.7 70.4 85.3 1

42

168

76

98

117

132

148

11 12th split
13th 14th 15th Yield, volume percentage of the crude oil ...
Characteristic values
specific weight 14.55
0.8581
37.5 48.4
0.9383
82.6
41.8 12.6
0.9497
517
88 0.9765
3500
(Redwood) 0.9377
350
(Redwood) Viscosity, SUS
at 38 ° C 79 (D 93) 204 (D 93) - 71 (D 93) at 54 ⁰ C at 99 ⁰ C at 49 ° C at 204 ⁰ C 82 (D 93) Softening point, ° C Penetration, 25 ⁰ C, 100 g, 5 seconds ..
Flash point, ⁰ C

11

split
13th

15th

Pour point, ⁰ C

Sulfur, weight percent

Nitrogen, weight percent

Sediment by extraction,

Weight percent

Coking residue,

Ramsbottom, ° / o

Coking residue,

C ο nr ad s ο n,%

insoluble in n-pentane,

Weight percent

Aniline point, ⁰ C

Octane number converted to a Reid vapor pressure of 0.7 kg / cm ²

Motor OZ, unleaded

Motor OZ + 0.528 ml BTÄ / 1 ..

Research-OZ, unleaded

Research-OZ + 0.528 ml BTÄ / 1 copper strip test, 5O ⁰ C, for 3 hours. Copper strip test, 100 ° C, 3 hours

Upper calorific value, g-cal / g

Hydrogen, weight percent

Lower calorific value, g-cal / g

Heat resistance

Distillation, ° C

Start of boiling

End of boiling

10%

30%

50%

70%

-12 0.60

+21 I 1.74

193 380 351 389 226 398 260 412 289 443 311 333

+27
1.48
0.2

0.01
1.69

+2
3.5

0.01

-15

2.5

0.03

10386

11.2
9817

10056

10.3
9528
No. 1 stable

10278

10.8
9722
No. 1 stable

Claims (4)

Claims: 40 1. A method for reducing the sulfur content and the pour point of heavy vacuum gas oil with a boiling range between about 343 and 577 ⁰ C, which contains a substantial amount of boiling in the range of about 399 to 577 ° C constituents, characterized in that the heavy vacuum gas oil by catalytic hydrogenating desulfurization under known conditions at a temperature between about 343 and 427 ⁰ C, a hydrogen partial pressure between about 36.7 and 105 kg / cm ² and a space velocity between about 0.2 and 10 at least 50% of the sulfur compounds removes by conversion into hydrogen sulfide, the gas oil obtained in the hydrogenating desulfurization in a manner known per se at an excess pressure between about 3.5 and 84 kg / cm ² , a temperature between about 427 and 538 ⁰ C and a space velocity between about 2.5 and 15.0 subject to heat splitting with the formation of about 10 to 15% light gasoline, from the product of the heat spa A distillate of high pour point and wax content with a boiling range between about 343 and 538 ° C is distilled off, this is recycled in an amount of 1 to 3 parts by volume per part of the fresh charge fed to the heat splitting stage, and as the bottom fraction in the distillation of the Separating the product of the heat dissociation, a high-boiling hydrocarbon mixture of relatively low sulfur content and pour point, this product optionally with the distillation residue of the product of the viscosity-breaking treatment of a concentrated crude oil and optionally also with part of the heating oil fraction obtained during the distillation of the product of the viscosity-breaking treatment of the concentrated crude oil and a Part of the heating oil fraction obtained in the distillation of the product of the heat dissociation is mixed and, if necessary, in the distillation of the product of the viscosity-breaking treatment of the concentrated Ro Helle's recovered heavy gas oil fraction is added to the feed of the hydrogenating desulfurization stage or the thermal cracking stage. 2. The method according to claim 1, characterized in that a constricted by vacuum distillation of crude oil having a specific gravity greater than about 0.986 and a boiling range above about 552 ° C a mild viscosity-breaking treatment under conditions known per se at temperatures of about 427-538 ⁰ C. , an overpressure of about 3.5 to 21 kg / cm ² and a throughput rate of about 2.5 to 15.0 with the formation of about 5 to 13% mineral spirits subjected, the product to the viscosity-breaking treatment and distilled at least a portion the residue obtained from this distillation with that from the desulfurization and heat gap treatment recovered high-boiling hydrocarbon mixture mixed. 3. The method according to claim 1, characterized in that the heavy gas oil fraction of the hydrogen desulfurization or heat splitting in an amount of about 4 to 15 percent by volume of the starting material fed to the hydrating desulphurisation. IO 4. The method according to claim 2 and 3, characterized in that the starting material for the Viscosity breaking treatment uses the bottom residue of the same crude oil from which the heavy material used as the starting material for the hydrogenative desulfurization is carried out by distillation Vacuum gas oil wins. Considered publications:
German Auslegeschriften No. 1 014 692.1 050 946; U.S. Patent Nos. 2,662,845, 2,687,986. 1 sheet of drawings 809 518/615 3. 68 © Bundesdruckerei Berlin