JPS5821674B2 - Hydrocarbon conversion method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to white oils, a class of oils that includes industrial white oils and pharmaceutical oils.

In the present invention, the industrial white oil is almost odorless and tasteless, and is defined as Saybolt (5aybolt) larger than +30.
) chromaticity and falls under FDA Standard No. 1212589.

According to the above standards, 280-289nm, 290-29nm
9nm.

The UV absorption of oil in the wavelength bands 300-329 nm and 330-350 nm is at most 4
．． 0, 3.3, 2.3 and 0.8.

Various sectors in which industrial white oils are widely used include the textile industry, plastic industry, cosmetic industry, paper industry and rubber industry.

In the present invention, the term medicinal oil has a Seibold chromaticity greater than +30 and has a Seibold chromaticity of greater than +30 [
Hot acid J test and FDA standard No. 12
Used to describe a tasteless and odorless hydrocarbon oil that complies with the requirements specified in No. 11146.

For the thermal acid test according to ASTM-D565, the oil is treated with concentrated sulfuric acid.

Both substances are heated and mixed. As a result, two layers are formed: an oil layer and an acid layer.

Inspect the color of these two layers.

To pass this test, the oil layer must not be totally thermally bleached.

The acidic layer may change color if only slightly.

However, it should not be darker than the given control solution.

Under the conditions specified in FDA Standard No. 1211146, the ultraviolet absorption of oil in the wavelength band of 260 to 350 layers is said to be at most 0.10.

Pharmaceutical oils are used in the plastics industry, among other uses.
Used on a large scale in the cosmetics, food and pharmaceutical industries.

White oil is produced on an industrial scale from a hydrocarbon mixture of suitable viscosity as a starting material, by successive treatment of this mixture with large amounts of concentrated or fuming sulfuric acid, neutralization and further treatment with solid adsorbents. Manufactured.

The amount of concentrated sulfuric acid or fuming sulfuric acid used in this process varies depending on the aromatic content of the feed oil and the type of white oil being produced.

Even in the preferred case of using mineral oil extracted with a solvent that selectively dissolves aromatic compounds as feedstock, the manufacturing process
Amounts of up to 0% by weight of fuming sulfuric acid (containing 30% of dissolved 5O3) are required to obtain medicinal oils.

However, if the corresponding mineral oil fraction, which has not been pretreated to reduce the aromatic content of the mineral oil, is used as feedstock,
Quite significant amounts of oleum may be required.

The above method has many drawbacks.

The main drawback concerns the acid tar obtained as waste with this process.

In view of the increasingly stringent requirements imposed by pollution prevention, the disposal of the acid tar, which is obtained in considerably large quantities by this process, has become an increasingly important problem.

Another drawback of the above method relates to yield.

Depending on the amount of undesirable components contained in the starting material and removed by acid treatment, the above process results in a relatively low yield of white oil.

Finally, the above method is somewhat expensive. In order to eliminate the above-mentioned drawbacks in the production of white oils, it is preferable to carry out mostly or entirely two-stage catalytic hydrogen treatment instead of acid treatment.

For this purpose, the feedstock is treated with a mixed sulfide catalyst in the first step,
In the second step, a mixed sulfide catalyst or a noble metal catalyst can be contacted at elevated temperature and pressure and in the presence of hydrogen.

In the present invention, a mixed sulfide catalyst refers to a sulfide catalyst containing nickel and/or cobalt and further molybdenum and/or tungsten on a carrier, and a noble metal catalyst refers to a sulfide catalyst containing one or two of Group Ⅰ on a carrier. Catalysts containing the above precious metals.

If the acid treatment is not carried out together with the catalytic hydrogen treatment, the second step of the catalytic hydrogen treatment may optionally be followed by treatment with a solid adsorbent.

If the acid treatment is carried out together with the catalytic hydrogen treatment, the acid treatment is carried out after the second step of the catalytic hydrogen treatment, followed by the treatment with the solid adsorbent.

When acid treatment is replaced by mostly two-stage catalytic hydrogen treatment, only relatively small amounts of concentrated or fuming sulfuric acid are used, so that acid tars are also formed in relatively small amounts and are discarded. Problems with objects are greatly reduced.

Furthermore, since most of the undesirable components contained in the feedstock are not removed in this process but are converted into valuable white oil components, this process is much more expensive than the process described above, which involves treatment with large amounts of concentrated sulfuric acid. Yield is obtained.

Finally, a process in which acid treatment is mostly replaced by a two-stage catalytic hydrogen treatment is less expensive than a process in which only a large amount of concentrated sulfuric acid or fuming sulfuric acid is used and no catalytic hydrogen treatment is performed.

The above-mentioned advantages regarding the reduced amount of acid tar produced, white oil yield and process cost become more important as concentrated or fuming sulfuric acid is used less and less acid treatment is replaced by a two-stage catalytic hydrogen treatment. As the processing takes place, the most interesting positions are of course reached.

As a result of research on the production of white oil, the applicant conducted two-stage hydrogen treatment with a mixed sulfide catalyst in the first step, and with a mixed sulfide catalyst or noble metal catalyst in the second step, and then post-treated with an acid. It depends on whether a mixed sulfide catalyst or a noble metal catalyst is used as the second stage catalyst, respectively, in the production of white oil in high yields with or without The temperature used is at least 25° C. lower than the temperature of the first step when a mixed sulfide catalyst is used as the second step catalyst, and lower than the temperature of the first step when a noble metal catalyst is used as the second step catalyst. Waxes have been found to be excellent starting materials for the production of these white oils when the temperature is at least 50° C. below.

Whether an acid post-treatment should be performed together with the catalytic hydrogen treatment depends primarily on the type of catalyst used in the second step.

For the production of industrial white oil and pharmaceutical oil, the second
It has been found that acid post-treatment is not necessary when noble metal catalysts are used in the process.

The necessity of acid treatment when a mixed sulfide catalyst is used in the second step depends, inter alia, on the aromatic content of the wax used as feedstock in this process, the reaction conditions used in the second step, It varies depending on the activity of the two-step catalyst and the type of white oil produced.

In most cases where mixed sulfide catalysts are used in the second step, acid work-up is not necessary.

However, if, for example, medicinal oils are to be produced from waxes with a high aromatic content, the use of mixed sulfide catalysts may require further acid post-treatment.

If acid post-treatment is not required, the two-stage catalytic hydrogen treatment may optionally be followed by treatment with a solid adsorbent.

If the production of white oil from wax is carried out by a two-stage catalytic hydrogen treatment followed by acid after-treatment, the treatment with the solid adsorbent is carried out after the acid after-treatment.

In addition to being a cheap starting material for the production of white oils, the waxes obtained primarily as by-products in the production of lubricating oils, with or without subsequent post-treatment with acids, by two-stage catalytic hydrogen treatment. The white oil thus obtained has a very low naphthene content.

Although the naphthene content of white oils is not included in the specifications for these oils, a low naphthene content can result in the formation of significant amounts of aromatics from dehydrogenation of naphthenes when white oils are subjected to high temperatures. It is very interesting that the naphthene content is very low, since the properties are lost.

Therefore, the present invention provides for the production of white oil by subjecting the wax to a two-stage hydrogen treatment, in the first step over a mixed sulfide catalyst and in the second step over a mixed sulfide catalyst or a noble metal catalyst,
The wax is then converted to a white oil, with or without acid after-treatment, and the temperature used in the second step is such that a mixed sulfide catalyst or a precious metal is used as the catalyst in the second step. They vary depending on the catalyst used, i.e.
The temperature used in the second step is at least 25° C. lower than the temperature in the first step when a mixed sulfide catalyst is used as the second step catalyst, and when a noble metal catalyst is used as the second step catalyst. If the temperature of the first step is less than that of the first step, both 50° C., and the above steps are carried out as follows, i.e. (a) if a noble metal catalyst is used in the second step,
subjecting the wax to the two-stage catalytic hydrogen treatment described above, optionally followed by treatment with a solid adsorbent, to produce a white oil; (b) if a mixed sulfide catalyst is used in the second step; A white oil is produced by subjecting the wax to the two-stage catalytic hydrogen treatment described above, optionally followed by treatment with a solid adsorbent, or after-treatment with an acid and further treatment with a solid adsorbent.

The present invention relates to a method for producing the white oil.

The waxes used as starting materials for the production of white oils according to the invention are preferably obtained as a by-product during the production of lubricating oils by conventional methods or in the production of lubricating oils by hydrocracking.

Conventional lubricant production is carried out as follows.

That is, petroleum crude oil is distilled under atmospheric pressure into a large number of fractions (particularly subsequently one or more gasoline fractions, dissolved oil fractions and light gas oil fractions) and residues (known as long residues). ).

This long residue is then distilled under reduced pressure into a number of fractions (particularly one or more heavy gas oil fractions, spindle oil fractions, light machinery oil fractions and intermediate heavy machinery oil fractions). ) and residual oil (known as short residual oil).

The corresponding lubricating oil is produced by refining from the lubricating oil fraction obtained by vacuum distillation.

The purification of spindle oil fractions, light machine oil cuts and intermediate heavy machine oil cuts is carried out by removing aromatics and waxes from these cuts.

In short residue refining, asphalt is first removed from the residue.

The deasphalted oil thus obtained is subsequently freed of aromatics and waxes.

The residual lubricating oil produced in this way is named Pritestock.

The wax obtained during the refining of various lubricating oil fractions is termed distillate slack wax or residual oil slack wax, depending on the type of lubricating oil fraction from which it is derived.

The above-mentioned distillate oil slack wax and residual oil slack wax (spindle oil slack wax, light machine oil slack wax, intermediate heavy machine oil slack wax and bright oil slack wax) are used in the white oil production of the present invention. It is an excellent starting material for

Lubricating oil production by hydrogenolysis is carried out as follows.

That is, heavy fractions of petroleum crudes, such as vacuum distillates, deasphalted oils or distillate slack waxes or residual slurry waxes, are passed over suitable catalysts under hydrocracking conditions.

The lubricating oil or oils containing residual lubricating fractions are separated from the hydrogenolysis products by distillation.

From the lubricating oil fractions thus obtained, corresponding lubricating oils are produced by removing the wax from these fractions.

The distillate oils and residual slack waxes, which are separated from the hydrocracked products, are also excellent starting materials for the white oil production of this invention.

If desired, mixtures containing one or more distillate oils and/or one or more residual slack waxes can be used as starting materials.

If the wax obtained as a starting material for the process of the present invention has a high aromatic content, it is preferable to deoil it before carrying out the catalytic hydrogen treatment.

used in the first step of the production method of the present invention, and also used in the second step.
Catalysts that may also be used in the process are sulfide catalysts containing nickel and/or cobalt and also molybdenum and/or tungsten on a support.

Preferably, the catalyst contains 1 to 30 parts by weight, especially 2 to 20 parts by weight of nickel and/or cobalt and furthermore 1 to 80 parts by weight of molybdenum and/or tungsten, especially 10 to 80 parts by weight, per 100 parts by weight of support.

The weight ratio of nickel and/or cobalt on the one hand to molybdenum and/or tungsten on the other hand is preferably in the range 1:1 and 1:10.

Suitable supports for mixed sulfide catalysts are, for example, amorphous oxides of elements of groups I, II and II of the Table of Elements, such as silica, alumina, magnesia, zirconia, doria and boria and oxides of these. Mixtures such as silica-alumina, silica-magnesia, silica-zirconia and silica-alumina-zirconia.

Catalysts containing alumina as support are preferred.

The metal can be deposited on a support by any method known in the art for the preparation of catalysts containing several components, for example by co-impregnating the support in one or more steps with an aqueous solution containing a salt of the metal and then drying. It can be added to the mixed sulfide catalyst according to the method of calcining.

If the impregnation operation is carried out in several steps, the material may be dried and calcined between the various impregnation steps.

In the first step of the hydrotreatment according to the invention, and if possible also in the second step, a catalyst is used in which the catalytically active metal is in the form of a sulfide.

The sulfurization of the catalyst can be carried out according to any method known in the art for catalytic sulfidation, for example by exposing the catalyst to a sulfur-containing gas such as a mixture of hydrogen and hydrogen disulfide, a mixture of hydrogen and carbon disulfide, or a mixture of hydrogen and a mercaptan such as butyl mercaptan. This can be carried out by contacting with a mixture of.

Sulfurization can also be carried out by contacting the catalyst with hydrogen and a sulfur-containing hydrocarbon oil, such as a sulfur-containing liquid or gas oil.

In the production method of the present invention, when the feedstock oil has a low sulfur content, in order to ensure that the catalyst maintains the sulfide form during the production process when a mixed sulfide catalyst is used,
It is desirable to continuously add small amounts of sulfur compounds to the feedstock.

Very suitable catalysts for use as mixed sulfide catalysts in the hydroprocessing of the present invention include (a) one or more nickel compounds and/or
or by impregnating alumina with a solution containing a cobalt compound, one or more molybdenum compounds and/or tungsten compounds, phosphate ions and peroxides, and then drying and calcining this composition. catalyst (b) one or more nickel compounds and/or
or a cobalt compound and one or more molybdenum and/or tungsten compounds in a concentration sufficient to provide the finished catalyst with a metal content of 30 to 65% by weight expressed as metal oxides. The alumina hydrogel, which is a catalyst prepared by adding to the hydrogel and then drying and calcining this composition, to which a metal compound is added, has a packed bulk density of 0.75 to L6g/L after drying and calcining. rrtl and pore volume 0.15
The hydrogel should yield a pserogel with ~0.5 ml/g.

(c) A composition containing alumina, water, one or more water-soluble salts of nickel and/or cobalt, and one or more water-soluble salts of molybdenum and/or tungsten is heated at 150°C or lower. A catalyst prepared by treating with a hydrogen disulfide-containing gas at a temperature and then heating this material in a hydrogen-containing gas to a final temperature of 200 °C or more,
110 in the drying gas in which the amount of water present in the composition treated with the hydrogen sulfide-containing gas is increased by 20-120% of the amount of water that the drying composition can hold in the pores of the carrier at 20°C. It should correspond to the amount of water present in the composition after drying at °C.

The catalytically active metal components of the sulfide catalyst used in the process of the invention are preferably nickel and molybdenum or nickel and tungsten.

In addition to the metals nickel and/or cobalt and molybdenum and/or tungsten, the sulfide catalyst used in the hydroprocessing of the invention preferably contains fluorine.

In principle, the introduction of fluorine into the catalyst can be carried out in two ways.

Fluorine can be incorporated into the catalyst during or after its manufacture by impregnating the catalyst with a suitable fluorine compound such as ammonium fluoride.

Fluorine can also be introduced into the catalyst by fluorinating the catalyst in situ at the beginning of the hydroprocessing for which the catalyst is used (for example during or after start-up of the process).

In situ fluorination of the catalyst can be carried out by adding a suitable fluorine compound, such as ortho-fluorotoluene or difluoroethane, to the gas and/or liquid stream passed over the catalyst.

In many cases, it is often advantageous to add more than 50% of the fluorine, especially nearly all of the fluorine, to the catalyst by in situ fluorination.

The sulfide catalyst preferably contains 0.5 to 15% by weight, especially 1 to 15% by weight.
Contains 7.5% by weight of fluorine.

Preferred conditions for carrying out the first step of the hydrogen treatment of the present invention are a temperature of 300 to 425°C, a hydrogen partial pressure of 10 to 250 bar, a space velocity of 0.1 to 5 kg of feed oil per catalyst 11 per hour,
The ratio of hydrogen/feedstock oil is 100 to 5 hydrogen per liter of feedstock oil.
00 ONl.

The first step of the hydrogen treatment of the present invention is preferably carried out under the following conditions.

That is, the temperature is 325-400°C, and the hydrogen partial pressure is 25-200°C.
bar, space velocity 0.5-2 feedstock per liter of catalyst per hour
kg, and the hydrogen/feedstock ratio is 500-250 ONA of hydrogen per kg of feedstock.

The second step of the hydrotreatment of the present invention can be carried out either in the presence of a mixed sulfide catalyst or in the presence of a noble metal catalyst.

When a mixed sulfide catalyst is used in the second step of the hydrotreating of the present invention, the temperature used in the second step is at least 70° C. but at least 25° C. less than the temperature used in the first step. Must-have.

If a noble metal catalyst is used in the second step of the hydrotreatment of the invention, the amount of Group 1 noble metal present on the support can vary within a wide range, but is often in the range 0.05 to 5% by weight. be.

The Group 1 noble metals present on the carrier are platinum, rhodium,
Ruthenium, iridium and osmium, with platinum being preferred.

Two or more of these metals may be present if desired.

The amount of Group 1 noble metal present in the catalyst is preferably 0.
1-2% by weight, especially 0.2-1% by weight.

As a support for the noble metals, consideration may be given as described hereinabove for mixed sulfide catalysts.

Alumina and silica-alumina are preferred as carriers for noble metal catalysts.

A highly preferred noble metal catalyst for use in the second step of the hydrotreating of the invention is a catalyst comprising one or more Group 1 metals on a support, the support being alumina 13-15
% by weight, with the remainder being silica.

The noble metal catalyst used in the second step of the hydrotreatment of the present invention may be prepared by any method known in the art for the production of catalysts containing one or more Group 1 noble metals on a support. can.

The catalyst is preferably prepared by impregnating a suitable support with an aqueous solution containing one or more noble metal compounds, and the composition thus obtained is dried and calcined.

The silica-alumina support suitable for the noble metal catalyst of the present invention is
For example, they are produced by co-precipitating silica and alumina, or by impregnating silica with an aluminum compound and then drying and calcining the material.

The latter precipitation method starts with an aqueous silicate solution (e.g. water glass), lowers its pH so that a silica hydrogel precipitates, ages the silica hydrogel, adds an aqueous solution of an aluminum compound, raises the pH and the resulting Alumina is precipitated onto a silica hydrogel and can be very conveniently carried out by drying and calcination.

Conditions suitable for carrying out the second step of hydrogen treatment of the present invention using a noble metal catalyst include a temperature of 175 to 325°C;
Hydrogen partial pressure 10-250 bar, space; rate per hour catalyst 11
0.1 to 5 kg of feedstock per kg of feedstock, and hydrogen/feedstock ratio of 100 to 500 ONl of hydrogen per kg of feedstock.
It is.

The second step of the hydroprocessing of the present invention using a noble metal catalyst is carried out under the following conditions: temperature 200-300°C, hydrogen partial pressure 25-200 bar, space velocity 0.5-2 Yu/h per catalyst 11, and The ratio of hydrogen/feedstock oil is 1
Preference is given to working with 500 to 250 ONl hydrogen per kg.

If a noble metal catalyst is used in the second step of the hydroprocessing of the present invention, the temperature used in the second step must be at least 50° C. lower than the temperature used in the first step.

After the two-stage catalytic hydrogen treatment, the hydrotreated product is cooled and separated into hydrogen-rich gas and liquid product.

The liquid product includes hydrocarbons boiling below the white oil boiling range and hydrocarbons boiling within said range.

Hydrocarbons boiling below said boiling range are separated from high-boiling residues by distillation.

The fractionation temperature of this distillation is such that it is the initial boiling point of the desired white oil;
Alternatively, if the higher boiling point resid is to be further divided into a number of white oil fractions by distillation, it is selected to correspond to the initial boiling point of the lightest desired white oil fraction.

In addition to the superior white oil component, the residual oil contains unconverted wax.

To produce a suitable white oil, the residual oil must be dewaxed.

Dewaxing may be carried out in any desired manner.

Dewaxing is preferably carried out using a mixture of methyl ethyl ketone and toluene at a temperature in the range -10 DEG to -40 DEG C. and in a volume ratio of solvent to oil in the range 1:1 to 10:1.

To increase the yield of white oil, it is preferred to recycle at least a portion of the separated wax to the first hydrotreatment step.

In the process of the present invention, when a mixed sulfide catalyst is used in the second step, the catalytic hydrogen treatment can optionally be followed by a post-treatment with an acid to obtain a medicinal oil and an industrial white oil. .

In principle, acid treatment in white oil production is concentrated sulfuric acid (80-1
00%) or fuming sulfuric acid (dissolution up to 80330%) at temperatures in the range 0-75°C and contact times of 5 seconds to 1 hour.

The amount of concentrated or fuming sulfuric acid to be used in the acid post-treatment according to the invention varies depending on the type of white oil to be produced.

In principle, the amount of oleum, expressed as concentrated sulfuric acid or fuming sulfuric acid containing 30% dissolved S03, used according to the invention for the production of industrial white oils does not exceed 2.5% by weight.

To prepare the medicinal oils of the invention, the amount of fuming sulfuric acid, expressed as concentrated sulfuric acid or fuming sulfuric acid containing 50330% dissolved, does not in principle exceed 10% by weight.

The fact that the amount of acid used is small as described above is that when acid treatment is carried out in the production method of the present invention, it is contrary to the acid treatment carried out in the conventional production of white oil, in which a very large amount of acid is used. ,
This clearly shows that the acid treatment of the present invention has the character of a post-treatment.

The acid post-treatment can be carried out in one step or in two or more steps, and can be carried out either batchwise or continuously.

At the end of the acid treatment, the acid sludge formed is removed from the oil.

The oil is then treated with an alkaline substance, such as an aqueous or alcoholic solution of sodium hydroxide, to neutralize the oil.

The used alkaline substances are separated from the oil, which is then washed, for example with water and/or alcohol.

As an alternative to the "wet" process described above to neutralize the oil, a "dry" process may also be carried out using an excess of a solid neutralizing agent, such as lime.

When the white oil production of the present invention is carried out by a two-stage catalytic hydrotreatment followed by an acid after-treatment (in this case, the white oil production when a mixed sulfide catalyst is used in the second step of the hydrotreatment) (as can occur in oil production), it is necessary to carry out treatment with a solid adsorbent after acid treatment.

When the white oil production of the present invention is carried out by a two-stage catalytic hydrogen treatment without post-treatment with an acid (in this case, white oil production when a precious metal catalyst is used in the second step of the hydrotreatment) Optionally, treatment with a solid adsorbent may be carried out after the catalytic hydrogen treatment (occurring in ).

Earth and clay come into consideration as solid adsorbents for this purpose.

Suitable solid adsorbents are, for example, Fuller's earth (Ful 1e
rs earth), bauxite and Filtrol, which may or may not be acid activated.

If desired, the oil may be heated during treatment with the solid adsorbent, and an inert gas such as nitrogen may be passed through the oil.

In principle, the amount of solid adsorbent used according to the invention ranges from 0.2B to 10.0% calculated for the oil to be treated.
% by weight, especially in the range from 0.5 to 5% by weight.

Various manufacturing processes (first and second steps of catalytic hydrogen treatment,
Regarding the order in which the toppings, product separation, dewaxing, after-treatment with acids and treatment with solid adsorbents are carried out, the following must be observed:

When separating the product, it is exposed to conditions, especially high temperatures, which can have an unfavorable effect on the properties of the final white oil.

In solvent dewaxing, the solvent is flushed away from the dewaxed oil so that any impurities originally contained in the dewaxing solvent are left behind in the dewaxed oil.

This also has an undesirable effect on the properties of the final white oil.

Any undesirable effects on performance caused by product separation and dewaxing can be offset by treating the oil with a solid adsorbent or by post-treating the oil with an acid and then with a solid adsorbent. can do.

Because white oils must meet strict specification requirements,
Therefore, if the process of the present invention includes treatment with a solid adsorbent or treatment with a solid adsorbent after post-treatment with an acid, these treatments are preferably carried out after dewaxing;
Also, if the process includes separation of the product, these treatments are preferably carried out after separation and dewaxing of the product.

Possible undesirable effects caused by product separation and dewaxing can also be offset by catalytic hydrogen treatment.

For this purpose. The second step of catalytic hydrogen treatment according to the invention is very suitable.

Accordingly, in one preferred embodiment of the white oil production of the present invention, dewaxing is carried out intermediate the first and second steps of the catalytic hydrotreatment, and if the process includes separation of the product, Product separation and.

Dewaxing is carried out between the first and second steps of the hydrogen treatment.

A specific example of the process according to the invention in which separation and dewaxing of the product is carried out between the first and second steps of the catalytic hydrogen treatment is the process according to the invention, which includes treatment with a solid adsorbent or post-treatment with an acid. Later treated with solid adsorbent.

This is particularly important if the process does not include

Next, in order to explain the present invention more specifically, the following examples are shown.

Two mixed sulfide catalysts (catalysts I and ■) and a noble metal catalyst (catalyst ■) were used in the production of medicinal oils and industrial white oils by two-stage hydrotreatment of two types of waxes (feedstock oils A and B).
was used.

The catalyst and feedstock oil are further shown below.

Catalyst I N containing 37 parts by weight of nickel, 70 parts by weight of tungsten and 4.6% by weight of fluorine per 100 parts by weight of alumina
i/W/F/A■203 catalyst.

The catalyst was prepared by mixing alumina hydrogel with an aqueous solution containing nickel nitrate, ammonium tungstate, and ammonium fluoride, the pH of which was adjusted to 6.5 using 25% ammonia.

The mixture was heated to 80° C. and the gel was filtered, extruded and calcined to dry.

The alumina hydrogel used to make this catalyst has a packed bulk density of 0.75 to 1.6 when dried and calcined.
g/ml and 0.15-0.5 rul/f! pserogels with pore volumes in the range of .

Catalyst ■ Pt/Al□03 catalyst containing 0.87% by weight of platinum ■ 10 parts by weight of nickel, 16 parts by weight of molybdenum and 3 parts by weight of phosphorus and 1.0 parts by weight of fluorine per 100 parts by weight of alumina.
Ni/Mo/P/F/A containing 6% by weight
l2O3 catalyst.

This catalyst co-impregnates an alumina support with an aqueous solution containing nickel nitrate, ammonium molybdate and phosphoric acid;
This composition was then produced by dry calcining.

The catalyst was fluorinated on the spot by adding 0-fluorotoluene to the feedstock oil at the initial stage of hydroprocessing.

Feedstock A: Residual lubricating oil fraction obtained by dewaxing residual lubricating oil fraction 1, which has been previously deasphalted with propane and extracted with furfural. Feedstock B: Residual lubricating oil fraction, which has been previously deasphalted with propane. The two residual lubricating oil fractions 1 from which feedstock oils A and B were obtained by dewaxing the residual fraction of hydrogenated cracked oil produced by hydrocracking 1 were: It was obtained as a residual oil when the atmospheric distillation residue of paraffinic crude oil was distilled under reduced pressure.

Dewaxing was carried out in the presence of a 1:1 mixture of methyl ethyl ketone and toluene by cooling the oil to a temperature of -30°C.

Catalysts ■ and ■ were used in sulfide form.

Sulfidation of the catalyst was carried out by contacting the catalyst with hydrogen and sulfur-containing gas oil.

Example 1 Feedstock A was hydrotreated in the first step using catalyst ① under the following conditions.

Namely temperature: 383°C Hydrogen partial pressure: 150 bar Space velocity:
0.8kb hydrogen/feedstock ratio:
150 ONl/was topped with 9 liquid reaction products at 310°C and mixed with 1:1 of methyl ethyl ketone and toluene.
When one fraction at 310°C is dewaxed at -30°C in the mixture,
15.6% by weight of top oil, 35.9% by weight of wax and 48.5% by weight of dewaxed oil were obtained.

The properties of the dewaxed oil were as follows.

Seibold chromaticity: +3 Kinematic viscosity at 100°F (37.8°C): 41.2 centistokes Aromatics content: 2.1 mmol/100 g Dewaxed oil meets FI) A-1212589 standard for industrial white oil did not match.

The dewaxed oil was divided into three portions and each of these portions was hydrotreated in a second step using catalyst ① under the following conditions.

Temperature: 225, 250 or 275 °G Hydrogen partial pressure: 150 bar Space velocity: 0.8 kg/A'/h Hydrogen/raw oil ratio: 165 ONl/mu The three oils thus obtained are tasteless It was odorless and had the following properties.

Temperature used in the second hydrogen treatment step ('C) 225 250 2
75 Oil Properties Kinematic Viscosity (centistokes) at 100°F (37,8°C) 45.1 45.3 4
5.4 Aromatics content (mmol/100g) 0.03 0.0
2 θ, 02 Seibold chromaticity 〉+30〉+30
〉+30 Results of FDA Exam No. 121258 Pass Pass Pass Results of FDA Exam No. 121114 Eel Fail Pass Pass Thermal acid test (
Hot aeid test) results
Pass Pass Pass The above results are for industrial white oil (225
Oils that fully comply with the specifications specified in this invention for oils produced at 250 °C (see oils produced at It has been shown that it can be produced according to the invention by two-stage hydrotreating of the wax using a mixed sulfide catalyst and a noble metal catalyst in the second step.

Example 2 Feedstock B was hydrotreated in the first step using catalyst ① under the following conditions.

Temperature: 365°C Hydrogen partial pressure: 140 bar Space velocity: 0.8 kg/l/h Hydrogen/feedstock ratio: 15oONl/ky The liquid reaction product of the first step is divided into two parts and these parts are were hydrogen-treated in the second step using Catalyst ① under the following conditions.

i.e. temperature: 275°C or 300°C
Hydrogen partial pressure: 140 bar Space velocity: 0.8 kg/l/h Hydrogen/feedstock ratio: 150 ON7/kg From the liquid reaction product of the hydrotreating step carried out at 275 °C, topping at 425 °C and at 425 °C Oil A was produced by dewaxing the C and higher fractions.

Oil A was obtained at a yield of 37.8% of the feedstock at 100°F.
The kinematic viscosity at (37.8°C) was 75.8 centistokes.

From the liquid reaction product of the hydrotreating step carried out at 300°G, it is topped at 270°C, and the fraction above 270°C is further divided into a fraction of 270-425°C (for production of B oil) and 42°C.
The distillate was divided into a fraction at 5° C. or higher (for production of oil C), and these fractions were dewaxed to produce two types of oils, oil B and oil C.

Oil C was obtained with a yield of 38.6% by weight of the feedstock oil, with a yield of 100
The kinematic viscosity at 'F (37.8°C) was 74.8 centistokes.

Dewaxing of the oil was carried out at -19°C using a 1:1 mixture of methyl ethyl ketone and toluene.

Oil D was produced from Oil B and Oil C by blending 63% by weight of Oil B and 37% by weight of Oil C.

Oil D had a kinematic viscosity of 15.0 centistokes at 100°F (37.8°C).

After treating A oil, C oil and D oil with 3% by weight of earth, it becomes a medicinal oil (odorless and tasteless, Saybolt chromaticity>+30, A
Hotacid by STMD-565
” testing and meeting the requirements specified in FDA No. 1211146) as well as the ultraviolet absorption as specified in the British and German Pharmacy Act. An oil was obtained that also met the requirements.

(According to the British Pharmacy Act, the ultraviolet absorption of oils in the wavelength band 240-280 nm must be at most 0.10.

According to the German Pharmacy Law DAB7, 275 nm, 296
The ultraviolet absorption of oil at wavelengths of 300 nm and 300 nm and above is up to 0.80, 0.04 and 0, respectively.
．． Must be 30.

Claims (1)

[Claims] 1. In the first step, on a sulfide catalyst containing nickel and/or cobalt and molybdenum and/or tungsten on a carrier, and in the second step, on a hydrogenation catalyst at a lower temperature than in the first step. A process for producing white oil by subjecting a hydrocarbon mixture to a two-stage hydrotreating process, comprising: using a wax as a starting material; using a mixed sulfide catalyst containing nickel and/or cobalt and molybdenum and/or tungsten or a noble metal catalyst containing at least one group 1 noble metal on a support; the temperature used in the second step is: If a mixed sulfide catalyst is used as the second step catalyst, the temperature is at least 25° C. lower than the first step temperature; if a noble metal catalyst is used as the second step catalyst, the temperature is at least 50° C. lower than the first step temperature. C
A method for producing white oil by subjecting a hydrocarbon mixture to a two-stage hydrogen treatment characterized by low