DE2456329A1 - METHOD FOR CATALYTIC CONVERSION OF HYDROCARBON RESIDUAL SOILS - Google Patents

Description

8 MON (X ¹ JEN. 40,

1 — uEPoiJ 34 50 6 /

DIPL. -PHYS. DR. JÜRGEN SCHIRDEWAHN Telegram address: invent / monchen

TELEX 5-29 68S

PATENT LAWYERS

u.z .: J 354 C K 5214

(j / WS / k) November 28, 1974

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. The Hague, Netherlands

——— ^ -————————__—— ι — ΓΓ1 — f ~~~~~ * ~ * ~ "* ~~ ^ ~~ i — in rmmnf ~ mnrtwmriTiiTwnTiM-i m ι» ππ- τιι »^ ιτΜ —— M ~ nwiTWn i- irr ι .τ ■ ti ι ι» »im liiiiiiinii» ι ni-mrwr-in

"Process for the catalytic conversion of residual hydrocarbon oils "(Addition to patent (patent application

P 23 34 2y3.O))

Priority: 3Q. November 1973, the Netherlands, no.7316 396 and 29 July 1974, the Netherlands, no.7410 162

The present invention relates to an improvement in the method for the catalytic conversion of residual hydrocarbon oils according to patent (patent application P 23 34 293.0),

according to which the oil is first demetallized and then catalytically converted v / ird and in which the demetallization at elevated temperatures and pressures and in the presence of hydrogen is carried out by contacting the oil with a catalyst comprising one or more hydrogenation-active metals

50-9 823/0684

on a carrier material and the following conditions Fulfills :

(1) p / d ^ 3.5 - 0.02 v, in which ρ is the specific mean pore diameter in nm, d is the specific mean particle diameter in mm and ν is the percentage of pores with a diameter P 100 nm Pore volume based on the total pore volume;

(2) the total pore volume is greater than 0.40 ml / g;

(3) ν is less than 50; and

(4) the surface area is greater than 1Θ0 m / g. And deJCKKatalysator is met, provided that ρ and d have such values that the quotient, p / d greater than 3.5 - 0.02 vj but less than 10 - 0.15 ν is, the following additional conditions :

' a) the pore volume determined with nitrogen: is greater than 0.60 ml / g,

b) the surface is larger than 150 m / g, and

c) ρ is larger than 5 nm.

The further investigation of the demetallization of hydrocarbons residual oils by means of catalysts' which meet the aforementioned conditions in terms of particle size and porosity meet, has shown that the activity of these catalysts, 0.1 to 15 parts by weight of several hydrogenation-active Metals per 100 parts by weight of silicon dioxide

Contain carrier material, to a large extent from their. Incandescent

509823/0684

loss under standard conditions.

In the present description, the term loss on ignition is used of a catalyst under standard conditions

the weight loss, expressed as a percentage understood -the in a sample of 5 to 10 g of the catalyst cm with a layer thickness of less than 1 vorlieg in a well ventilated drying oven *, after heating, of blank t &mperatur'auf 500 ⁰ C in The term "Glüfoverlust" defined above, "determined under standard conditions" is abbreviated in the description below as "ignition loss".

It has been found that these catalysts are the best possible Exhibit activity when their loss of ignition. less than 1.0 weight percent and, provided these are catalysts Vanadium or a combination of vanadium .. with one or contain several other metals active in hydrogenation, is less than 0.5 percent by weight. . . _

The invention accordingly relates to an improvement of the method for the catalytic conversion of residual hydrocarbon oils

according to which the oil is first demetallized and then catalytically converted, and in which. the demetallization at elevated temperatures and pressures and in the presence of hydrogen by contacting the oil with a catalyst is carried out, the one or more hydrogenation

509823/0684

contains active metals on a carrier material and fulfills the following conditions:

(1) p / d greater 3.5 - 0.02 v, in which ρ is the specific mean pore diameter in nm, d is the specific mean particle diameter in mm and. v. the. Percentage of the pore volume consisting of pores with a diameter greater than 100 nm, based on the total perennial volume ; ■ - ■

(2) the total pore volume is greater than 0.40 ml / g;

(3) ν - is less than 50; and ·

(4) the surface is greater than 100 m / g and the catalyst fulfilled, provided that ρ and d have such values that the quotient p / d is larger than 3 »5 - 0.02 ν but smaller than 10 - 0.15 ν, the following others. Conditions :

a) the pore volume determined with nitrogen is larger than 0.60 ml / g,

b) the surface is larger than 150 m / g, and

c) ρ is larger than 5 nm,

according to patent (patent application P 2 234 293.0)

the dadureh is marked that the. EntnretaHisierung carried out in the presence of a catalyst ;, is; which contains 0.1 to 15 parts by weight of one or more hydrogenation-active metals per 100 parts by weight of silicon dioxide support material and which has a loss on ignition of less than 1.0 percent by weight and, if the catalyst,, vanadium or a combination of vanadium with one or more others

509823/06 * 8 4

contains active hydrogenation metals, of less than 0.5 percent by weight having.

According to the invention, a catalyst is preferably used which has a loss on ignition of less than 0.75 percent by weight and, if the catalyst contains vanadium, less than 0.2 weight percent.

In the process according to the invention, it is important that the catalyst has a Annealing loss of less than 1.0 percent by weight. and, if .. äeT. • .Catalyst contains vanadium, .of less than .0.5 .:% by weight. This can be achieved by carefully calcining the catalyst and also by handling it carefully. In the present description, "careful calcination of a catalyst" is understood to mean that the calcination is carried out in such a way that: a. Catalyst with a loss on ignition of less than 1.0 percent by weight and, if the catalyst contains "vanadium", of less than 0.5 percent by weight... Careful calcination can be achieved by calcining the extremely thin layer present catalyst with sufficient ventilation of the room in which the calcination is carried out. Under "careful handling" of the catalyst is understood in the present description "that after careful calcination of the catalyst it is ensured that, among other things, during the storage, and des

50 9823/068

Transport of the carefully calcined catalyst, as well as during the charging of the demetallization reactor - This catalyst the loss on ignition of the catalyst, increases as little as possible and below a value

-of 1.0 percent by weight, and provided the catalyst is vanadium

contains, among others, remains of 0.5 percent by weight. This can / thereby can be achieved that as far as possible an adsorption of moisture by the catalyst, ζ.B..dureh, contact of the Catalyst with moist air, is avoided. When the catalyst not sufficiently carefully calcined or; ..when a appropriately carefully calcined catalyst. not sufficient carefully handled., been., isty: is ^ t ". es v.in spite of this possible, a suitable one for the invention -Vea? .fatmen; To produce a catalyst by reducing the moisture content of the catalyst to a sufficient extent, which is e.g.

; by drying the catalyst in a dry gas Temperatures or by repeated calcining of the catalyst before contacting .with '. "the. to be demetallized Feeding can be achieved. This reduction in the moisture content of the catalyst: feann e.g. be carried out when the catalyst is already in the demetallization reactor is located.

size
The / dependence of the activity of a demetallization catalyst

sators in the process according to patent .....; (Patent application P 23 34 293.0), 0.1 to 15 parts by weight of one or several hydrogenating metals per 100 parts by weight Contains silicon dioxide carrier material, the glow of which

'· ■ · - "50 9 823/0 684" ""

loss / -and "the fact that these catalysts show their best possible activity when the pleasure less than 1.0 percent by weight and if so

the catalysts contain vanadium, less than 0.5 percent by weight is extremely surprising,

if you consider that the activity of very similar,

they just end up with aluminum oxide instead of silicon dioxide carrier material /

Catalysts are not dependent on loss on ignition. having.

Catalysts are preferably used in the process according to the invention used as hydrogenation-active metals': one or several metals from the group nickel, cobalt, ..Molybdenum and Contains vanadium. These catalysts also contain preferably at least one metal from the group consisting of nickel and cobalt and at least one metal from the group consisting of molybdenum and Vanadium and also have an atomic ratio of nickel and / or cobalt on the one hand to molybdenum and / or vanadium on the other hand from 0.05 to 3.0. Suitable metal combinations are nickel-vanadium, cobalt-molybdenum and nickel-molybdenum. The catalysts contain preferably from Θ / 5 to 10 parts by weight and in particular from 2.0 to 7.5 parts by weight hydrogenation-resistant metals {per 100 parts by weight of silicon dioxide carrier material. In particular, demetallization catalysts are used according to the invention which are approximately 0.5 parts by weight Nickel and about 2 parts by weight vanadium each Contain 100 parts by weight of silicon dioxide carrier material, as well Catalysts containing approximately 1 part by weight of nickel or

"* 509823/0684 ~

Contain cobalt and approximately 4 parts by weight of molybdenum per 100 parts by weight of silicon dioxide support material. The metals can be on the carrier material in metallic form or in In the form of their oxides or sulfides. Preferably be Catalysts are used which contain the metals in the form of their sulfides on the support material.

The sulfiding of the catalysts of the invention can be carried out using any known method for sulfiding Catalysts are carried out. In addition to the hydrogenation-active Metals contain the catalysts used according to the invention optionally promoters, such as phosphorus ,, .. boron roder a Halogen. ......

The catalysts used in the demetallization according to the invention can be produced after application of the metals in question to a silicon dioxide carrier material with such a porosity that after application of the metal a catalyst is obtained which meets the inventive conditions either as such or after adaptation, the specific corresponds to the mean particle diameter of the catalyst. As described in patent ..... (patent application P 23, 34 293.0), the porosity of a catalyst support material is mainly determined by the process by which the catalyst was produced. Processes for influencing the porosity of the catalyst support material are described in the aforementioned DT-OS.

The catalysts can be used by any known means

5 0 9 8 2 3/0 6 β Λ

Process for the production of catalysts on a carrier material getting produced. It is not necessary to apply the metals to a finished silicon dioxide carrier material. The metals can also be incorporated into the silica support material during manufacture, e.g. prior to molding, be applied.

Siliciuffidioxyd -trägermaterialieri are usually made by precipitating a silicon dioxide hydrogel und.ansohliessendes molding and. Calcining produced. Typically, the silica hydrogel is allowed to age prior to molding. Particularly active ^{according to the invention:} ss'ge; suitable properties of the metalization catalysts can be obtained by incorporating the metals in question into a silicon dioxide hydrogel before it is shaped. The incorporation of the metals into the silica hydrogel is preferably carried out after the gel has aged. A particularly active demetallization catalyst suitable according to the invention is obtained zr; Bv: \ dureh; Incorporation of such amounts of a nick «! and vanadium compound. cases in a silica hydrogel according to the off -. and the ^T, aging of the gel, but prior to its shaping and Kalz-ination to obtain a finished catalyst, of about, 0,5.Gewichtsteile nickel and about 2 Gewiehtstei- le .vanadium; 3 © contains 100 parts by weight of finished catalyst carrier material.

Another advantageous process for the production of according to the invention suitable demetallization catalysts consists of a single or multi-stage mixed impregnation of a catalyst

509823 / 06.84

lysator carrier material with an aqueous containing one or more compounds of a hydrogenating metal Solution followed by drying and calcining.

Suitable water-soluble metal compounds which can be used for the preparation of the catalysts which can be used according to the invention are suitable, for example, the nitrates, chlorides ,. Formates and acetates of nickel and cobalt, ammonium molybdate, vsnadyl oxalate, sulfate and acetylacetonate and ammonium vanadate.

Particularly suitable carrier materials for the invention Suitable catalysts are silica particles obtained by spray drying a silica gel. .and then-

Microparticles send shaping of the spray-dried / to. Larger ones Parts, e.g., by extrusion, have been obtained, are, and spherical silica particles produced by the well-known oil droplet process.

For the inventive catalytic hydrogenating, demetallization of hydrocarbon residue oils, ^% are generally

a common catalyst particle with / value d of 0.4 to 5.0 mm used. Catalyst particles with a value d of 1.0 to 4.0 mm and in particular 1.5 to 3.5 mm are preferred used.

In the process according to the invention, a catalyst is used which has such values ρ and d that the quotient p / d is greater than 10.0-15 ν, and preferably becomes a Catalyst used, which has a total pore volume of at least

509 82 3/0684

at least 0.50 ml / g 'and a specific surface area above 150 m / g.

This relates to the demetallization stage of the invention Process-related example explains the invention,

• Example

A residual hydrocarbon oil with an overall: -Vanadiura- and nickel content of 0.0062 percent by weight; a content of Gc-asphaltenes of 6; 4 percent by weight and a sulfur content of 3.9 percent by weight, the residue in the atmospheric distillation of a Middle Eastern crude oil (Oil.B according to patent ............ (patent application

"P 23 34 293,0J), is at different air flow velocities and hydrogenated demetallized in the presence of 13 different catalysts. For this purpose the oil is used a temperature of 420 ° C, a total pressure of 150 bar and a gas velocity (measured at the reactor outlet) of 250 Nl of hydrogen per kg of fresh catalyst together with Hydrogen passed from top to bottom through a cylindrical, vertically arranged fixed catalyst bed.

The preparation of the 13 catalysts used in the demetallization experiments is described below. The results of the demetallization tests, the space flow rates used and the catalyst properties are summarized in the table.

50 9823 / 06.84

Catalyst manufacture

Catalysts A and B

These containing 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of silicon dioxide support material Catalysts are through. Impregnation of a silicon dioxide carrier material with an aqueous solution containing vanadyl oxalate and nickel nitrate. After drying

The impregnated material ^{is calcined at 120 °} C. for one hour at 500 ^° C. as a 6 cm thick layer in a non-ventilated drying oven. The calcined material is divided into two parts. One part is carefully calcined again in a layer less than 1 cm thick for one hour at 500 ^° C. in a well-ventilated drying oven.

: and as catalyst A with exclusion of moisture in the Entmetallization reactor fed. The other part is transferred to the "demetallization reactor" as catalyst B.

Catalysts C and D

These catalysts containing 1.0 parts by weight of cobalt and 4.0 parts by weight of molybdenum per 100 parts by weight of silicon dioxide support material are made using the same silicon dioxide support material as in the preparation of catalysts A and B, by impregnating the silicon dioxide support material with an aqueous cobalt nitrate . and solution containing ammonium molybdate. After drying the impregnated material at 12O ⁰ C wird_dieses in a> 10 cm thick layer in a non-ventilated drying oven

509823/0684

calcined at 50O ⁰ C for one hour. The calcined material is divided into two samples. A sample is carefully calcined again in a layer less than 1 cm thick in a well-ventilated drying oven for one hour at 500 ^° C. and fed into the demetallization reactor as catalyst C with the exclusion of moisture. The other sample is transferred to the demetallization reactor as catalyst D. ·

Catalysts E and F

These catalysts, which contain 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of silicon dioxide support, like catalysts A and B, are made by impregnating a silicon dioxide support material with an aqueous one containing vanadyl oxalate and nickel itate Solution made. After drying the impregnated material at 120 ⁰ C of this "is gently for one hour at 60O calcined ⁰ C in a less than 1cm thick layer in a well ventilated drying oven. The calcined material is divided into two samples. One sample is to the exclusion of Moisture is transferred to the demetallization reactor as catalyst E. The other sample is contacted with moist air for one week and then fed into the demetallization reactor as catalyst F.

Catalysts G, H and I

These, 1.0 parts by weight of nickel and 4.0 parts by weight of molybdenum

• 509823/06 8 U

Catalysts containing 100 parts by weight of silicon dioxide carrier material are prepared using the same silicon dioxide carrier material as in the preparation of catalysts E and F, by impregnating the carrier material with an aqueous solution containing nickel nitrate and ammonium molybdate. After drying the impregnated material at 120 ⁰ C of this carefully em in a less than 1 thick layer is calcined for one hour at 600 ° C in a well ventilated drying oven. The calcined material is divided into three samples. The first sample is transferred to the demetallization reactor as catalyst G with exclusion of moisture. The second sample, becomes 2.4. Contacted hours with moist air and then fed as catalyst H into the demetallization reactor. The third sample is contacted with moist air for two weeks and then transferred to the demetallization reactor as catalyst I.

Catalysts J and K

These catalysts containing 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of aluminum oxide carrier material are prepared by impregnating an aluminum oxide carrier material with an aqueous solution containing vanadyl oxalate and nickel nitrate. After the impregnated material has been dried at 120 ^° C., it is carefully calcined for ^{one hour at 500 °} C. in a layer less than 1 cm thick in a well-ventilated drying oven. The calcined material is divided into two samples. A sample will be

5 0 9.82 3/06 84

transferred as catalyst J with exclusion of moisture in the demetallization reactor. The other sample will contacted with moist air for two months and then fed into the demetallization reactor as catalyst K.

Catalysts L and M

These catalysts containing 1.0 parts by weight of nickel and 4.0 parts by weight of molybdenum per 100 parts by weight of aluminum oxide support material are produced using the same aluminum oxide support material as in the production of catalysts J and K, by impregnating with an aqueous, nickel nitrate and Solution containing ammonium molybdate prepared. After drying the impregnated material at 120 ⁰ C of this carefully cm in less than a 1 thick layer is calcined for one hour at ⁰ C 5OQ in a well ventilated drying oven. The calcined material is divided into two samples. One sample is fed into the demetallization reactor as catalyst L. The other sample is brought into contact with moist air for one month and then transferred to the demetallization reactor as catalyst M.

509823/0684

Table - page 16 -

it'§§-Iδ219 !! - If

Catalyst # A'BCDEPGHIJKLM

Room air flow. Speed X. l " ^1st hour ~ ¹ 6.1 3.3 5.2 4.5 5-0 4.1 5-0 4.9 4.0 4.6 4.6 4.9 4.9

Specific upper

I area, m7g 193 193. 198.198 252 252 250 250 250 225 225 230 230

Total pore

volume, ml / g 0.79 0.79 0.80 O.'8O 0.80 0.80 0.79 0.79 0.79 0.57 0.57 Ο.58 Ο-.58

With nitrogen adsorption:

° pore volume? ⁶⁸ ml / g ° * ⁷⁸ ° 78 'Ο.78 0.78 0.76' 0.76 0.77.0.77 0.77 0.56 Ο.56 0.57.0.57

· V, percent 6 6 7 .7 "7. 7 6 6 6 <0.5 <0.5« 0.5. '<0.5

^ d, mm 2.4 2.4 2.4, 2.4 2.2 2.2 2.2 2.2 2.2 0.7 0.7 0.7 0.7

P, nm 10.1 10.1 10.1 10.1 11.0 11.0 11.0 11.0 11.0 10.2 10.2 10.2 10.2

. Glühyerlust, ""

Weight percent 0.0 0.9 0.1 1.2 0.0 1.5 0.0 0.6 2.0 0.0 5.9 0.1 6.3

V + Ni distance '' _ ν

'(after I in weight
^ percent) after treatment.

one given number of
, Tons of feed per kg
-Catalyst (according to II in

Metric tons)

; I.

■ II

II

47 ' 46 49.5 49 48 47 ■ 48 .5 48 .5 .48 ' 50 50.5 51 .5 ro
JP-
51 ^ ¹
'cn J = -
OO VJl 5
48 VJl VJl j = ·
vo Oi • 5
48- 5 VJI 5 5 VJl 5 2 2 2 CM

According to patent (patent application P 23 34 293.0)

must be a suitable catalyst among those used in these demetallization attempts applied conditions meet the criterion that after treatment of 5 tons of oil B over the catalyst at a space flow velocity of at least 2.9 1 · 1 · - · hours even more than 40 percent by weight of the Total vanadium and nickel content of oil B can be removed.

All experiments given in the table in which the catalyst satisfies the aforementioned condition with regard to the weight percentage of nickel + vanadium removed

Demetallization tests according to the invention according to the patent

(Patent application P 23 34 293 * 0). R

Experiments 1 to 9 »in which catalysts were used that met the condition 10.0-0.15 ν * · p / d > -3.5 - 0.02 ν meet, show that the catalysts used also the additional Requirements according to the aforementioned patent specification with regard to ν (<50 percent), ρ (> 5 mn), with regard to the pore volume determined by means of nitrogen adsorption (> 0.60 ml / g) and the specific surface area (> 150 m / g).

In tests 10 to 13, in which catalysts are used which meet the condition p / d> 10.0 - -0.15 ν, the catalysts used also meet the requirements according to the aforementioned patent specification with regard to ν (<50 percent), the total pore volume (> 0.40 ml / g) and the specific surface (> 100 m / g).

509823/0684

245632S

In all of the experiments listed in the table, catalysts are used used with a metal loading suitable for the invention (0.1 to 15 parts by weight of metal per 100 parts by weight of catalyst support material).

Of the experiments listed in the table, the Experiments 1 and 5 (in which Ni / V / SiO ^ catalysts with a

Loss on ignition of less than 0.5 percent by weight can be used), Experiment 3 (in which a Co / Mo / SiOp catalyst with a loss on ignition - of less than 1.0 weight percent is used) and experiments 7 and 8 (in which a Ni / Mo / SiOp catalyst with a loss on ignition, less than 1.0 percent by weight is used), demounting attempts according to the invention.

Experiments 2, 4, 6 and 9 to 13 do not represent any according to the invention Demetallization experiments. They were · βμβ reasons for comparison included in the table. In experiments 2 and 6, Ni / V / SiOp catalysts are used with a loss on ignition

used by more than 0.5 percent by weight. In experiments 4 and 9, Co / Mo / SiOg- or Ni / Mo / SiO2 ~ Catalysts with a loss on ignition - of more than 1.0 percent by weight used. Trials 10 to 13 are using aluminum oxide as a carrier material Catalysts carried out.

The influence of the moisture content of the catalysts on their demetallizing activity becomes clear when one compares the results of experiments 1, 3 »5, 7/6 with those of .Versuche 2 _f

5Q9823 / 0684

4, 6 and 9 compares. It appears that the Ni / V / SiOp catalysts A and E suitable according to the invention (which have a loss on ignition - '"of less than 0.5 percent by weight) which were used in experiments 1 and 5, and those suitable according to the invention Co / Mo / Ni SiOp- and / SiOg catalysts C, G and H (containing a Glühverliist 'of less than 1.0 weight percent have) which have been used in the tests 3, 7 and 8, approximately the same percentage of Vanadium + NiGkel removal after processing 5 tons of feed per kg of catalyst, such as the Ni / V / SiOp catalysts B and F, which are not suitable catalysts according to the invention (loss on ignition of more than 0.5 percent by weight), which were used in experiments 2 and 6, and how those also not used according to the invention

• Baren Co / Mo / SiO ₂ - and Ni / Mo / Si0 ₂ catalysts D and I (with a loss on ignition _; of more than .1.0 percent by weight), which were used in experiments 4 and 9.

; -. It must be noted here, however, that in the various Experiments deviating room flow velocities have been used and that by means of the inventive 5 catalysts have an approximately equal degree of demetallization can be achieved at considerably higher room flow velocities than with the 4 other catalysts.

The difference in sensitivity .... on the other hand Water between the vanadium-containing according to the invention. Catalysts and the metals other than vanadium-containing inventive catalysts is clearly based on a process

509 8 2 3/06 8 4;

like experiments 1 and 7 with experiments 2 and 8. The Ni / V / SiO ₂ catalyst B with a loss of energy

-between 0.5 and 1.0 percent by weight, which was used in experiment 2, shows a significantly lower demetallization activity than the Ni / V / Si0 ₂ catalyst Α with an ignition loss of less than 0.5 percent by weight, which in Experiment 1 has been used, while the Ni / Mo / Si0 ₂ catalyst H with a loss on ignition between 0.5 and 1.0 percent by weight, which was used in Experiment 8, has practically the same demetallizing activity as the Ni / Mo / Si0 ₂ catalyst G with a loss on ignition - of less than 0.5 percent by weight shows.

A comparison of the results of tests 10 and 12 with the results of tests 11 and 13 shows that the demetallizing activity of catalysts according to the invention on aluminum oxide carrier material regardless of the moisture content of the catalytic converter. Although the loss on ignition

- The catalysts K and M, which were used in experiments 13 and 15, 5.9 and 6.3 percent by weight, respectively and the loss on ignition of the tests 10

and 12 used catalysts J and L 0.0 and 0.1 weight percent, respectively is, in these with two catalysts each with practically the same space flow velocity tests carried out practically the same demetallizing activity observed. -.

509823/0684

Claims (1)

Claims 1.' Process for the catalytic conversion of residual hydrocarbon oils, according to which the oil is first demetallized and then catalytically converted, and in which the demetallization is carried out at elevated temperatures and pressures and in the presence of hydrogen by contacting the oil with a catalyst which has one or more Hydrogenation-active metals ■ contains on a carrier material and the following conditions are met -: _r (1) p / d> 3.5 - 0.02 v, in which ρ is the specific mean Pore diameter in nm, d the specific mean particle diameter in mm and ν the percentage - the one made of pores with a diameter greater than 100 nm existing pore volume, based on the total gore volume, are; (2) the total pore volume is greater than 0.40 ral / g; (3) ν is less than 50; and (4) the surface is greater than 100 m / g and the The catalyst fulfills if ρ and d have such values that the quotient p / d is greater than 3.5 - 0.02 ν but is less than 10 - 0.15 ν, the following additional conditions: ' a) the pore volume determined with nitrogen is 5 09823 / 068A -22- 245632S greater than 0.60 ml / g, b) the surface is larger than 150 m / g and c) ρ is larger than 5 nm, according to patent (patent application P 23 34 293.0), characterized in that the demetallization is carried out in the presence of a catalyst containing 0.1 to 15 parts by weight of one or more "hydrogenating active metals" per 100 parts by weight Contains silica support material and which has a loss on ignition:. -of less than 1.0 percent by weight and, if the catalyst is vanadium, or a combination of vanadium with one or more others contains hydrogenation-active metals, of less than 0.5 percent by weight. 2 .. The method according to claim 1, characterized in that the demetallization in the presence of a catalyst is carried out, which has a ·> 'loss on ignition less than 0.75 percent by weight and, if the catalyst contains vanadium, less than 0.2 percent by weight having. 3. The method according to claim 1 or 2, characterized in that the demetallization in the presence of a catalyst which has been carefully calcined and handled with care. 50 98 2 3/068 4 4. The method according to claim 1 to 3> characterized in that that the demetallization is carried out in the presence of a catalyst which is 0.5 to 10 parts by weight and preferably 2.0 to 7 »5 parts by weight of one or more hydrogenating metals per 100 parts by weight of silicon dioxide carrier material contains. 5. The method according to claim 1 to 4, characterized in that the demetallization in the presence of a catalyst is carried out, which is used as a hydrogenation-active .Metalle or contains several metals from the group consisting of nickel, cobalt, molybdenum and vanadium. 6. The method according to claim 5 »characterized in that the demetallization is carried out in the presence of a catalyst which acts as hydration-active metals at least a metal from the group consisting of nickel and cobalt and at least one metal from the group consisting of molybdenum and vanadium contains. . 7. The method according to claim 6, characterized in that the demetallization is carried out in the presence of a catalyst having an atomic ratio of .Nickel and / or cobalt on the one hand to molybdenum and / or vanadium on the other hand from 0.05 to 3.0. .8 * The method according to claim 7i, characterized in that the etching is carried out in the presence of a catalyst containing approximately one part by weight of nickel 509823/0684 or cobalt and about 4 parts by weight of molybdenum per 100 parts by weight Contains silicon dioxide carrier material. 9. The method according to claim 7 »characterized in that the de-metallization in the presence of a catalyst is carried out, the approximately 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium · per 100 parts by weight of silicon dioxide support material contains. 10. The method according to claim 1 to 9 »characterized in that the demetallization in the presence of a catalyst is carried out, which contains the hydrogenation-active metals in the form of their sulfides. . . . 11. The method according to claim 1 to 10, characterized in, that the demetallization takes place in the presence of a catalyst is carried out by incorporating the hydrogenation-active metals in a silicon dioxide hydrogel before Shaping and preferably after the aging of the hydrogel has been produced. 12. The method according to claim 1 to 10, characterized in that the demetallization in the presence of a catalyst is carried out, which is carried out by impregnating a silicon dioxide carrier material with one or more stages an aqueous one, one or more. Compounds of hydrogenation-active Metals containing solution and subsequent drying and calcining have been produced is. 509823/068 A 13. The method according to claim 12, characterized in that the demetallization is carried out in the presence of a catalyst, which is either a support material by spray-drying a silica gel and then shaping the spray-dried microparticles into larger ones Particles made of silica particles or from spherical silica particles that contain have been produced by means of the oil droplet process. 14. The method according to claim 1 to 13 »characterized in that that the demetallization in the presence of a catalyst is carried out, which has a value d of 1.0 to 4.0 mm and preferably from 1.5 to 3 »5 mm. 15. The method according to claim 1 to 14, characterized in that the demetallization in the presence of a catalyst is carried out, which has such values ρ and d, that the quotient p / d is greater than 10 - 0.15 ν and whose total pore volume is at least 0.50 ml / g and whose specific surface area is more than 15.0 m / g. 50 98 2 3/0684