JPH0356591A - Production of hydrocarbon mineral oil without containing aromatic - Google Patents

Abstract

PURPOSE:To produce various solvents for cleaning, coatings, etc., extremely rich in naphthenic content by carrying out selective hydrogenolysis of a mineral hydrocarbon oil under specific conditions in two stages. CONSTITUTION:A mineral hydrocarbon oil is brought into contact with H2 in the presence of a group VIII iron family metal and/or VIb group metal-based catalyst under relatively mild conditions to provide a hydrogenolysis product, which is then fractionated to afford a heavy fraction having >=300 deg.C initial boiling point. The resultant fraction is subsequently brought into contact with H2 in the presence of the same catalyst under relatively severe conditions to provide a hydrogenolysis product again. The aforementioned product is then brought into contact with H2 in the presence of a group VIII iron family metal- based catalyst to selectively hydrogenate aromatics and afford a hydrocarbon mineral oil substantially without containing the aromatics.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an economical process for producing various mineral oils that are substantially free of aromatics.

[Prior Art] In recent years, due to the harmful nature of aromatics, it has become an urgent issue to make solvents and lubricating oil fractions non-aromatic. Therefore, in order to dearomatize a lubricating oil fraction, for example, as disclosed in Japanese Patent Publication No. 1-14278, generally undesirable raw materials are hydrocracked in the presence of a sulfur-resistant catalyst,
A method has been proposed in which the sulfur content in the oil is then lowered by a desulfurization reaction in the presence of a sulfur-resistant catalyst, and finally a food-grade mineral white oil is produced in the presence of a Group I noble metal catalyst.

In this method, in the final step, a noble metal catalyst is used to perform de-aromatization, and since sulfur becomes a catalyst poison for the metal catalyst, a desulfurization step is provided in the first stage.

In addition, if the distillation properties are various solvents of kerosene and gas oil fractions,
As a solvent, solubility for various pigments and the like is important. It is generally said that the solubility of these solvents is highest in the order of paraffins, naphthenes, and aromatics, and in particular, when using non-aromatic solvents, those with a large amount of naphthenes are preferred from the viewpoint of solubility.

From this point of view, a method for producing danlubento rich in naphthenes has been proposed by hydrogenating a mixed oil in which an aromatic fraction is added to a hydrocarbon oil (U.S. Pat. No. 4,038).
．． Publication No. 734).

[Problems to be Solved by the Invention] The present invention does not require a desulfurization process for removing sulfur, which is a catalyst poison of various noble metal catalysts, as disclosed in the above-mentioned Japanese Patent Publication No. 1-14278, and also solves the problems disclosed in U.S. Patent No. 1-14278. 4.036,734
As disclosed in the publication, hydrogenolysis is carried out in two stages without further addition of an aromatic fraction to the hydrocarbon oil, which is preferable for Group W metal catalysts useful for aromatic hydrogenation. Various raw material fractions that do not contain substantially sulfur are co-produced at the same time, and these are brought into contact with molecular hydrogen in the presence of a group II metal catalyst as feedstock oil to produce various solvents that do not contain substantially aromatics [turning oil]. (boiling point 140-200℃
Distillates), paints, pesticides, ink solvents (boiling point 200-3
00℃ fraction) and lubricating oil (fraction with a boiling point of 300℃ or higher)
] is aimed at manufacturing.

Another object of the present invention is to produce various solvents for cleaning, paint, etc. that are extremely rich in naphthenes by selectively hydrogenating two-stage hydrocracked oil.

[Means for Solving the Problems] In order to achieve the above object, the present invention provides the following: (a) At least one metal selected from iron group metals, group VIb metals and mixtures thereof. Contacting a mineral hydrocarbon oil with molecular hydrogen under relatively mild hydrocracking conditions in the presence of a hydrocracking catalyst consisting of a support containing activated alumina as an active ingredient to obtain a hydrocracking product; (b) Fractionally distilling the obtained hydrocracked product to obtain a heavy fraction whose initial boiling point boils at a temperature higher than 300°C; (c) iron group metal, group VIb metal and The product oil from step (b) is subjected to relatively harsh hydrocracking conditions in the presence of a hydrocracking catalyst consisting of a carrier comprising activated alumina with at least one metal selected from the mixture as an active ingredient. (d) a catalyst consisting of a refractory inorganic oxide support with at least one metal selected from iron group metals and mixtures thereof as an active component; contacting the hydrocracked product from step (c) with molecular hydrogen under selective hydrogenation conditions in the presence of selective hydrogenation of aromatics in the hydrocracked product from step (c). The present invention provides a method for producing a substantially aromatic-free hydrocarbon mineral oil comprising the steps of:

The raw material oil used in the present invention is a mineral hydrocarbon, and in particular, a hydrocarbon oil having a boiling point range of about 360 to 590°C is preferably used. Examples include vacuum distillation distillate oil and deasphalted oil.

In step (a) of the present invention, "relatively mild hydrogenolysis"
means temperature 380-450℃, preferably 400-430℃
, pressure 70 to less than 110 K g/cm2・G1 preferably 90 to 100 Kg/am″eG1 liquid hourly velocity (L
HSV) 1.0 to 3.0V/V/H1 preferably 1.
2 to 1.7 V/V/H1 and hydrogen to hydrocarbon feedstock ratio 1.500 to 3, OOOs. c. f/bbl - feedstock oil, preferably 2,500 to 3,000s. c. f/bb
i- Hydrocracking of feedstock oil under mild conditions.

The hydrocracking catalyst used in step (a) of the present invention is a group IV iron group metal, such as a metal such as nickel or cobalt, and a group VI metal.
A carrier containing activated alumina containing at least one active metal of Group B metals, such as molybdenum and tungsten;
For example, in addition to activated alumina, the catalyst is preferably supported on an inorganic oxide such as silica or boria.

The active metal of the catalyst may be present in the form of a metal, an oxide or a sulfide.

The amount of active metal supported (as oxide) is 1 to 15% by weight, preferably 2 to 10% by weight for Group I iron group metals.

Group VIb metal is 5-30% by weight, preferably 10-3
It is 0% by weight.

In step (b) of the present invention, the hydrocracked oil obtained in step (a) is fractionated into a light fraction and a heavy fraction by vacuum distillation or the like. Among these, the heavy fraction with an initial boiling point higher than 300°C is transferred to the next step (c).

In the present invention, instead of part of the heavy fraction transferred to step (c), vacuum distillation distillate oil, which is a raw material for mild hydrocracking, can be mixed.

"Comparatively severe hydrocracking" in step (c) of the present invention
means a temperature of 3θO to 450°C, preferably 370 to 420°C,
Pressure 110 to 210Kg/am2@G1 preferably 120 to 170Kg/cm” eG, liquid air J
I velocity (LHSV) 0.2 to 2.0 V/V/H, preferably <lt0.3 to 0.9 V/V/H1 and hydrogen to hydrocarbon feedstock ratio 2,500 to 4,500 s. c. f/
bbl - feedstock oil, preferably L 000 to 4+ OO
Os. c. t/bbl - Hydrocracking of feedstock oil under severe conditions.

The hydrocracking catalyst used in step (c) of the present invention is (a)
A catalyst similar to that used in the process can be used.

The product oil hydrocracked under severe hydrocracking conditions can then be fractionated into naphtha, kerosene, gas oil, and lubricating oil fractions by conventional distillation operations. Gas oil fractions and lubricating oil fractions produced under severe hydrocracking conditions can also be dewaxed prior to the selective hydrogenation step.

A conventional method is used for the dewaxing method. For example, benzene, toluene, acetone, or benzene, tonoleene, MEK (methynolethyl ketone) as a defrosting solvent.
Solvent dewaxing method using a mixed solvent such as ZSM-
A catalytic dewaxing method using No. 5 zeolite or the like can be mentioned.

Furthermore, lubricating oil fractions produced under severe hydrocracking conditions contain relatively more polycyclic aromatics (aromatics with two or more rings, typified by naphthalene) than naphtha, kerosene, and gas oil fractions.

Selective hydrogenation of polycyclic aromatics thermodynamically requires a higher hydrogen partial pressure than single-ring aromatics, so lubricating oil fractions are sent to the selective hydrogenation process after solvent refining. is preferred.

Solvent purification can be carried out by conventional methods. For example, the furfural method uses furfural as an extraction solvent.

The hydrocracked oil from step (c) of the present invention is fed to the selective hydrogenation step of step (d).

Selective hydrogenation in step (d) is performed at a pressure of 20 to 100 Kg/
cmQ●61 preferably 25-60Kg/cm' ”G
s temperature 100-350℃, preferably 120-300℃
°C, liquid space velocity 0.5 to 8.0 V/V/H, good 1 < is 1
．． O ~4.0V/V/H, and hydrogen to feedstock ratio 50
~3. OOOs. c. f/bbl - feedstock oil, preferably 400 to 1,500 s. c. Aromatics are selectively hydrogenated under conditions of f/bbl - feedstock oil.

Examples of the catalyst used in the selective hydrogenation step of step (d) of the present invention include Group (1) iron group metals and Group (1) noble metal group metals. Nickel is particularly preferred as the Group (I) iron group metal. The nickel is a reduced nickel-containing catalyst, and as long as it contains reduced nickel, most of the nickel form may be an oxide or a compound with other anions.

Examples of the carrier include refractory inorganic oxides, such as diatomaceous earth, pumice, silica, alumina, and acid clay. Alternatively, these may be mixed.

The supported amount of metal is nickel content (as oxide) of 6 to 90% by weight, preferably 15 to 50% by weight, and reduced nickel content of 5 to 70% by weight, preferably 10 to 50% by weight. The range is appropriate.

Further, as the Group (1) noble metal group, platinum or palladium is preferable.

Examples of the carrier include refractory inorganic oxides, preferably alumina, and the alumina may contain a small amount of silica, zirconia, magnesia, etc.

The above-mentioned noble metal component may exist in either a metal form or an oxide form.

The supported amount of the noble metal component is 0.1 to 2.
0% by weight, preferably in the range of 0.3-0.7% by weight. Further, the amount of the oxide is in the range of 0.1 to 2.3% by weight, preferably 0.3 to 0.8% by weight.

The catalyst used in the present invention is preferably packed into a reaction column as a fixed bed. The catalyst can be in any shape such as extrudates, spheres, granules, tablets, etc.

【Example] Next, the present invention will be explained in more detail with reference to Examples.

Practical Example 1 3.0% by weight of nickel (as oxide) and 10% of molybdenum using activated alumina boria (15% by weight of B2ss based on A1aOa) as a carrier was prepared from vacuum distillation distillate of Middle Eastern crude oil shown in Table 1. At a temperature of 434° C. in the presence of a catalyst containing 0% by weight (as oxides), a hydrogen to feedstock ratio of 2.IO
Os. c. f/bbl - raw material oil, pressure 95Kg/cm2
*G, The reaction was carried out at a liquid hourly space velocity of 1.82 V/V/H, and the product was subjected to atmospheric and reduced pressure distillation to obtain each distillate oil shown in Table 2.

Next, 89% by weight of the lubricating oil fraction in Table 2 and 11% by weight of the vacuum distillation distillate in Table 1 were mixed to form silica-activated alumina (S).
In the presence of a catalyst containing 9.3 wt. % nickel (as oxide) and 16.4 wt. % nickel (as oxide) on a carrier of 325 wt. Raw material oil ratio L 500s. c-
f/bbl - raw material oil, pressure 130kg/Cm" *
G1 liquid space a! 0.32V/V/}{The product was subjected to normal pressure and reduced pressure distillation to obtain each distillate oil shown in Table 3.

The gas oil fractions of Table 3 were heated at 200° C. in the presence of a selective hydrogenation catalyst containing 64% by weight of nickel (as oxide) supported on silica-alumina (23% by weight of Al*Oi relative to S i OQ). , hydrogen to feedstock ratio 1.400s. c.
．． The reaction was carried out using f/bbl - feedstock oil at a pressure of 30 kg/cm 2 -G1 and a liquid hourly space velocity of 2.0 V/V/H to obtain a non-aromatic solvent having a gas oil fraction boiling point range that does not substantially contain aromatics.

The properties are shown in Table 4.

Note that no substantial decrease in aromatic hydrogenation activity was observed up to 48 barrels of the two-stage hydrocracking gas oil shown in Table 3 for 11 pounds of this selective hydrogenation catalyst.

Hiroyuki Hong L The two-stage hydrocracking kerosene fraction shown in Table 3 was treated in the presence of a selective hydrogenation catalyst containing 0.6% by weight of platinum using alumina as a carrier at a temperature of 280°C and a simple ratio of hydrogen to raw material 1. .400s. c.
．． f/bbl - raw material oil, pressure θO K g/cm
” ●G React at a liquid space velocity of 5.0 V/V/H,
A non-aromatic solvent in the kerosene fraction boiling range that is substantially free of aromatics was obtained. The properties are shown in Table 5.

The lubricating oil fraction produced by two-stage hydrocracking in Table 3 was converted into lubricating oil fraction 10.
0 parts by volume, furfural 150 parts by volume, temperature 10 parts by volume
Furfural extraction is carried out under conditions of 0 to 130°C, and the lubricating oil fraction after the extraction is reacted with the selective hydrogenation catalyst of Example 1 under selective hydrogenation conditions to obtain a lubricating oil substantially free of aromatics. A fraction was obtained. The properties are shown in Table 6.

Hiki IL When the gas oil fraction produced by first-stage hydrocracking in Table 2 was reacted with the selective hydrocracking catalyst of Example 1 under the same selective hydrogenation conditions, the aromatic content ranged from 32% by weight to 28% by weight. %, and it was not possible to produce a gas oil distillate containing substantially no aromatic content.

Density 15℃ (g/cm3 Kinematic viscosity 50℃ (cSt) 100℃ Viscosity index Pour point (℃) Distillation ("C) IBP EP Sulfur content (wt%) ) 0. 49. 9. 89 42. 301 585 1 9219 71 303 70 Table 4 Density 15℃ (g/Cm3 Distillation ('C) IBP EP Hue (Saybold) Pour point ('C) Aniline point ('C) Sulfur content (ppm by weight) Nitrogen content (ppm by weight) Naphthene Minutes (weight%) ) 0. 828 226 341 +30 or more -10.0 90.7 1 or less 1 or less 71 Table 5 Density 15°C (g/am3 Distillation ('C) IBP EP Hue (Saybold) Pour point (°C) Aniline point ('C) Sulfur (weight ppm) Nitrogen content (weight ppm) Naphthene content (weight %) ) O.787 136 237 +30 or more -45 or less 71 1 or less 1 or less 81 Table 8 Furfural extraction density of the lubricating oil fraction produced by two-stage hydrocracking 1
5℃ (g/cm') Kinematic viscosity 50℃ (cSt) 100℃ Viscosity index pour point (℃) Distillation ('C) IBP EP Sulfur content (weight ppm) Nitrogen content (weight ppm) Aniline point ('C) Naphthene content (% by weight)) 0. 1 1. 3. 137 35. 3 18 551 122. 65 8469 O8 702 1 or less 1 or less [Effects of the invention] The present invention performs hydrocracking in two stages without providing a desulfurization step to remove sulfur, which is a catalyst poison for the noble metal catalyst used in selective hydrogenation. By this method, various substantially sulfur-free feedstock fractions, which are preferable for Group II metal catalysts useful for aromatic hydrogenation, are simultaneously co-produced, and these are used as feedstock oils to react with molecules in the presence of Group II metal catalysts. contact with hydrogen,
Various solvents and lubricating oils can be produced that are substantially aromatic-free.

In addition, by selectively hydrogenating the two-stage hydrocracked oil, various solvents for cleaning, paint, etc., which are extremely rich in naphthene content, can be produced.

Claims (1)

[Scope of Claims] (1) (a) A hydrocracking catalyst comprising at least one metal selected from iron group VIII metals, group VIb metals and mixtures thereof as an active ingredient and a carrier containing activated alumina. (b) contacting a mineral hydrocarbon oil with molecular hydrogen under relatively mild hydrocracking conditions to obtain a hydrocracking product; and (b) fractionating the resulting hydrocracking product. (c) at least one metal selected from iron group VIII metals, group VIb metals and mixtures thereof as an active ingredient; contacting the product oil from step (b) with molecular hydrogen under relatively harsh hydrocracking conditions in the presence of a hydrocracking catalyst consisting of a support comprising activated alumina to again obtain a hydrocracking product; (d) step (c) under selective hydrogenation conditions in the presence of a catalyst consisting of a refractory inorganic oxide support with at least one metal selected from iron group VIII metals and mixtures thereof as active component; contacting the hydrocracked product from step (c) with molecular hydrogen to selectively hydrogenate aromatics in the hydrocracked product from step (c). Method for producing hydrogen mineral oil. 2. The method according to claim 1, further comprising the step of dewaxing the hydrocarbons produced in step (c) prior to selectively hydrogenating the hydrocarbons produced in step (c). 3. The production method according to claim 1, further comprising the step of fractionating the hydrocarbons produced in step (c) into naphtha, kerosene, light oil, and lubricating oil fractions prior to the step of selectively hydrogenating the hydrocarbons produced. (4) The production method according to claim 1, further comprising a solvent purification step prior to the step of selectively hydrogenating the hydrocarbons produced in step (c). (5) Mild hydrogenolysis conditions are at a temperature of 360-450℃
, pressure 70 to less than 110 Kg/cm^2.G, liquid hourly space velocity (LHSV) 1.0 to 3.0 V/V/H, and hydrogen to hydrocarbon feedstock ratio 1,500 to 3,000 s. c. f
The production method according to claim 1, wherein the raw material oil is /bbl-stock oil. (B) Severe hydrocracking conditions at a temperature of 360 to 450°C
, pressure 110-210 Kg/cm^2.G, liquid hourly space velocity (LHSV) 0.2-2.0 V/V/H, and hydrogen to hydrocarbon feedstock ratio 2,500-4,500 s. c. f/
The manufacturing method according to claim 1, wherein the raw material is bbl-stock oil. (7) Selective hydrogenation conditions are temperature 100~350℃, pressure 20~100Kg/cm^2・G, liquid hourly space velocity (LH
SV) 0.5 to 6.0 V/V/H, and hydrogen to hydrocarbon feedstock ratio 50 to 2,500 s. c. Claim 1: f/bbl-stock oil
Manufacturing method described. (8) The manufacturing method according to claim 4, wherein the purified solvent in the solvent purification is furfural.