JPS6022039B2 - Hydrocarbon conversion methods - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the catalytic conversion of hydrocarbons in the presence of hydrogen and, in particular, to the preparation of high viscosity index lubricating oils for hydrocracking mixtures of heavy hydrocarbons.

When a mixture of heavy hydrocarbons is hydrocracking to prepare a high viscosity index lubricating oil, the low viscosity index compounds present in the feedstock are converted to high viscosity index compounds.

At the same time, the nitrogen, sulfur and oxygen content of the oil is significantly reduced. When hydrocracking mixtures of heavy hydrocarbons to prepare high viscosity index lubricating oils, the suitability of the catalyst used depends on the required temperature, aromatic retention and selectivity as defined below.

Starting from a certain raw material in order to prepare a lubricating oil with a predetermined viscosity after dewaxing under certain operating conditions, “
``required temperature'' refers to the temperature that must be used to obtain such a lubricating oil, ``aromatic retention'' refers to the percentage of aromatics present in the lubricating oil relative to the aromatic content of the feedstock, and ``required temperature'' refers to the temperature that must be used to obtain such a lubricating oil; ” is the yield of the above lubricating oil. The lower the required temperature and aromatic retention of the catalyst, and the higher the selectivity, the higher the viscosity index by hydrocracking a mixture of heavy hydrocarbons. In the past, a large number of catalysts have been provided for hydrocracking mixtures of heavy hydrocarbons to prepare lubricating oils with high viscosity index.

These catalysts are generally W-group catalysts supported on a carrier consisting of one or more oxides of group L, M-group, or W-group elements.
Contains one or more metals of group B, group B, and/or skin group metals, or their sulfides or oxides. These catalysts may further contain promoters such as phosphorus or shelf elements and halogens such as chlorine or fluorine. The applicant has carried out extensive research into the suitability of catalysts of the type mentioned above for the preparation of lubricating boar oil with a high viscosity index by hydrocracking mixtures of heavy hydrocarbons and has found that their suitability for this purpose is It has been found that this depends greatly on the type and amount of metals and halogens present in the carrier, as well as the type and properties of the carrier. A number of research catalysts of the type mentioned above have been completely unsuitable for such purposes because their required temperatures and aromatic retention are very high and their selectivities are very low.

Most catalysts were not very suitable for such purposes. However, either the required temperature, aromatic retention or selectivity of these catalysts were inadequate to obtain optimal catalytic activity. A few catalysts of the type mentioned above are
However, it has shown excellent performance when hydrocracking mixtures of heavy hydrocarbons to prepare lubricating oils with high viscosity index. The required temperature and aromatic retention of these catalysts were very low, while their selectivity was necessarily high. When hydrocracking mixtures of heavy hydrocarbons to prepare high viscosity index lubricating oils, further research on the types of catalysts mentioned above shows that these catalysts work best under the following conditions: It became clear that we had to satisfy the following. The finished catalyst has at least 0. It must have a bulk specific gravity of total/secretion and contain at least 3 parts by weight of nickel and at least 2 parts by weight of tungsten and external fluorine for every 10 parts by weight of the alumina support. The compacted bulk density of a material in this patent application refers to the ratio of the weight of a given amount of material to its volume after compaction, and this compaction is very preferably carried out with an electric vibrator. The catalyst must be prepared from an alumina hydrogel.

This alumina hydrogel has a 0.0% density when dried and dried. Definitely/
It must have the properties to yield a xerogel having the following compacted bulk specific gravity. The method of preparing the catalyst from this hydrogel depends on the pore volume coefficient of the xerogel. In this patent application, the pore volume coefficient of a material is the ratio of the mercury pore volume to the total pore volume of the material, and the mercury pore volume is determined by 7. It is defined as the volume of pongee pores present in pores with a diameter larger than the rule m, and the total pore volume was determined by the pongee pores present in pores with a diameter smaller than 6 mm determined with nitrogen and mercury. It is defined as the total volume of pores present in the pores having a diameter of at least 6 m. If the pore volume coefficient of the xerogel is at least 0.5, the preparation of the catalyst can in principle be carried out in two ways, which can be expressed as the hydrogel method and the xerogel method: if the pore volume coefficient of the xerogel is at least 0.5. If it is less than 5, the hydrogel method is the only suitable method for preparing the catalyst. 0.7 after drying and baking
g' desk and compacted bulk specific gravity of less than or equal to and at least 0.5
The preparation of the catalyst by the xerogel method from an alumina hydrogel yields a xerogel with a pore volume coefficient of It is done by baking.

The preparation of the catalyst by the hydrogel method from an alumina hydrogel, which is dried and calcined to yield a xerogel having a compacted force specific gravity of less than 0.7 g/' and a pore volume coefficient of at least 0.5, and optionally introducing fluorine into the alumina hydrogel, drying and soaking the composition.

Dry and roast the shrimp to 0. Preparation of a catalyst by the hydrogel method from an alumina hydrogel that yields a xerogel with a compacted bulk specific gravity of Drying and heating the composition: In this catalyst preparation, the amount of fluorine to be introduced into the alumina hydrogel is determined by drying and lighting the alumina hydrogel into which fluorine has been introduced without introducing any metal. The amount is such that the pore volume coefficient is at least 0.5.

In addition to its use as a catalyst in the hydrocracking of heavy hydrocarbon mixtures to prepare highly viscous lubricating oils,
The catalyst according to the invention is also suitable for use in other processes for converting hydrocarbons at high temperatures, high pressures and in the presence of hydrogen. Therefore, the present invention provides for the production of hydrocarbons at high temperatures, high pressures, and in the presence of hydrogen.
It relates to a process for the conversion of hydrocarbons in contact with a fluorine-containing nickel-tungsten catalyst supported on alumina, the catalyst used being at least 0. The compacted bulk on the foundation has a specific gravity of at least 3 parts by weight of nickel and at least 2 parts by weight of tungsten per 100 parts by weight of the carrier, and when dried and dried, has a specific gravity of not more than 0.7 g/'. A xerogel having a compacted bulk specific gravity is prepared from an alumina hydrogel as follows: '1- If the pore volume coefficient of the xerogel is at least 0.5, the preparation of the catalyst is carried out using alumina Drying and annealing the hydrogel, introducing metal and optionally fluorine into the xerogel,
The method is carried out by drying and baking the composition, or by introducing metal and optionally fluorine into the alumina hydrogel, and drying and baking the composition.2) Pore volume coefficient of the xerogel is less than 0.5, the preparation of the catalyst is
The metal and fluorine are introduced into the alumina hydrogel, and the composition is dried and dried. The amount should be such that the pongee pore volume coefficient of the xerogel obtained is at least 0.5.

Only certain alumina hydrogels are suitable for preparing catalysts that can be used in the present invention.

To determine whether an alumina hydrogel can serve as a starting material for catalyst preparation and, if so, to further determine how to prepare the catalyst, one sample of the hydrogel was collected.
Dry at 2 and 0°C and heat at 550°C. Determine the compacted bulk specific gravity and pongee pore volume coefficient of the produced hydrogel.
The hydrogel is suitable for use as a starting material for catalyst preparation only if the compacted specific gravity of the xerogel is less than or equal to 0.71. The pore volume coefficient of the xerogel determines the method by which the catalyst should be prepared. When the pore volume coefficient of the xerogel is at least 0.5, both the xerogel method and the hydrogel method are suitable; when the pore volume coefficient is less than 0.5, only the hydrogel method is suitable; During the preparation of the catalyst by the hydrogel method, it should be ensured that a significant amount of fluorine is introduced into the hydrogel. The minimum amount of fluorine to be introduced into the hydrogel during catalyst preparation is determined by introducing different amounts of fluorine into a number of samples of the hydrogel, drying the fluorine-containing hydrogel at 120 ml, and drying it at 550°C. be able to. The string pore volume coefficient of the produced fluorine-containing xerogel is then determined. The minimum exothermic amount mentioned above is the amount that produces a fluorine-containing xerogel with a pore volume coefficient of 0.5. When using the xerogel method for the preparation of the present catalyst, the alumina hydrogel is first dried and allowed to cool, then introduced into the metal and optionally fluorine-bearing material, and finally the composition is dried and baked.

The introduction of metal into the material is most preferably carried out by impregnating the material with an aqueous solution containing nickel and tungsten compounds. Fluorine can be introduced into the catalyst by impregnation or in situ fluorination. If fluorine is introduced by impregnation into the catalyst, it can be carried out together with nickel and tungsten or in a separate impregnation step using an aqueous solution of the fluorine compound. The introduction of fluorine to impregnate the catalyst is preferably carried out in a separate impregnation step after introducing nickel and tungsten into a material that has been roasted and roasting it again. In situ catalytic fluorination is the initial phase of a process that uses a catalyst;
This can be done by feeding an amount of fluorine compound into the gas and/or liquid stream passed over the catalyst until the catalyst reaches the required fluorine content. When using a catalyst prepared by the xerogel method in the method according to the present invention, it is preferable to use a catalyst into which fluorine is fluorinated on the spot. When using the hydrogel method for the preparation of the present catalyst, the metal and optionally fluorine are introduced into the hydrogel and the composition is then dried and calcined.

The introduction of metals into the hydrogel is most preferably carried out by treating the hydrogel with an aqueous solution containing a nyl compound and a tungsten compound. This process is suitable for 5 or more, especially 6
Preferably, it is carried out at a temperature of 0 to 250 qo. The element can be introduced while the alumina is present as a hydrogel, or after aging the composition, or fluorinated in situ. If the alumina is still present as a hydrogel, the introduction of fluorine into the catalyst is preferably carried out by treating the hydrogel with an aqueous solution containing a nickel compound, a tungsten compound and an evolving compound. In the method according to the present invention,
When using catalysts prepared by the hydrogel process, it is preferred to use catalysts which introduce at least small amounts of fluorine, especially significant amounts of fluorine, while the alumina is still present as a hydrogel. Catalysts suitable for use in the process of the invention contain at least 3 parts by weight of nickel and at least 2 parts by weight of tungsten per 10 parts by weight of alumina.

When the catalyst is prepared by the xerogel method, a catalyst containing 3 to 75 parts by weight of nickel and 20 to 75 parts by weight of tungsten per 100 parts by weight of alumina, especially a catalyst further with a weight ratio of nickel to tungsten of 1:5 to 1:7. is preferred.

Catalysts prepared by the xerogel method preferably contain 0.5 to 2 parts by weight of fluorine per 10 parts by weight of alumina. When used for preparing lubricating oil,
The fluorine content should preferably be between 0.5 and 1 part by weight per 10 parts by weight of alumina, and these catalysts are suitable for hydrocracking mixtures of heavy hydrocarbons to prepare light hydrocarbons. The fluorine content should preferably be between 10 and 2 parts by weight per 100 parts by weight of alumina. If the catalyst is prepared by the hydrogel method, the catalyst contains 25 to 5 parts by weight of nickel and 50 to 8 parts by weight of tungsten per 10 parts by weight of alumina, especially in addition a nickel to tungsten ratio by weight of 1:1.5.
~1:5 catalyst is preferred.

The catalyst prepared by the hydrogel method preferably contains 10 to 3 parts by weight of fluorine per 10 parts by weight of alumina.
When these catalysts are used for the preparation of viscous lubricating oils by hydrocracking mixtures of heavy hydrocarbons, their pyrocarbon content is preferably between 10 and 25 parts by weight per 100 parts by weight of alumina. and when these catalysts are used for hydrocracking heavy hydrocarbons to prepare light hydrocarbons, the fluorine content is preferably between 20 and 30 parts by weight per 10 parts by weight of alumina. Should. If the alumina hydrogels used as starting material for the preparation of the catalysts are dried and parboiled to give xerogels with a compacted bulk specific gravity of 0.7 g', the catalysts prepared on the basis of these hydrogels are At least 0. It must have a compacted bulk specific gravity of chick's.

The specific gravity of the compacted bulk increases especially when metal is introduced, and further increases if the amount of metal used is not large. The compacted bulk specific gravity is determined by pressurizing the hydrogel, for example, by pressing,
It increases further due to extrusion, etc., and increases further as the pressure increases. When hydrogels are pressed under high pressure through narrow openings such as slits, the compacted bulk density increases considerably. The compacted bulk density, which increases when a hydrogel is pressurized, can be further increased somewhat by introducing certain additives to the hydrogel, such as nitric acid and aluminum salts. In addition to fluorine, the catalyst may include other promoters such as phosphorus and shelf atoms. Metallic nickel and tungsten or their oxides or sulfides can be present in the catalyst.

Preferably, the catalyst is used as a sulfide. Sulfurization of the present catalyst can be carried out by a known catalyst sulfurization method. Sulfurization can be carried out by contacting the catalyst with a sulfur-containing gas, such as a mixture of hydrogen and hydrogen sulfide.
Sulfurization can also be carried out by contacting the catalyst with a sulfur-containing hydrocarbon oil, such as a sulfur-containing gas oil. The catalyst is of particular interest for use in hydrocracking mixtures of heavy hydrocarbons to prepare high viscosity lubricating oils. Preferred mixtures of heavy hydrocarbons that can be used as starting materials for the preparation of lubricating oils according to the invention include waxy lubricating oil fractions obtained by distilling the atmospheric distillation residues of waxy crude oils under reduced pressure; The waxy lubricating oil crab is a wax obtained from the waxy lubricating oil crab prepared by hydrocracking.
An example of such a waxy lubricant is spindle oil (S
O), light machine oil (LMO), medium machine oil (MMO) waxy distillate and de-asphalted oil (DAO), S○, waxy raffinate of LMO and MMO, furfural from the above lubricating oil fractions. mouth-like bright stock obtained by treating the latter with a solvent that is selective for aromatics, and S0, LM○, MM○, DAO and This is Satoshi's Slackworks. Mixtures of one or more lubricating oil distillate fractions and/or one or more lubricating oil residues and/or one or more slack waxes are also a starting point for the lubricating oil preparation according to the invention. Can be used as a substance.

Hydrocracking of heavy hydrocarbon mixtures to prepare high viscosity lubricating oils according to the invention is carried out by contacting the heavy hydrocarbon mixture with a catalyst at high temperature, high pressure and in the presence of hydrogen. , is preferably present in one or more beds of particles having a diameter of 0.5 to 3 bars.

Suitable hydrocracking conditions are as follows: temperature 325-450 qo, pressure 10-250 bar.
Hydrogen/feedstock ratio 100-5000 (NI of hydrogen per unit k9 of feedstock) and space velocity 0.2-5.0 (k9 of feedstock per unit of catalyst per unit time).

Preferably the following conditions are used: temperature 350-425o
o, pressure 100-200 bar, hydrogen/raw material ratio 500
~2500 (NI of hydrogen per unit k9 of feed) and space velocity 0.5 to 1.5 (k9 of feed per unit of catalyst per unit time). The aromatic content of the lubricating oil prepared according to the present invention is low. A lubricating oil with a lower aromatic content can be obtained in the present invention by providing a hydrofinishing step after the hydrocracking step. Hydrofinishing of a hydrocracking product can be carried out by contacting the product with a hydrofinishing catalyst at high temperature, high pressure, and in the presence of hydrogen. The pressures, space velocities and gas velocities used in the hydrofinishing step can be selected within the same ranges as in the hydrocracking step described above. The hydrofinishing temperature is preferably selected between 225 and 40°C, especially between 275 and 375°C. The temperature used in the hydrofinishing process is at least 25q below the hydrocracking temperature.
o Should be lower. Suitable hydrofinishing catalysts include one of the Group WB, Group B or Blood Group metals on a support.
Or a catalyst containing two or more. The effluent from the hydrocracking device, or in the case of hydrofinishing, the effluent from the hydrofinishing device, is cooled and separated into hydrogen-rich gas and liquid products. The liquid product includes hydrocarbons boiling below and above the boiling range of the lubricating oil. Hydrocarbons boiling below the above range are separated from the high-boiling residue, preferably by fractional distillation. The cutting point of this distillation is preferably chosen such that the initial boiling point of the high-boiling residue is in the range 350-550 oo. In addition to being a good lubricating oil component, this residue contains n-paraffins that generally solidify at room temperature, thus lowering the pour point of the lubricating oil. Therefore, in order to obtain a suitable lubricating oil from the residue, it is preferable to dewax the residue. The dewaxing treatment can be performed by any desired method. Preferably, the dewaxing is carried out using a mixture of methyl-ethyl-ketone and toluene at a temperature of -10 to -4030 °C and a solvent/oil volume ratio of 1:1 to 10:1. To increase the lubricating oil yield, it is preferred to recirculate at least a portion of the separated paraffin to the hydrocracking device. In addition to being used as a catalyst in the hydrocracking of mixtures of heavy hydrocarbons to prepare high viscosity index lubricating oils, the catalyst is suitable for use in gas oils, flash distillates and mixtures of flash distillates and de-asphalted oils. It is also very suitable for use in the first stage in a two-stage process in the preparation of light hydrocarbons such as.

Examples of other processes according to the invention in which the present catalyst can be used effectively are: preparation of light hydrocarbons from mixtures of heavy hydrocarbons by single-stage hydrocracking, to improve dust spots; hydrogenation of aromatics present in light fuels such as kerosene, hydrodesulfurization of distillates and residual hydrocarbons;
- Hydrofinishing of lubricating oils and preparation of refined white medicinal oils with reduced aromatic content, hydrotreating mineral oil fractions. Next, the present invention will be explained according to examples.
A total of 37 catalysts were tested for converting hydrocarbon oils at high temperatures, high pressures, and in the presence of hydrogen.

Among these 37 catalysts, one sphere catalyst belongs to the present invention (catalysts 1 to 19), and 18 catalysts belong to the present invention (catalysts A to T). The catalyst was prepared as follows.
Catalysts 1-13 These catalysts were dried and illuminated to give xerogels with a compacted bulk specific gravity of 0.3' and a pore volume coefficient of 0.8. ) was prepared by the xerogel method.

Catalysts 1 to 7 were prepared by drying, extruding and extruding alumina hydrogel 1, impregnating the extrudate with an aqueous solution containing a nickel compound and a tungsten compound, and drying and extruding the impregnated extrudate. .

Catalyst 8 was prepared by drying, extruding and baking alumina hydrogel 1, impregnating the extrudate with an aqueous solution containing a nickel compound, a tungsten compound and a shelving compound, and drying and baking the impregnated extrudate. went.

Fluorine was introduced by fluorinating the catalyst in situ.

Catalysts 9 to 13 were prepared by drying alumina hydrogel 1,
The extrudate is impregnated with an aqueous solution containing a nickel compound and a tungsten compound, the impregnated extrudate is dried and annealed, the extrudate is impregnated with an aqueous solution containing a fluorine compound, and the extrudate is impregnated with an aqueous solution containing a fluorine compound. The impregnated extrudates were dried and fired. New fluorine was introduced by fluorinating catalysts 10 to 13 on the spot. Catalysts 14-19 These catalysts were prepared by the hydrogel method.

Catalysts 14-17 were prepared from alumina hydrogel 1 above. Catalysts 18 and 19 are dried and calcined to give 0
．． A xerogel was prepared from an alumina hydrogel (alumina hydrogel) yielding a compacted bulk specific gravity of 7 g/' and a pore volume coefficient of 0.3. The catalyst 14 is prepared by mixing an aqueous solution containing a nickel compound and a tungsten compound with alumina hydrogel 1, and forming a mixture.
After maintaining the metal-loaded hydrogel at a moderately high temperature and separating it from the mixture, the hydrogel was dried, extruded, and extruded. *The element was introduced by fluorinating catalyst 14 on the spot. Catalysts 15 to 19 were prepared by combining an aqueous solution containing a nickel compound, a tungsten compound, and a fluorine compound with alumina hydrogel 1 (in the case of preparing catalysts 15 to 17) or alumina hydrogel LO (in the case of preparing nutrients 18 and 19). After mixing and maintaining the mixture at a high temperature to separate the metal and thermoelement-loaded hydrogel from the mixture, the hydrogel was dried, extruded, and fired.

New fluorine was introduced by chemically converting shark media 1017 and 19 on the spot. Catalysts A-E These catalysts were prepared from the above alumina hydrogels 1 and 0 by the xerogel method.

Preparation of catalysts A and B consisted of alumina hydrogel 1 (catalyst A
(in the case of the preparation of catalyst B) or alumina hydrogel 0 (in the case of the preparation of catalyst B) by drying, extruding and holding the extrudate and/or
Alternatively, it was impregnated with an aqueous solution containing a tungsten compound, and the impregnated press was dried and baked.

Fluorine was introduced by fluorinating catalysts A and B in situ.
Catalysts C to B were prepared by drying, extruding and firing alumina hydrogel, impregnating the extrudate with an aqueous solution containing a nickel compound and a tungsten compound, drying the impregnated extrudate, and drying the extrudate. The extrudates were impregnated with an aqueous solution containing the beauty compound, and the impregnated extrudates were dried and baked.

New fluorine was introduced by fluorinating Catalysts D and E in situ. Catalysts F and G These catalysts were prepared from the above alumina hydrogel by a hydrogel method.

Catalyst F is prepared by mixing an aqueous solution containing a nickel compound and a tungsten compound with alumina hydrogel, maintaining the mixture at a very high temperature, separating the metal-incorporated hydrogel from the mixture, and then drying and extruding the hydrogel. And grilled shrimp.

Fluorine was introduced by fluorinating the catalyst in situ. Catalyst G is prepared by mixing an aqueous solution containing a nickel compound, a tungsten compound, and a fluorine compound with alumina hydrogel, maintaining the mixture at a very high temperature, and separating the metal and fluorine-introduced hydrogel from the mixture. The hydrogel was dried, extruded, and fired.

New fluorine was introduced by fluorinating catalyst G on the spot.
Catalysts H to T These catalysts were prepared by impregnating a calcined carrier with an aqueous solution containing one or two metal compounds and optionally a shelving compound or a phosphorous compound, and then drying and brazing the composition. .

The catalyst was prepared by impregnating a silica-zirconia structure with an aqueous solution containing a platinum compound, and then drying and drying the composition.

Catalysts J to N were prepared by impregnating an alumina support with an aqueous solution containing a nickel compound, a molybdenum compound, and a phosphorus compound, and then drying and grinding the composition.

Fluorine was introduced by fluorinating catalysts K to M on the spot. Catalyst N was prepared by impregnating an alumina support with an aqueous solution containing a nickel compound, a tungsten compound, and a shelving compound, and then drying and holding the composition for some time.

For the preparation of catalysts P to R, an alumina loss body (in the case of preparing catalyst P), a silica-alumina support (in the case of preparing catalyst Q), or a silica-magnesia support (in the case of preparing catalyst R),
After impregnating with an aqueous solution containing a nickel compound and a tungsten compound, the composition was dried and fired.

The preparation of catalysts S and T is carried out after impregnating a fluorine-containing Flumina support with an aqueous solution containing a nickel compound and either a tungsten compound (in the case of the preparation of catalyst S) or a molybdenum compound (in the case of the preparation of catalyst T). , the composition was dried and calcined.

The chemical composition and other data for the various catalysts are set forth in Tables A and B.

Table A) Catalyst 8 consisting of newly added 4 parts by weight of shelf elements per 100 parts by weight of alumina support.

When preparing catalysts 18, 19 and G, the amount of fluorine introduced into the hydrogel was such that the pore volume coefficient of the xerogel obtained by drying and drying these fluorine-containing hydrogels was 0.7 and 0.7, respectively. The amounts were 0.6 and 0.4. Table B Example 1 - After dewaxing with 30 qo, 40 qo with town 130
The required temperature, aromatic retention, and selectivity of a number of catalysts shown in Table A were compared in hydrocracking tests conducted under the following conditions to prepare ten lubricating oils.

Raw material: Oil obtained by removing and asphalting the residue produced when distilling the atmospheric distillation residue of Middle Eastern crude oil under reduced pressure.

Properties of raw materials: - W after dewaxing at 30qo: 77 Sulfur content: 2.1% by weight Nitrogen content: 63 bwn Aromatic content: 13 mol/10 female Hydrocracking conditions: Pressure: 150 bar Space velocity: 1 and/or so. hr. Hydrogen/raw material ratio: 200N so/ku The catalyst was used as a sulfide.

The sulfidation of the catalyst was carried out in contact with a mixture of hydrogen and hydrogen sulfide in a volume ratio of 7:1 at a temperature of 75-375 qo and a pressure of 10 bar for 5 hours. Dewaxing is performed using a 1:1 ratio of methyl-
It was carried out using a mixture of ethyl-ketone and toluene.
In-situ fluorination of the catalyst was carried out by feeding 30 pm pmw of fluorine in the form of o-fluoro-toluene into the feed during the first test phase until the required catalytic fluorine content was obtained. .

The catalyst was tested as a 1.5 side extrudate. In this test, an optimal catalyst should have a required temperature of at most 420q0, an aromatic retention of at most 30% and a selectivity of at least 35% by weight.

The test results are shown in Table C.

Table C Example 2 - 375o with river 128 after de-owing at 2000
The required temperature, aromatic retention, and selectivity of a number of catalysts shown in Tables A and B to prepare o+ lubricating oils were compared in hydrocracking tests conducted under the same conditions as those described in Example 1. did.

Raw material: Oil obtained by de-asphalting the residue produced when distilling the atmospheric distillation residue of Middle Eastern crude oil under reduced pressure.

Properties of raw materials: W after dewaxing at -20 qo: 81 Sulfur content: 2.5 wt% Nitrogen content: 78 ybwm Aromatic content 310 melon hmol/100 g Catalyst bed: 10
The catalyst was tested as particles with a diameter of 0.5 to 1.4 bars.

For this test, an optimal catalyst should have a required temperature of no more than 420 pm, an aromatic retention of no more than 30%, and a selectivity of at least 40% by weight.

The test results are shown in Table D.

Table D *) Under the test conditions it was not possible to prepare a lubricating oil with a catalyst date of 128.

The catalyst dates shown in Table D are for the preparation of oils having a town of 112.

Example 3 After dewaxing at -200°C, hydrolysis was carried out under the following conditions for the required temperatures and selectivities of a number of catalysts shown in Tables A and B to prepare 43 and 000 lubricating oils having W96. Comparison was made in a cracking test.

Raw material: Waxy carcass distillate lubricating oil fraction of Middle Eastern crude oil.

Properties of raw materials: W after dewaxing at -20q○: 37 Sulfur content: 3% by weight Nitrogen content: 1250pbwm Hydrocracking conditions: Hydrogen partial pressure: 14 Lugor Space velocity: lkg'so. hr Hydrogen/raw material ratio: 200kg Catalyst bed: 250 kites [ The catalyst was tested as a 1.5 mm extrudate.

The conditions for catalyst sulfidation and in-situ hydrogenation and oil dewaxing were the same as described in Example 1. In this test, the optimal catalyst should have a required temperature of at most 405q0 and a selectivity of at least 51% by weight.

The test results are shown in Table E.

Table E Example 4 A number of the catalysts shown in Tables A and B were used in hydrocracking tests for the preparation of lubricating oils having 150 and 390 qo after dewaxing at 130 qo.

Raw material: Brightstock Slutswax Properties of raw material: Oil content: 3% by weight Sulfur content: 0.7% by weight Nitrogen content: 86 pbwm Then hydrocracking is carried out under conditions of 7% by weight Hydrogen partial pressure: 130 bar Space velocity: lk9/〆. hr. Hydrogen/Feed Ratio: 1500 Sono K9 Catalyst Bed: 250 Top Catalyst was tested as a 1.5 side extrudate.

The conditions for catalyst sulfidation and in-situ fluorification and oil de-oxygenation were the same as described in Example 1. The test results are shown in Table F'.

Table F Tables C-F' The results shown here indicate that very similar catalysts (catalysts A-G) and hydrocracking of lubricating oils outside the scope of the present invention, when hydrocracking to prepare high viscosity index lubricating oils. Other catalysts previously proposed for the preparation (
Catalysts H to T), catalysts according to the present invention (Catalysts 1 to 1)
9) clearly shows that it is superior.

Example 5 A number of the catalysts shown in Table A were used in the first stage of a two-stage process in hydrocracking heavy hydrocarbon oils to prepare gasoline and middle distillates.

material: Flash distillate of Middle East crude oil.

Properties of raw materials: Initial boiling point: 300q0 Final distillate boiling point: 52020 Second base weight % nitrogen content of raw materials boiling below 370q0:
65 bwm Polyaromatic content: 6 hmol/10 hmol Hydrocracking conditions: Temperature: 370 ○ Pressure: 13 rules Space velocity: 1.7〆/so. hr. Hydrogen/raw material ratio: 100 Iso/K catalyst was used as sulfide.

The sulfidation of the catalyst was carried out in one vowel contact with a mixture of hydrogen and hydrogen sulfide in a volume ratio of 7:1 at a temperature of 75 DEG -450 DEG C. and a pressure of 10 bar. In situ fluorination of the catalyst is carried out during the first test phase until the required catalyst fluorine content is obtained.
The feedstock was fed with 200 pmw of acetic acid in the form of fluorotoluene. The catalyst was tested as a 1.5 skin extrudate. The test results are shown in Table G'.

Table G The results shown in Table G show that in the first stage of a two-stage process for the preparation of gasoline and middle distillates by hydrocracking, a very similar catalyst (catalyst A) outside the scope of the invention The catalysts according to the present invention (catalysts 2 to 7, 12)
and 13) are clearly shown to be superior.

Claims (1)

[Claims] 1 Hydrocarbons at high temperatures, high pressures, and in the presence of hydrogen are catalyzed by fluorine-containing nickel-tungsten catalysts supported by alumina (
The catalyst has at least 0.8 g/ml compaction (com
pacted) having a bulk specific gravity and containing at least 3 parts by weight of nickel and at least 20 parts by weight of tungsten per 100 parts by weight of support, said contact being obtained by the following catalyst preparation method: A catalyst was prepared as follows from "alumina hydrogel that can be dried and baked to obtain a xerogel having a compacted bulk specific gravity of 0.79/ml or less", and (a) When the pore volume coefficient of the xerogel is at least 0.5, the preparation of the catalyst comprises
(a) drying and baking the alumina hydrogel, introducing metal and optionally fluorine into the xerogel, and drying and baking the composition; or (b) introducing metal and optionally fluorine into the alumina hydrogel. (b) When the pore volume coefficient of the xerogel is less than 0.5, the preparation of the catalyst is carried out by drying and baking the composition. However, in this case, the amount of fluorine introduced is determined by the amount of xerogel obtained by drying and baking the alumina hydrogel into which fluorine is introduced without introducing any metal. A method for converting hydrocarbons, characterized in that the amount is such that the pore volume coefficient is at least 0.5.