DE2360092A1 - PROCESS AND CATALYSTS FOR THE MANUFACTURING OF MULTIPLE RANGE OILS WITH IMPROVED PROPERTIES - Google Patents

Description

The present invention relates to a process for the production of lubricating oils of high viscometric quality and especially of direct multi-range motor oils, by hydroisomerization of paraffins, preferably of paraffins from hydrocracking.

Multigrade oil is an oil that is divided into several SAE categories are to be classified at the same time, i.e. an oil, the viscosity of which changes less with temperature than that of an ordinary non-multigrade oil is.

In the table below are the viscometric Identifiers of the main multigrade oils indicated as shown on the graphic representation by J.QROEP are defined, modified according to ASTM D 567-53 (SAE Handbook 1966).

A0982A / 1013

Table 1

Mehrbereidis oils W. 20th V. 1. (ASQIM D 567) 145 Visibility cStbai 37, $ j until 50 70 85 Viscosity oSt until 9.6 10 W. 30th 100 to 150 30th until 77 until 120 5.8 until 13th 10 W. 40 130 to 50 until 150 9.6 until 17th 10 W. 20th l40 130 until 13th until 9.6 20th W. 30th -20 to 138 42 = 5.8 until 13th 20th VJ 40 90 to 143 70 9.6 until 17th 20th 110 to 85 13th

A multigrade oil is today generally prepared by mixing a very fluid base oil with varying amounts of a polymer, for example, on the nature of the polymethacrylate is intended to improve the viscosity properties as a function of temperature and zi 'leioii which makes oil-viscous. The viscosity additives used are generally less stable to mechanical effects (shear) and temperature effects than the actual oil.

So, as you can see, it would be extraordinarily interesting about To have multigrade oils that do not contain any viscosity additives and thus have greater stability. The process of the present invention enables such oils to be made.

When these oils are obtained directly from a refining process, they are referred to as "multigrade direct oils".

The direct multigrade oils obtained with the process according to the invention However, in order to obtain other types of multigrade oils, they may or may not be used together with conventional viscosity additives.

409824/1013

The paraffins treated in the process according to the invention are preferably the paraffins of hydrocracking obtained by dewaxing the lubricating base oil derived from a hydrocracking or hydro refining process of vacuum distillates and / or deasphalted vacuum residues, as for example in French patent specification No. 1 582 758 ". These paraffins are normally "at Baum temperature (20 ⁰ G) firmly. It should also be on the excess sludge Patent 3,560,370 and French patent application 7,112,416 and the US Patent Application 241,690 from 6 April 1972.

Prior art can be seen in US Pat. No. 3,365,390, according to which a lubricating oil that is not a direct multigrade oil is, by hydroisomerization of a normally solid paraffin in the presence of a reforming catalyst such as Platinum is produced on alumina, taking on the hydroisomerization stage a dewaxing stage follows.

It has now been found that the yield of direct Mehrbereiehsölen can be increased by on the one hand uses a catalyst that is a critical. Contains amount of halogen, and on the other hand under a critical ammonia pressure is working.

Thus, in the present invention, a process for the production of multi-grade oils is described, in which a mixture of hydrogen and a paraffin is brought into contact at a temperature of 300 to 450 C with a catalyst consisting of an aluminum oxide carrier, at least one noble metal from Group VIII periodic table of elements and 0.1 to 5 Gew.?& a halogen, and in that the one - subjecting oil obtained after Itaktionieren of the total product i to dewaxing in order to extract at least a portion of the unconverted paraffins; the method is characterized in that said contact takes place under a partial ammonia pressure of 1 to 500 g / cm ² . '

A09824 / 1013

The normally solid paraffins of hydrocracking can be obtained by reacting, brings hydrogen and crude oil vacuum distillates and / or deasphalted crude oil vacuum residues, whose boiling point is at least partially above 45O ⁰ C under Hydrokrackungsbedingungen with a Hydrokrackungskatalysator in contact that fractionating the product obtained for example by, to isolate a fraction having a boiling point usually above 380 ⁰ C and preferably above 430 ° C, and in that said Iraq ion by a known method such as is described, for example below in conjunction with the isomerized paraffin dewaxed.

As already stated, the hydrocracking catalysts contain usually one or more metals or compounds of metals of groups VI and / or VIII, e.g. molybdenum, tungsten, Nickel, cobalt and / or platinum, which is an acidic carrier, e.g. silicon dioxide-aluminum oxide or halogen-containing aluminum oxide, added or applied to it. The process conditions are, for example, the following:

Temperature between 300 and 480 ⁰ C pressure between 30 and 200 kg / cm

Hourly liquid flow rate of hydrocarbons

0.3 to 5 volumes per volume of catalyst, hydrogen throughput 500 to 5000 liters per liter of charge.

The hydrocracking paraffins obtained in this way have, at least for the most part, a molecular weight above 500; the middle one Molecular weight of the paraffin charge is approximately above 400. They generally have a viscosity of 8 to 20 cSt at 98.9 ° C, a viscosity index on the order of 130, a sulfur content below 30 ppm by weight and a nitrogen content below 5 ppm by weight

The hydroisomerization reaction takes place between 250 and 450.degree. C., preferably between 300 and 3900.degree. The pressure is, for example, 10 to 150 kg / cm ² and preferably 30 to 100 kg / cm 2. Man

409824/10 13

v / ends advantageously an hourly Yoliimendiirchatz (VTH) of 0.2 "to 5 Mt er, -preferably 0.5 to 2 liters of liquid hydrocarbons per liter of catalyst. The throughput of gaseous hydrogen is, for example, 300 to 3000, preferably up to 1500 liters per liter of liquid hydrocarbons, under normal temperature and pressure conditions. Under these conditions the hydrocarbon charge is practically 100% liquid. The charge can be introduced into the reactor from above, then one works in a trickle phase in a hydrogen atmosphere also work with an ascending stream of the reaction components.

It has been found that the properties of the oil obtained as the end product can be further improved by part of the oil that is obtained after suitable treatment, e.g. distillation and / or dewaxing, of that which flows out of the reactor receives, recycled.

On the one hand there are the special catalysts, on the other hand it is the purity of the batch that make it possible for the conversion to take place under light conditions (pressure between 50 and 80 kg / cm, temperature between 300 and 390 C) can be carried out and oils are obtained whose aromatic content is almost zero amounts to. Thus, in the presence of a catalyst made of platinum on fluorine-containing aluminum oxide at 350 ° C., 45% by weight of oil with the Viscosity index 135, the aromatic content of which is practically the same Is zero, while at 420 C the oil obtained contains 15 / ^ aromatic hydrocarbons. Due to the fact that this The aromatic hydrocarbon content is close to zero, it is not necessary to use the liquid products of the invention to undergo final hydrotreatment, which is of great economic interest.

The hydroisomerization treatment according to the invention is carried out in Presence of catalysts consisting of one or more noble metal (s) of group YIII and / or their alloys, which in an acidic carrier of the type of alumina,

409824/1013

to which a halogen has been added, incorporated or applied are. The use of precious metals is because of high purity of the batch and in particular the very low sulfur content possible. Mixtures of metals can also be used e.g. platinum-f-iridium, platinum + bhenium, platinum + cobalt, Platinum + g-ermanium, platinum + gold.

It has been found that the catalysts that are suitable for the invention Most suitable processes which are platinum-alumina-halogen catalysts, with the halogen being preferred da3 is fluorine. The halogen content of the catalyst can be advantageous between 0.1 and 5 wt.5 ^ and preferably between $ 0.3 and $ 0.8 in the case of fluorine and between $ 0.3 and $ 3 in the case of chlorine.

The halogen and the noble metal can by known methods be introduced into the catalyst, e.g. by means of those used in the manufacture of the reforming catalysts.

This is done by using ammonia at the same time and a catalyst containing a halogen are surprising. Ammonia has a negative effect (reduced yield) when used with a platinum on alumina catalyst with no halogen.

The hydroisomerization product can be fractionated as follows, for example:

- and which results in a fraction, whose boiling point is above 380 ⁰ C after the dewaxing a G-around oil whose viscosity index is between eg 130 and 150, having a viscosity at 98.9 ⁰ C above 7 cSt and having a melting point of, for example, -20 C; this basic oil is at least in the range of the multigrade oils 10 W 20;

- into a gas oil fraction (250 to 380 ° C) with a diesel index above 90 is or is 90; their cetane number is above 70 (engine gas oil specification: cetane number> 50);

409824/1013

- In a jet fuel fraction (150 "to 25O ⁰ C), the smoke point is above 45 mm (kerosene specification: smoke point> 21 mm);

- into a fraction of strongly isoparaffinic character (80 to 150 ° C), which is practically free from naphthenes and aromatics and can be a good reform batch or an interesting part of the "pool" gasoline;

- in a light fraction (<80 ° C) that is rich in isoparaffins is (Iso-Cg, Iso-C, - and Iso-C.).

The excellent quality of the by-products and their very low content of impurities (nitrogen and sulfur) give the conversion an additional fourth: The jet fuel fraction appears particularly interesting because it ^{makes up about 50 $ of the fraction boiling between 80 and 380 0} C, that is a yield of $ 10 to $ 20 relative to the starting paraffin. ·

The dewaxing treatment to which the oil obtained from hydroisomerization is subjected can be carried out by any known method, for example by treatment with a solvent such as methyl isobutyl ketone or with a solvent pair such as the mixture of methyl ethyl ketone and toluene, at a temperature between 0 and -70 ⁰ C. the present invention is not limited to a particular type of dewaxing. The paraffin obtained can also be de-oiled using known methods.

The after dewaxing the fraction above 380 ° C. The paraffins that have been retained can be recycled, if necessary, before or after a temporary oil removal, depending on whether one works with or without oil recycling. In all cases, however the oil yield is increased by a second de-oiling.

The fluids of the invention can be made according to that described above Treatment can be used directly, e.g.

4098 24/1013

as multigrade engine oils 10 W 20 or as hydraulic fluids according to the standard SAE 71 R 1. They can also be used in a mixture with different additives, especially those, which improve the viscosity, e.g. with polyisobutenes or methacrylic polyesters.

The oils according to the invention are also particularly interesting insofar as than they have a remarkably homogeneous distribution of viscosity and viscosity index. This distribution can can be determined by thermal diffusion of the rheological characteristics of the various fractions obtained of the base oil.

In the examples below, the hydroisomerization charge is used manufactured in the following way:

One has the hydrorefining of a deasphalted vacuum residue (d |. ° = 0.928, S = 2.58 wt ^, N = 800 ppm by weight and viscosity at 98.9 ⁰ C = 35.7 cSt) in the presence of a catalyst with the following Mark made:

composition

Al ₂ O ₃ 56 </ o (in weight) /G SiO ₂ 20? O Il MoO ₃ 1,696 Il HiO 8fo Il 250 m ²

Specific surface

The catalyst is previously sulfurized H ₂ S, which is diluted with H ^v _2, under the following conditions:

T = 32O ⁰ C (6 hours) H ₂ S / H ₂ = 4/100 (in moles)

409824/1013

The process conditions used were as follows:

pressure 120 kg / cuT liter YVH = 0.5 liter batch per hour Catalyst and pro T = 400 ⁰ G H ^ / hydrocarbons

serstοffcharge

1000 liters / liter

The oil obtained is distilled and the residue from this distillation, the boiling point of which is above 380 ° C., is recovered. Subjecting to a dewaxing at -22 ⁰ C by Methylisobuty! Ketone. On the one hand, an oil with a viscosity index of 125 (yield 42% by weight ) and, on the other hand, solid paraffins (yield 8% by weight), which form the hydroisomerization charge of the examples below and whose main characteristics are given in Example 1, are obtained.

40.9824 / 1013

(Comparative example)

Production of a direct multigrade oil 1O W 20 by hydroisomerization of hydrotreated paraffins with a catalyst that does not contain halogen, in the absence of ammonia.

Identification of the batch:

d | ° 0.850

S ......... <(2O ppm in wt.

M <2 ppm by weight

Viscosity "at 98.9 ° C 10 cSt

Mean molecular weight ... 620

GH ₃ / CH ₂ ratio 0.065

Catalyst platinum on aluminum oxide:

Composition: AIpO, ... 99.2%

Pt 0.8 i °

Specific Surface area ......... 232 m ² / g

Process conditions:

Pressure 60 kg / cm

T 410 ⁰ C

WH 1

Gaseous hydrogen / liquid hydrocarbons = ^:. · '. .

1000 liters / liter (TPN) Partial ammonia pressure ......... 0

After the hydroisomerization, the effluent from the reactor is subjected to distillation, so that the following fractionation is made possible:

Boiling point <C 80 ⁰ C light petrol

80 to 150 ° C naphtha

150 to 25O ⁰ C jet fuel

250 to 38O ° C engine gas oil

409824/1013

38O ^{+ 0} C lubricating fraction

The lubricating fraction is then at a temperature of -20 C by means of a methyl ethyl ketone-toluene mixture in the ratio 1/1 (by volume) dewaxed.

Under these conditions, the oil is obtained with a yield of 40% by weight and unconverted paraffins with a yield of 25 wt. . '

The oil obtained corresponds to the specification 10 ¥ 20 (Table 1) and has the following characteristics:

Viscosity at 37.8 ° C 40.9 cSt

Viscosity at 98.9 ° C 7 cSt

Viscosity index 134

Pour point - 18 ⁰ C -

Initial boiling temperature 380 ° C

Cleveland ignition point 228 ° C

■ CH ₃ / CH ₂ 0.08

S wt.ppm 10

N wt.ppm 2

Coke residue according to Konradson 0.02

2 (comparative example)

In this example, the batch from Example 1 is treated in the presence of the same catalyst which is obtained by impregnation with Bi ¹ ^ H 0.5 wt. ^. Fluorine added.

The process conditions are as follows:

Pressure .. 60 kg / cm ²

T 35O ⁰ C

■ - 'WH 1

H ₂ / HC 1000 liters / liter '(TPN)

Partial NBL pressure 0

409824 / 101-3

The effluent is fractionated as in Example

Under these conditions, 41% by weight of oil and 25% by weight of oil are obtained unconverted paraffins. ·

The oil obtained does not meet the specifications 10 W 20; it has the following characteristics:

Viscosity at 37.8 ° G 32 cSt

Viscosity at 98.9 ° C 5.5 cSt

Viscosity index .. 133

Pour point - 18 ° C

Initially boiling temperature 380 ⁰ C

Cleveland ignition point 228 ⁰ C

₃₂ 0.10

S wt.ppm ^ 10

N G-ew.ppm <2

Coke residue according to Konradson .. ^ 0.02

The batch of Example 1 is treated with the catalyst of Example, but with a partial ammonia pressure in the Reactor of 30 g / cm.

The process conditions are as follows:

Pressure 60 kg / cm ²

_{Partial.UH 3} rDruQk ... 0.03 kg / cm ²

T 35O ⁰ C

WH 1

H ₉ / HC 1000 liters / liter

After proceeding as in Example 1, 45 wt Oil 10 ¥ 20 and 28 wt. ^ Unconverted paraffins. The oil has the following characteristics:

409824/1013

Viscosity at 37.8 ⁰ G ............. 41 cSt

Viscosity at 98.9 ⁰ G .... ,, ..., ... 7 cSt

Viscosity index .. 135

Flow point .... - 18 ⁰ C

Initial boiling temperature ............ 380 C

Cleveland ignition point. .. 232 ° C

₃₂ «... 0.16

S wt.ppm ... f. <10

N wt.ppm <2

Coke residue according to Konrads on ...... <C 0.02

The transition from 0.065 to 0.16 of the ratio CH ~ / CH ₂ explains the isomerizing effect sought.

As for the hydrocarbons, the oil has the following composition;

Isoparaffins, »,,,.,.,« ·· .. «« 83 _? 7th

The yields of other products obtained from the reaction are as follows:

_Weight ^ / batch C ₁₊ C ₂₊ O ₃ ... fM 0.97

C ₅ - 80 ⁰ C, ", .. 1.32

80-150 ⁰ C 2.40

150-250 ° C 8.80

250-35O ° C 8.80

This example is given for comparison »(catalyst with excessive fluorine content).

409824/1013

The batch from Example 1 is mixed with the catalyst from Example 1 treated by impregnating Bi ^ H 6 wt. $ £ fluorine added.

The process conditions are as follows:

Pressure 60 kg / cm

HH ^ partial pressure 0.03 kg / cm ²

T 35O ° C

WH 1

H ₂ / HC 1000 liters / liter (TPN)

In this way 34% by weight of oil and 22% by weight of unconverted oil are obtained Paraffins. The oil has the following characteristics:

Viscosity at 37.8 ° C 18 cSt

Viscosity at 98 _f 9 ° C 4 cSt

■ Jiaosity index ............ 130

ilLosing point * ..... - 18 ⁰ G

Initial boiling temperature ...... 380 G

Cleveland ignition point. . 220 ° C

₃₂ 0.15

S weight ppm <10

Coke residue according to Konradson <0.02

This oil does not have the characteristics of a multigrade oil 10 W 20 on.

Example 3 is repeated, but after the first dewaxing a second deoiling of the paraffins was carried out.

In this case the global oil and paraffin yields are as follows:

409824/1013

Paraffins .................. 25

Oil 48 wt

So in this Pall the yield of oil could get through 10 ¥ 20, one second deoiling around. 3 points to be increased; the rheological Properties of this oil are the following:

Viscosity at 37.8 ° C ...... 44 cSt

Viscosity at 98.9 ° C 7.2 cSt

Viscosity index 135

So in addition to increasing the yield, it is also an easy one Viscosity improvement come; which is advantageous: "■ ·, -is., the deoiling, after the first dewaxing of the hydroisomerization product, the recovery of heavy ones Allows compounds with a strongly paraffinic character.

Example 3 is repeated, with the catalyst of Example 1, which is 0.5 wt. $ By means of hydrofluoric acid Fluorine added.

An oil 10 × 20 was obtained, the characteristics of which are practically identical to those of the oil obtained in Example 3. The yield of oil has reached 44 ° i, and it has 29 wt. ^ Obtained unconverted paraffins.

409824/1013

Claims (11)

P_a_ t_e_n_ t _a_n_s_ £ _r_ü_c_li_e A process for the production of reversible oils, a mixture of hydrogen and a paraffin with a catalyst consisting of an aluminum oxide carrier, at least one noble metal of group VIII and 0.1 to 5% by weight of a halogen a temperature of 300 to 450 C and the oil obtained is subjected to dewaxing in order to extract at least some of the unconverted paraffins, v / ob.ei the process is characterized in that said contact is carried out under a partial ammonia pressure of 1 up to 500 g / cm. 2) The method of claim 1, wherein the treated paraffin is a Is paraffin of hydrocracking. 3) The method of claim 2, wherein the partial ammonia pressure is 10 to 100 g / cm ² . 4) The method according to claim 2, v / obei the catalyst 0.3 to 0.8 wt. Io contains fluorine. 5) Method according to claim 2, wherein the catalyst contains 0.3 to 3 wt. $ Chlorine. 6) The method according to claim 2, v / obei the pressure under which the contact takes place, 40 to 150 kg / cm ² . 7) .The method according to claim 2, v / obei the pressure under which the contact takes place is 50 to 80 kg / cm ² . 8) The method according to claim 2, v / obei the group VIII metal Is platinum. 9) The method according to claim 2, v / obei is the average molecular weight the batch is above 400. 409824/1013 2360Ö32- 10) Method according to Claim 1., V / obei the treated paraffin through Dewaxing a crude oil fraction is obtained whose boiling point is in the range of lubricating oils. 11) The method according to claim 1, v / obei the unconverted paraffins be brought into contact again with the catalyst and the hydrogen. 40 98 2 Ul IQI 3