CA1088884A

CA1088884A - Process for the conversion of hydrocarbons

Info

Publication number: CA1088884A
Application number: CA249,299A
Authority: CA
Inventors: Wouter C. De Gruijter
Original assignee: Shell Canada Ltd
Current assignee: Shell Canada Ltd
Priority date: 1975-05-30
Filing date: 1976-03-31
Publication date: 1980-11-04
Also published as: GB1546398A; DE2624023C2; FR2312550B1; JPS51146502A; NL182452C; FR2312550A1; NL7506416A; DE2624023A1

Abstract

ABSTRACT
A process for the hydroconversion of hydrocarbons over a Co/Mo/F/Al2O3 or Ni/Mo/F/Al2O3 catalyst having a high compacted bulk density, which catalyst has been prepared from an alumina hydrogel with a low compacted bulk density by incorporating the metals and optionally fluorine into the hydrogel followed by calcining the composition; if the pore volume quotient of the hydrogel is below 0.5, a specified minimum amount of fluorine has to be incorporated into the hydrogel.

Description

-- 2 ~
The present invention relates to a process for the catalytic conversion Or hydrocarbons in the presence of hydrogen and in particular to the preparation o~ high-viscosity-index lubricating oils by hydrocrackin~ a mixture of heavy hydrocarbons.
In the preparation o~ hi~h-viscosity-index lubricatin~ oils by hydrocracking a mixture of heavy hydrocarbons lo~_viscosity~index compounds present in the feed are converted into high-viscosity-index ~;
compounds. At the same time the nitrogen, sulphur and oxygen contents of the oil are considerably reduced.
The suitability of catalysts for use in the preparation of ~ ;
high-viscosity-index lubricating oils by hydrocracking a mixture o~ heavy hydrocarbons depends on their temperature requirement, aromatica retention and selectivity, which are defined as follows.
Under ~iven operating conditions and startine from a F,iven feed ~ ~;
for the preparation of a lubricating oil with a previously selected ~ `` ;`;
viscosity index after dewaxing, the "temperature requirement" ;
, is the temperature that must be applied to obtain such a lubricatin~
oil, the "aromatics retention" is the percentage of aromatics present ;`~
in the said lubricating oil calculated on the aromatics content o~ the feed, and the ~selectivity~' is the yield of the said lubricating oil. Accordin~ as the temperature requirement and the aromatics retention o~ the catalysts are lower and the selectlvity higher, the~ are better suited to the preparation of high-viscosity-index lubricatin~ oils by hydrocracking a mixture of heavy hydrocarbons.
:
Over the years a great number of catalvsts have been proposed :
for the prep~ ation of hi~h-visaosity-index lubricatin~ oils by hydrocrackin~ a mixture Or heavy hydrocarbons. As a rule they contain one or more metals of Groups VIB, VIIB and/or VIII or sulph1des or oxidesthereof supported on a carri0r consisting of one or more ~ ;
.~
oxides of elements of Groups II, III or IV. These catalysts may also contain promoters such as phosphorus or boron and a halo~en, :` '`
, 3'~

such as chlorine or ~luorine.
An extensive in~estigation b~ the Applicant into the suitability of catalys~s of the type described herelnbefore for the preparation of high-viscosity-index lubricating oils by hydrocracklng a mixture of heavy hydro-carbons has shown that their suitability for this purpose largely depends on the kind and the quantit~ o~ metals and halogen present on the carrier and on the type of carrier and its properties.
A number of the catalysts of the type described hereinbefore in-vestigated proved to be perfectly unsuitable for the said application, because their temperature requirement and aromatics retention were far too high, whereas their selectivity was far too low. Most of the catalysts investigated were moderately suitable for the said application. However, either the tem-perature requirement, or the aromatics retention, or the selectivity of these catalysts was-insufficient for an optimum performance of the catalysts. How-ever, a small group of catalysts of the above-mentioned type showed excellent performance in the preparation of high-viscosity-index lubrica~ing oils by hydrocracking a m~xture of heavy hydrocarbons. The temperature requirement and aromatics retention of these ca~alysts were very low, whereas the selecti-vity was ver~ high. A further investigation of catalysts of the above-mentloned type for the preparation of high-viscosity-index lubricating oils by hydrocracking a mixture of heavy hydrocarbons has shown that the catalysts must meet the following requirements to obtain optimum performance.
The ready catalyst should have a bulk density of at least 0;8 g/ml and contain at least 3 pbw nickel and/or cobalt and 10 pbw molybdenum, re-spectlvely, per 100 pbw alumina carrier and in addition fluorine. In this patent application the term bulk densit~ of a material should be taken to designate the quotient of the weight of a certain quantity of the material and its volume after th~rough compactlon, which may very suitabl~ be done with -the aid of an electric vibration.

In addition to the:ir apr)lication as cataly~tFJ for th~ pre~aration of high-viscosity-index lubricating oils by hydrocracking a mixture of heavy hydrocarbon~, the catalysts accordin~ to t.he invention are also suitnble for a~plication in other processes in which hydrocarbons ~ , are converted at elevated temperature and preasure and in the presence of hydrogen.
The present invention therefore relates to a process for the :~ `
conversion of hydrocarbons in which the hydrocarbons are contacted at elevated tem~erature and pressure and in the presence of bydrogen with a fluorine-containing catalyst containing nickel and/or cobalt . ~ .
and, in addition, molybdenum on alumina as the carrier, which catalyst has a bulk density of at least o.8 g/ml, contains at least 3 pbw nickel and/or cobalt and at least 10 pbw molybdenum, res~ectively, per 100 pbw carrier and has been prepared as follows, starting from an alumina hydrogel from which a xeroeel with a bulk denslty of less than o . a g/ml can be obtained by drying and calcining: ~ i !, ' ` ' ' "
a) When the pore volume quotient of the sald xeroge.l is ab least ~ ~ -0.5, the catalyst preparatlon i~ ef~ected by incorporation of the metals and, if desired, ~luorine in the alumina hydrogel and by dryin~ and calcining the composit;on.
b) When the pore volume quotient of the said xerogel is Iess than 0.5, the catalyst prepa~ration is effected by incorporation of the ;.
metnls and at least part o~ the fluorine in the alumina hydrogel .. . .
and by drying and calcining the composition, it being understood ~ ;:
that in the latter case enough fluorine is incorporated in:the alwmlna hydrogel to insure that from this ~luorine-containin~ alumina hydrogel a xerogel can be obtained b~ drying and calcining whose pore volume quotient is at least 0.5.
For the preparati~on of oatalysts that can~be applied according to the present lnvention only certain~alumina hydrogels are eligible. ~ 2;~
: ~ ~o establish whether an alumina hydrogel is suitable to be used as starting material for the catalyst preparation and, if so, to ': : : ~

1088~38~
1~

For the prep~ration of the catalyst a pr;mary requirer~ent i9 that tile starting material should be an alumina hydrogel. Thls alumina hydrogel must have the property that a xerogel with a bulk density of less than 0 o &/ml can be~ obtained from i.t by dry;n~
and calcinin~. The course of the catalyst preparation startinf, ~rom this hydrogel depends on the pore voll~e quotient of the said xerogel. In this ~atent application the term pore volume quotient of a material should be taken to desi~nate the quotient of the mercury pore volume and the tot~1 pore vol~ne of the material, the mercury ~ore volume being defined as the pore volume present in pores with a diameter larger than 7.5 nm determined with mercury, and the total pore volume as the sum of the pore volume present in pores with a diameter smaller than 60 nm determined with nitro~en :
and -the pore volume present in pores with a dia~eter of at least .: .:
60 mn determined with mercury. ~ "

The pre~aration of the catalysts starting from an alumina hydrogel from which a xerogel w;.th a bulk density of less than ~

O.o g/n~ and a pore volume quotient of at least 0.5 can be obtained ~ :
by drying and calcining, is effected by incorporation of the metals and, if desired, fluorine in the alumina hydrogel and by drying and calcining the composition. .. ~ .
The prepQration of the cntalysts starting from an alumina `;
hydrogel from which a xerogel with a bulk density of le58 than `~
0,ô ~/ml and a pore vol~unc quotient of less than 0.5 can be obtained .;
by drying and calcination, i~ effected by incor~oration of the metals and a.t least part of the fluorine in the alumina hydro~,el and by drying~and calcinin& the composltion; in this catalyst preparatlon :~ ~ :

enough flùorine has to~be incorporated~in the slumina hgdrogel~
to ensure that from this fluorine-contalning~alumina hydroeel:a ~
xerogel can be obtained by drying and calcining who~e pore~:volume quotient i5 a.t least 0.5~

. . .
"~

:

esta61ish furt~er in which way the catalyst preparation has to be carried outJ a sample of the hydrogel concerned is dried at 120C
and calcined at 550C. OE the xerogel thus obtained the bulk densi-ty and the pore volume quotient are determined. Only if the bulk density of the said xerogel is less than 0.8 g~ml, is the hydrogel ~, , , eligible for use as starting material in the catalyst preparation.
The pore volume quotient of the said xerogel determines in which `~
~ay catalyst preparation should take place. If the pore volume ~ :
quotient of the said xerogel is less than 0.5, care should be taken ~` ;
that sufficient fluorine is incorporated in the hydrogel during the catalyst preparation. The minimum quantity of fluorine to be in-corporated in the hydrogel in the catalyst preparation can be determined by incorporating various quantities of fluorine in some ~ `~
samples of the hydrogel concerned and by drying the fluorine-containing hydrogels at 120C and calcining them at 550C. Of ;~
the fluorine-containing xerogels thus obtained the pore volume .
quotient is determined. The above-mentioned minimum quantity of fluorine is that which leads to a fluorine-containing xerogel with ~ ;
a pore volume quotient of 0.5.
... ,~ .
In the preparation of the present catalysts the metals and, i$ desired, fluorine are incorporated in the hydrogel and the composition is subsequently dried and calcined. Incorporation o~ the metals ln the hydrogel may very suitably be effected by treating it with an aqueous solution conkainlng a nickel and/or `
cobalt compound and, in addition, a molybdenum compound. This treatment ls preferabiy carried out at a temperature above 50~C
and in particular at a temperature between 60 and 250~C. Fluorine may ~e incorporated in the catalysts, ei~her when the alumina is still in the hydrogel form, or after calcination of the composition, 3n or by fluoriding in situ. Fluoriding in situ o~ the catalyst may `~
be effected in the initial stage of the process for which the .~ , ,~ , 1~8~

catalyst is used by adding a certain quantity of a 1uorine compound to ~he gas and/or liquid stream that is passed through the catalyst until the required fluorine con~ent of the catalyst has been reached.
Incorporation of fluorine in the c~talyst while the alumina is still in the hydrogel form, is preferably carried out by treating the ;
hydrogel with an aqueous solution containing a nickel and/or cobalt `
compound, a molybdenum compound and a 1uorine compound. In the process according to the invention use is preferably made of a catalyst in which at least part of the fluorine and more in particular substantially all the fluorine is incorporated while the alumina is still in the hydrogel orm.
Catalysts eligible for use in the process according to the in~ention contain at least 3 pbw nickel and/or cobalt and 10 pbw ,...... ... . .
molybdenum, respectively, per 100 pbw alumina. Preference is given to catalysts containing 25-80 pbw nickel and/or cobalt and 50-80 pbw molybdenum per 100 pbw alumina and in particular to catal~sts in ; ;
which moreover the weight ratio between nickel and/or cobalt on the one hand molybdenum on the other, lies between 1:1 and 1:5. -~
The catalysts preferably contain 10-30 pbw fluorine per 100 pbw alumina, it ~eing understood that, if the catalysts are used for the preparation o high-viscosit~-index lubricating oils by hydrocracking a mixture o~ heavy hydrocarbons, their ~luorine content will preer- ; !
ably be 10-25 pbw per 100 pbw alumina, whereas, i~ they are used for ~ ~
the preparation of light hydrocarbons by hydrocracking heavy hYdro- ;
carbons, their fluorine content will preerably be 20-30 pbw per 100 pbw alumina.
Whereas the alumina hydrogels that are used as starting material in the catalyst preparation have the property that a xerogel ~ ": ~
having a bulk density of less than 0.8 g/ml can be obtained from ~hem, by drying and calcining the catalysts prepared on the basis o ~ -~

these hydrogels should have a bulk density of at least 0.8 ml/g. -u '''`~

" ,'.'`, During catalyst preparation an increase ln bulk denslty must there-fore be realized. An increase in bulk denslty occurs, for instance, upon incorporation of metals, the increase in bulk dcnsity being larger according as a higher metal load is applied. An increase in ~ulk density may ~urther be realized by exerting pressure on the hydrogel, for instance by kneading, pressing or extruding, the in~
crease in bulk density being larger according as a higher pressure is exerted. Forcing the hydrogel under high pressure through a narrow opening such as a slit also leads to a considerable increase ~ ~;
in bulk density. The bulk-density-increaslng effec~ of exerting pressure on the hydrogel can be considerably enhanced by incorporat-ing certain additives in the hydrogel such as nitric acid and aluminium salts.
In addition to fluorine the present catalysts may con~
tain other promoters such as phosphorus and boron.
The metals nickel and/or cobalt and molybdenum may be present in the catalysts concerned as such or in the form of their oxides or sulphides. The catalysts are preferably applied in the sulphidic form. Sulphiding of the present catalysts may be carried

2~ out according to any process for sulphiding catalysts known in the art. Sulphiding may for instance be effected by contacting the catalysts with a sulphur-containing gas such as a mixture of hydrogen and hydrogen sulphide. Sulphiding may also suitably be effected by contacting the catalyst with a sulphur-containing hydrocarbon oil such as a sulphur-containing gas oil, ~ ;
The present catalysts are especiall~ important for use in the preparation of high-viscosity-index lubTicat mg oils by hydro~
cracking a mixture of heavy hydrocarbons. As mixtures of heavy hydrocarbons that may serve as starting materials for the preparation of lubricating oils according to the invention preference is given to ~axy~lubr~cating oil fractions obtained in the distillation at reduced pressure of at~ospheric distillation resldues of wax~ crude oils and waxes o~tained from these waxy lubricating oil fractions pre-pared by hydrocracking. Examples of such waxy lubricating oil frac-t~ons are spindle oil ~S0) waxy dis~illates, light machine oil (LM0) waxy distillates and medium machine oil (MMO) waxy distillates and de-asphalted oils (DAO), So, LMO and MMO wa~y raffinates and waxy bright stocks (BS~ obtained from the aforementioned lubricating oil fractions by treating them with a selective solvent for aromatics such as furfural, and S0, LMO, MM0, DA0 and BS slack waxes obtained from the aforementioned lubricating oil fractions b~ dewaxing. Blends of one or more distillate ~ ~
lubricating oil fractions and/or one or more residual lubricating oil ~ -fractions and/or one or more slack waxes may also be used as starting materials for the preparation of lubricating oil according to the in- ~ `
vention. `
Hydrocracking of a mixture of heavy ~ydrocarbons for the ;~
preparation of high-viscosity-index lubricating oils according to the invention is carried out by contacting the mixture of heavy hydrocarbons ~~' at elevated temperature and pressure and in the presence of hydrogen wlth the catalyst, which is preferably present in one or more beds of particles with dimensions between 0.5 and 3 mm.
Suitable hydrocracking conditions are: a temperature of from 325 to 450C, a pressure of from 10 to 250 bar, a hydrogen/feed ratio~
of rom 100 to 5000 Nl H2/kg feed and a space velocity of from 0.2 to 5.0 kg feed per litre of catalyst per hour. Preferably the following conditions are applied: a temperature of from 350 to 425C, a pressure o~ from 100 to 200 bar, a hydrogen/eed ratio of from 500 to 2500 Nl H2/
kg feed and a space velocity of from 0.5 to 1.5 kg feed per litre of : ;
catalyst per hour.
Lubricating oils prepared according to the invention have a

3~ lo~ aromatics content. Lubricating oils with an even lower aromatics content ma~ ~e prepared according to the in~ention if the hydrocracking ~: : ::
step is followed by a hydrofinishing step. Hydrofinishing of the _ g .. . .

S~3~
1 o --~ .
hydrocracked product may be carried out by con-tacting the hydro-cracked product at elevated temperature and pres~ure and in the presence of hydroeen with a hydrofinishing catalyst. The pressure, space velocity and gas flow rate that are applied in the hydrofinishing ~ -step may be chosen within the same limits as given hereinbefore ~ ;
for the hydrocrackin~ step. The hydrofinishing temperature is preferably chosen between 225 and 400C and in particular between 275 and 375 C. 'The temperature applied in the hydrofinishing step should be at least 25 C lower than the temperature at which the hydrocracking~
step is carried out. Suitable hydrofinishing catalyst~i are catalysts`~
containing one or more metals of Groups VIB~ VIIB or VIII on a carrier.
T'he effluent from the hydrocracking reactor, or, if hydro~
finishing is applied, the effluent from the hydrofinishing reactor is cooled and separated into a gas rich in hydrogen and a~liquid product.;The liquid product contains hydrocarbons boiling beloW
the boiling r:nge of lubricating oil and hydrocarbons;boiling within ~ ?
this ranee. The hydrocarbons boiling below the s~aid range ar: ~eparabed from~the higher-boilin~ residue, preferably by fr:ctiona1 dist11lation.
The~cutting puint of this distillation is preferabl~ chosen in ~
such a way that the higher-boiling residuè has an~in1tial boiling point in the range of 350-550 C. In addition to excellent lubricating oil compon:nta this residue gener:lly co~tains n~parafrins th:t solidify at ambient temperature and consequently have an adverse effect on the pour point~ of the lubricating oil. In order to obtain ~ ~ .
a suitable lubricating oil from the residue it is therefore preferred to d:wax thie r:sldue. The dewaxing process may be carried out ln any deelred way.~Dewàxing ls preferably~carr1ed out w1th :~mlxture ;~ of~m:thgl~ethyl~ketone :nd toluene t : temper:ture between~-10 and~-40C and at a~solvent/oil ~olumé ratio between~ and 10~
In order to increase;the yield of 1ubrlcatiDg o~ t~ls prefera~e .
.
:

to recycle at least J~art of the separated paraffins to the hydrocracking reactor.
In addition to -their ap~lication as catalysts in the hydrocracking of a mixture of heavy hydrocarbons for the preparation of hi~h-vis-cosity-index lubricating oils the present catslysts are also suitable for use in the first sta~e of a two-stage process for the preparation of light hydrocarbons such as gasolines and kerosines by hydrocracking ~ -a mixture of heavy hydrocarbons such as gas oils, flashed distillates and deasphalted oils. As examples of other processes according to the invention in which the present catalysts may be used advantaeeously may be mentioned: the preparation of light hydrocarbons from a mixture : ;~
of heavy hydrocarbons by single-stage hydrocrackin~, the hydrogenation~
of aromatics present in light fuels such as kerosines for the improvement~
of the smoke point, the hydrodesulphurization of distillate and residual hydrocarbon fractions, the hydrofinishing of lubricating oils and the preparation of technical white oils and medicinal oils by catalytic ~ ;::
hydrogen treatment of mineral oil fractions poor in aromatics. ~
The invention will DOW be elucidated with the aid of~the :following examples.
For the preparation of high-viscosity-index lubricating olls by hydrocracking 19 catalysts were tested. Of these 19 catalysts 6 were within the scope of the invention (catalysts 1-6) and the .~
other 13 were outside the scope (catalysts A-N). 'rhe preparation ~.~;. .. : .
of the catalysts was carried out ss follows.
~5 CatAlysts 1-6, A and B
. ..
For the preparation of catalysts 1-4 the starting Dlaterlal wa~s sn alumina hydrogel from which by drying and calcining a xerogel~
could be obtained with a bulk density of 0.35 g/ml and a pore volume ;
quotient of o.8 (slumina hydrogel I). For the preparation of catalysts:

7, 6, A and B the starting material was an alumina hydroeel from :, ~ . : . .
"

38~3~
_ 12 -which by dry;n~ and calcining a xerogel could be obtained with a bulk density of 0.7 g/ml and a pore volume quotient Or 0.3 ~alurnina hydrogel II).
The preparation of catalysts 16 and 3 was effected by mixing an aqueous solution containing" in addition to a molybdenum and a fluorine compound, either a nickel compound (for the preparation of catalysts 1-3, 5, 6 and B), or a cobalt compound (for the preDaration of catalyst 4), either with alumina hydrogel I (for the preparation of catalysts 1-4), or with alumina hydrogel II (for the preparation~
of catalysts 6 and B) and maintaining the mixture for some time at elevated temperature, separating the hydrogel loaded with metals and fluorine from the mixture and subsequently dryin6S extrudin~
and calcining it, In catalysts 6 and B an additional quant1ty Or;
fluorine was incorporated by fluoriding in situ.
The preparation of catalyst A was effected by mlxing an aqueous ~ ,s~
solution containing a nickel and a molybdenum compound withialumina~
hydroeel II and maintaining the mixture for some time at elevated~
tempsrature, separatin~ the hydrogel loaded with metals from~the;
mixture and subsequently drying. ~xtruding and calcining it. In catalyst A fluorine was incorporated by fluori~ing in SltU. ;

Cstslysta C-N
'rhese catalysts were preparsd by impregnation of calcined carrisrs with an aqueous aolution contsinin~ one or two metal compounds and,~
if desired, a boron or a phosphorus;compound, followed by~ drylng and calcining of the com~ositions.
The preparation of catalyst C~was effected by impr~gnation of a silica-zirconia carrisr with an aqusous solution containing~a platinum~
compound followed by dryin~ and calcining of the composition.

The prspa ation or~catalysts~D-G was~effectsd by~imprsgnation~
of~an alumina carrlsr wlth an aqusous~solution~containing g nickèl, a molybdenum and a phosphorus compound. ~ollowed by dryine snd calcining;~
o~ the composition. In catalysts E-G ~Iuorlne was incorporatsd by ~luoridin~ in situ.

:

~0~

Th~ preparntlon Or ca-talyst 11 was efrected by impre~,nation of an alwnirla csrrier with an aqueous solut;on containine a nickel, a tune~ten and a boron compound, followed by drying and calcinin~
of the composition.
The preparation of catalysts J-L was effected by impregtlation of either an alumina carrier (for the preparation of catalyst J), or a silica-alumina carrier (for the preparation of catalyst or a silics-magne~ia carrier (for the preparation of catalyst L)~
with an aqueous solution containing a nickel and a tungsten compound, followed by drying and calcining of the compositions.
The preparation of catalysts M and N was effected by Impregnati~o~
of a fluorine-containing alumina carrier with an aqueous solution containint~ a nickel compound and either a tungsten compound (for the preparation of catalyst M), or a molybdenum compound (for the preparstion of catalyst N), followed by drying and calcininE of the compositions.
The chemical composition as well ss some further information about the vari.us c~talysts is given in Tables A ~nd B.

~L~3W8~

~ I N N ~ C) a ~ ~ Y 3'~ o o " a ~ b~

a ~ u ~ a ~3 1 + + +
~¦ O a ~¦ H + + + ~ 3 s~
a ~ ~ o o o o ~' ~ C~

T~BL~ B
Cat. ~ataly~t composition in pbw per 100 pbt~ c~rrier Cataly~t ~~~~~~~~~~~~~~~~~~~~~~~-- carrler No, Ni lilo W P-t P B F
____ ____ ____ ___ ____ ~___ ____ ____ _~~____,__ C o.6 SiO2-ZrO2 D 3.0 10.5 1.8 Al23 E 3.8 16.0 4 3 ~l23 F 2.7 15.6 2 2.5 ~l23 G 10 20 2 2 Al23 Il 7.9 35.8 4 Al203 J l~,9 ~6.3 ~l2 3 K 2.3 11,0 SiO2 Al203 L 3.5 11.0 SiO2-~gO
M 2.3 11.0 2.5 Al203 N 2.3 14.4 2.5 Al23 EXAMP~
Temperature requirement, aromatics retention and selectivity of the catalysts mentioned in ~able A in the prepar;ation of a 400C
lubricatine oil with a VI of 130 a~ter dewax1ng at -30C were compared ~
in a bydrocracking experiment carried out under the following conditions.
Feed~
Oil obtained by deasphalting a residue from the distillation at reduced pressure of an atmospheric distillation residue of a crude oil from the Middle East.
Prope~ties of the feed~
VI after dewaxing at-30~C : 77 `
sulphur content : 2.1 %w ;~
nitro~en content : 630 ppm~
aromatics content : 135 mmol/iOO g ;
15 llydrocr~cking conditions:
pressure : 150 bar space velocity 1 l,l~1,h~
hydrogen/feed ratio : 2000 Nl.l ~

~he catalysts were applied in the sulphided form. Sulphiding o~ the catalysts was carried out by contacting them for 5 hours with a mixture of hydrogen and hydrogen sulphide in a volume ratio o~

7:1 at a -temperatur~ between 75 and 375 ~ and a pressure of 1U ~ar.
~e~raxing was carried out with a mix-ture of methyl ethyl ketone and toluene in a ratio of 1:1. In-situ fluoriding of eligible catalysts was effec-ted by adding 3~0 ppmw fluorine as ortho-fluorotoluene to the feed durine the initial sta~e of the ex~eriment until the required fluorine content of the catalyst had been reached. The catalysts were tested in the ~orm of 1.5 mm extrudates.
In this experiment for an optimum catalyst the temperature require-ment should be at most 420 C` 9 the aromatics retention at most 30 and the selectivity at least 35 %w.
The results of this experiment are given i.n Table C.

TABLE C
Catalyst Temperature ~electivity, Aromatics tested,requirement, %w on feed retention, No. C %
__________________.__ ____________ _______ __ .

3 l~o8 37 9.5

4 418 36 15 _ = = = = = _ = = =

E ~ E II
Temperature requirement, aroma-tics retention and selectivity of a m~lber Or the catalysts mentioned in Tables A and B in the preparation of a 375C lubricating oil with a VI of 128 after dewaxing at -20 C
were compared in a ~drocracking experiment carried out under the same conditions as the experiment according to Example I.
Feed:
Oil obtained by deasphalting a residue from the distillatian at reduced pressure of an atmospheric distillat;on residue of a crude oil from the Middle East.

Pro~erties of the feed:
VI after de~raxing at -20C : 81 sulphur content : 2.5 %w nitrogen content : 780 ppmw aromatics content : 100 mmol/100 g catalyst bed: 100 ml ~he catalysts were tested in the form of particles with a dia_ :~
meter Or 0 5~ n~.
In this experiment for an optimum catalyst the temperature re-quirement should be at most 420C, the aromatics retention at most 30% and the selec-tivity at least 40 %w.
The results o~ this experiment are siven in Table D.
TABLE D
Catalyst TemperatureSelecti~ity, Aromatics ~ :
tested,requirement, ~w on feed retention, No. C %
____________________ ____________ ____ _____ ~
2 40~ 45 20 3 l~05 46 18 ; ~`

C~ ~40 36 80 ::
D 433 38 47 ~::
G 429 39 113 ~:
l35 38 53 .
421 I~o 40 M 426 43 : 35 Under the conditions of this experiment it was not possible to prepare n lubricatin~ oil with a VI of 128 with catalyst CO ~;~
The fi~ures for catalyst C given in Table D refer to the ~ :
prepnration of an oil with a V1 of 112.

~XAMYLE~
Temperature requirement and selec-tivity of a number of the catalysts mentioned in Tables A and B in the preparation o~a 430 C lubricating ;~
oil with a VI of 96 after dewaxing at 20 C were compared in a hydro-~
cracking experiment carried out under the following conditions.

,, ~-,.. ~, .

3~a Feed:
;~axy heavy distillate lubricating o:il fraction of a crude oil from the ~!iddle Eas-t.
Properties of the ~eed:
VI after dewaxing at-20 C : 37 sulphur con-tent : 3 %w nitroeen content : 1250 ppmw Hydrocracking condit;ons:
hydrogen partial pressure : 140 bar space velocity 1 k l~1 h-hydro~en/f`eed ratio : 2000 Nl.kg Cntalys-t bed: 250 ml The catalysts were tested in the ~orm o~ 1.5 mrn extrudates.
The conditions regarding sulphiding~ and in-situ M uoriding o~ the catalysts as well as dewaxing of the oils were the same as giYen in Example I.
In this experiment ~or an optimum catalyst the temperature requirement should be at most 405C and the selectivity at least 51 ~w.
The results o~ this experiment are given in Table E~ .
TABLE E
CatalystTemperatureSelectivity, tested,requirement, %w on feed No. C
____________________ ____________ ~ Ol~ 52 ~ o5 49 =======a=============--===================_ EXIU~LE IV
Temperature requirement, aromatics retention and selectivity of a number of the catalysts mentioned ;n Tables A and B in the preparation o~ a 400 C lubric&ting oil with a VI o~ 95 after dewaxing at -20C

. .. ..

were compared in ~ hydrocr~ckine exper:iment carried out under -the following conditions. ~:
Feed:
Waxy heavy distillate lubricnting oil fraction of a crude ~ -oil from the Middle East.
Properties of the feed:
VI after dewaxing at -20C : 44 ~;
sulphur content : 205 %w nitrogen content : 1200 ppmw aromatics content : 150 mmol/100 g Hydrocracking conditions:
hydrogen partial pressure : 140 bar space velocity 1 1 1-1 h-1 hydrogen/feed ratio : 2000 Nl.kg catalyst bed : 250 ml The catalysts were tested in the form of 1.5 mm extrudates The conditions regarding sulphiding~ and in-situ ~luoriding o~ the catalysts as well as dewaxing of the oils were the same as given in ExQmple I.
In this experiment Por an optimum catalyst the temperature requirement should be at most 40SC, the aromatics retention at most 45~ and the æelectivity at least 60 %w.
The results of this experiment are given in Table F.
, ~

.,'.-: ':
. ' ' ,~ , ~`, , ~ , - - - . ~ - :
. - . ... .- ~ ~ , ~o~
- 2() -TABL~ l;' Cstalyst Temperature3~1ectivity,Aromatics tested, requirement,~w on f'eedretention, No. C ~
_______ ____ __w_________ ~_______________ 1 401 61 1l2 2 39l~ 62 3l~

4 401 62 I~3 F 40g 58 5 H 407 . 59 44 The results given in Tables C-F clearly show that Gatalysts according to the .invention (catalysts 1-6) are su~erior ~or the preparation of high-viscosity-index lu~ricating oils by hydrocracking in comparison with closely related catalysts outside the scope o~
the invention (catalys-ts ~ and B) as well as other catalysts proposed for the preparation of lubricating oils by hydrocracking (catalysts C-N).

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the conversion of hydrocarbons, char-acterized in that the hydrocarbons are contacted at elevated temperature and pressure and in the presence of hydrogen with a fluorine-containing catalyst containing nickel and/or cobalt and, in addition, molybdenum on alumina as the carrier, which catalyst has a bulk density of at least 0.8 g/ml, wherein the bulk density is the quotient of the weight of a given quantity of material and its volume after thorough compaction, contains at least 3 pbw nickel and/or cobalt and at least 10 pbw molybdenum, respectively, per 100 pbw carrier and has been prepared as follows, starting from an alumina hydrogel from which a xerogel with a bulk density of less than 0.8 g/ml can be obtained by drying and calcining:
(a) when the pore volume quotient of the said xerogel is at least 0.5, wherein the pore volume quotient is the quotient of the mercury pore volume of a material and the total pore vol-ume, the catalyst preparation is effected by incorporation of the metals and, if desired, fluorine in the alumina hydrogel and by drying and calcining the composition;
(b) when the pore volume of the said xerogel is less than 0.5, the catalyst preparation is effected by incorporation of the metals and at least part of the fluorine in the alumina hydrogel and by drying and calcining the composition, it being understood that in the latter case enough fluorine is incorpor-ated in the alumina hydrogel to ensure that from this fluorine-containing alumina hydrogel a xerogel can be obtained by drying and calcining whose pore volume quotient is at least 0.5.

2. A process according to claim 1, characterized in that a catalyst is used in the preparation of which the metals have been incorporated in the hydrogel by treating it at a tempera-ture above 50°C and preferably between 60 and 250°C with an aqueous solution containing a nickel and/or cobalt compound and, in addition, a molybdenum compound.

3. A process according to claim 1, characterized in that a catalyst is used containing 25-80 pbw nickel and/or cobalt and 50-80 pbw molybdenum per 100 pbw alumina.

4. A process according to claim 3, characterized in that a catalyst is used in which the weight ratio between nickel and/or cobalt on the one hand and molybdenum on the other, lies between 1:1 and 1:5.

5. A process according to any one of claims 1-3, char-acterized in that a catalyst is used containing 10-30 pbw fluorine per 100 pbw alumina.

6. A process according to any one of claims 1-3, char-acterized in that a catalyst is used in which at least part of the fluorine and preferably substantially all the fluorine is incorporated, while the alumina is still in the hydrogel form.

7. A process according to any one of claims 1-3, char-acterized in that the catalysts are used in the sulphidic form.

8. A process according to any one of claims 1-3, char-acterized in that high-viscosity-index lubricating oils are prepared by hydro-cracking a mixture of heavy hydrocarbons.

9. A process according to any one of claims 1-3, char-acterized in that for the preparation of lubricating oils by hydro-cracking a mixture of heavy hydrocarbons a catalyst is used containing 10-25 pbw fluorine per 100 pbw alumina.

10. A process according to any one of claims 1-3, char-acterized in that high-viscosity-index lubricating oils are prepared by hydro-cracking a mixture of heavy hydrocarbons selected from the group formed by (a) waxy lubricating oil fractions obtained in the distillation at reduced pressure of atmospheric distillation residues of waxy crude oils;
(b) waxes that have been separated from these waxy lubricating oil fractions;
(c) waxes that have been separated from lubricating oil fractions obtained by hydro-cracking; and (d) blends of two or more mixtures of heavy hydro-carbons mentioned under (a), (b) and (c).

11. A process according to claim 1, characterized in that high-viscosity-index lubricating oils are prepared by hydro-cracking a mixture of heavy hydrocarbons at a temperature of from 325 to 450°C, a pressure of from 10 to 250 bar, a space velocity of from 0.2 to 5.0 kg feed per litre of catalyst per hour and a hydrogen/feed ratio of from 100 to 5000 N1 H2/kg feed.

12. A process according to claim 11, characterized in that it is carried out at a temperature of from 350 to 425°C, a pressure of from 100 to 200 bar, a space velocity of from 0.5 to 1.5 feed per litre of catalyst per hour and a hydrogen/feed ratio of from 500 to 2500 N1 H2/kg feed.

13. A process according to any one of claims 1-3, char-acterized in that high-viscosity-index lubricating oils are prepared by hydro-cracking a mixture of heavy hydrocarbons followed by hydrofinishing of the hydro-cracked product.

14. A process according to any one of claims 1-3, char-acterized in that high-viscosity-index lubricating oils are prepared by hydro-cracking a mixture of heavy hydrocarbons, separation of the effluent from the hydro-cracking reactor, or, when hydrofinishing has been applied, separation of the effluent from the hydrofinishing reactor, by distillation into one or more light fractions and a residual fraction with an initial boiling point between 350 and 550°C, dewaxing of the residual fraction and recycling to the hydro-cracking reactor of at least part of the separated paraffin wax.

15. A process according to claim 1, characterized in that light hydrocarbons are prepared by hydro-cracking a mixture of heavy hydrocarbons.

16. A process according to claim 15, characterized in that for the preparation of light hydrocarbons by hydro-cracking a mixture of heavy hydrocarbons a catalyst is applied containing 20-30 pbw fluorine per 100 pbw alumina.