JP2521873B2 - Lubricating base oil manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a general-purpose hydrofinini.
The present invention relates to a method for producing a lubricating base oil in which a slush (hydrofinishing) lubricating base oil and a lubricating base oil having a high viscosity index are produced in one reactor.

[0002]

2. Description of the Related Art Hydros for the production of general-purpose lubricating base oils
Finishing is usually carried out on an alumina carrier on the Periodic Table VI.
Using a catalyst supporting a metal selected from Group A and Group VIII Period 4 elements, a vacuum distillation fraction having a boiling point in the range of 250 to 700 ° C at atmospheric pressure, and a propane deasphalted treated residue of the vacuum distillation residue. Or a sulfur content of 0.5 to 3 wt.%, Such as raffinate, which is solvent-refined using furfural.
%, A lubricating base oil production intermediate containing 10 to 400 ppm by weight of nitrogen, under a hydrogen pressure of 50 to 100 kg / cm ² , a hydrogen / oil ratio of 100 to 2000 1 / l, a ratio of 0.5 to 5
The liquid hourly space velocity (LHSV) of hr ⁻¹ and the temperature of 250 to 380 ° C. are used.

On the other hand, the lubricating base oil having a viscosity index of 130 or more is
For example, it can be obtained by treating a wax-containing oil or slack wax by a method such as hydrogenolysis or isomerization. Of these, the lubricating base oil obtained by isomerizing slack wax has excellent properties in terms of viscosity characteristics, oxidation stability, and evaporation characteristics, and is an attractive base material for the production of high-performance lubricating base oils. There is also an advantage that the slack wax can be effectively used. Among the catalysts for the isomerization of slack wax, those containing a noble metal (see, for example, JP-A-1-281148) have a sulfur content which may be a poisoning component of the catalyst when processing a general-purpose lubricating base oil raw material. However, since it contains a large amount of nitrogen and aromatics, general-purpose lubricating base oil raw materials cannot be directly processed. Further, also in the processing of slack wax, it is necessary to perform processing for sufficiently removing the sulfur content in advance.

On the other hand, there has been proposed a method for producing a lubricating oil having a high viscosity index by using a catalyst composed of nickel and / or cobalt and molybdenum and / or tungsten and phosphorus oxide (Japanese Patent Publication No. 54-2204).
This includes residual oil from which the catalyst has been dewaxed, namely
It is disclosed that it can be applied to the treatment of general-purpose lubricating base oil raw materials as well as the treatment of slack wax. However, there is no description of filling this reactor in one reactor and treating these raw materials alternately, nor is there any suggestion that they can be treated.

[0005] General-purpose lubricant base stock hydro Fi Nissin
In sulfur, it is important to remove the sulfur, nitrogen, and oxygen contained in it, but isomerization of slack wax requires a catalyst that exhibits a completely different activity, so it is a general-purpose catalyst. Hydrofinishing for the production of lubricating base oils
It has been considered necessary to provide separate reactors for the production of high viscosity index lubricating base oils by the treatment of slag and slack wax. Therefore, when the production of the lubricating base oil is to be newly started by isomerizing the slack wax, a new reactor has to be installed, which is an economic problem.

[0006]

DISCLOSURE OF THE INVENTION The present invention has solved the above-mentioned problems, and an object of the present invention is to provide a single reactor with a hydrate.
It is an object of the present invention to provide a method for producing a general-purpose lubricating base oil that has been subjected to a rofinishing and a lubricating base oil having a high viscosity index by isomerizing a wax. Another object of the present invention is to produce a high-viscosity index base oil by isomerizing wax, and to produce a general-purpose lubricant base oil by hydrofinishing of a sulfur-containing lubricating base oil production intermediate, to reduce the catalytic activity over a long period of time. It is to provide a way to continue without.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, in the presence of hydrogen,
The sulfur-containing lubricating base oil manufacturing intermediate is contacted with the catalyst Hydro
After finishing , the decrease in the isomerization activity that occurs when the feedstock oil is switched and the wax is brought into contact with it is recovered within a relatively short time, and the isomerization reaction proceeds smoothly. Hydrofinishing activity is maintained even when switching to a sulfur-lubricated base oil production intermediate,
It has been surprisingly found that the production of a high viscosity index lubricating base oil by isomerization of a general-purpose lubricating base oil and a wax can be alternately repeated. Further, it was found that by passing wax, the amount of carbon deposited on the catalyst during hydrofinishing , which causes deterioration of the catalyst, is reduced, and the catalytic activity is maintained for a long time.

The present invention has been made on the basis of such findings, and the present invention provides at least one element selected from elements of Group VIA and Group VIII, Period 4 of the Periodic Table as an essential component of a refractory oxide carrier. A catalyst supporting a metal component, particularly preferably, a catalyst in which molybdenum, nickel and phosphorus are supported on alumina or an alumina carrier containing silica is used as a raw material, and a sulfur-containing lubricating base oil production intermediate and a wax are used as raw materials.
Box alternately supplying, 5 sulfur-containing lubricant base oil production intermediate
250 to 380 under hydrogen pressure of 0 to 100 kg / cm ^2.
Hydrofinishing operation at a temperature of ℃ and wax under a pressure of 50 to 150 kg / cm ² of hydrogen, 320 to
It is a method for producing a lubricating base oil, which comprises alternately performing isomerization at a temperature of 450 ° C. in the same reactor.

Examples of the refractory oxide carrier of the catalyst used in the present invention include alumina, silica, aluminosilicate,
Titania, magnesia, zirconia, etc. or these 2
Examples of the porous carrier include those containing the above, and it is particularly preferable to use alumina or an alumina carrier in which silica is contained in alumina. This alumina carrier is 20
Those having a specific surface area of 0 m ² / g or more and a pore volume of 0.5 ml / g or more are preferable, and silica is 30% by weight.
The following contents are preferable.

The metal of Group VIA and Group VIII, Period 4 of the Periodic Table, which is an essential component to be supported on the carrier, is preferably molybdenum, tungsten, cobalt, nickel or the like. Alternatively, or two or more kinds of these metals may be combined and supported, and in addition to these metals which are essential components, other metals such as phosphorus and boron may be combined and supported.

The amount of the metal supported is preferably 3 to 30% by weight, particularly 10 to 20% by weight, as the total amount of the metal components, and elements other than the metal are preferably supported at 10% by weight or less. Particularly, it is preferable to use a catalyst supporting 8 to 15% by weight of molybdenum, 2 to 5% by weight of nickel, and 1 to 5% by weight of phosphorus.

The intermediate for producing a lubricating base oil, which is the feedstock for hydrofinishing according to the present invention, is an intermediate obtained in a conventional process for producing a lubricating oil, typically 250 at a boiling point converted to atmospheric pressure. A vacuum distillation fraction in the range of ˜700 ° C., a propane deasphalted oil of the vacuum distillation residue, or a raffinate obtained by solvent refining them with furfural, or a mixture of two or more of these, and a sulfur content Of 0.5 to 5 wt% and nitrogen content of 10 to 400 wtppm can be used. Also this
Hydrofinishing, 50~ 100 kg / cm ²
Hydrogen / oil ratio of 100-2000 l / l, liquid hourly space velocity (LHSV) of 0.5-5 hr ⁻¹ , 25
It is advisable to carry out under conditions of a temperature of 0 to 380 ° C. Note that lubrication
There are two methods for hydrorefining oil, one is hydro
Hydrofinishing, the other is hydrogenation
In processing (hydrotreating)
It The former hydrofinishing has a relatively low temperature.
And hydrogenate at low hydrogen pressure, conventional sulfuric acid, clay finish
Instead of trace amount of polar substances and impurities
The latter hydrotreatment is relatively expensive.
Conventional lubricating oil that is hydrogenated at high temperature and high hydrogen pressure
By omitting the solvent extraction method used in the manufacture of
Chemically transform raw materials to produce high quality lube base oils
Is a process. The present invention refers to the former hydro in the above sense.
It means finishing.

On the other hand, the wax which is a raw material for isomerization is
The slack wax obtained in the dewaxing process, which is one of the lubricating oil manufacturing processes,
Solvent dewaxing of deasphalted processed oil from vacuum distillation medium, heavy fraction or vacuum distillation residue with solvent purification using furfural and / or hydrorefining equipment, or without treatment Those obtained by applying the apparatus are preferable. This slack wax contains 10 to 80% by weight of n-paraffin measured by gas chromatography using a capillary column. This slack wax may be treated individually for each fraction, or may be treated by mixing with other fractions. This isomerization is carried out under a hydrogen pressure of 50 to 150 kg / cm ² ,
Hydrogen / oil ratio of 100-3000 L / L, 0.5-1 hr
The liquid hourly space velocity (LHSV) is ^-1 and the temperature is preferably 320 to 450 ° C.

In the present invention, the above hydrofinishing and isomerization are alternately carried out in the same reactor. This is to switch the feedstock species supplied to the reactor and then reset the conditions or change the conditions. After resetting, it may be performed by any method after which the type of raw material oil is switched. Hyde
At the initial stage of switching from lofinishing to isomerization, the activity of the catalyst is not sufficiently exerted, so that a lubricating base oil having desired properties cannot be obtained. This is high
This is because the isomerization active sites on the catalyst are poisoned during the dolo-finishing , but the activity is restored within a relatively short period of time, and it becomes possible to obtain a lubricating base oil having the desired properties. .

In this case, if the reaction temperature is made higher than the temperature required to obtain the desired reaction level immediately after switching, the recovery of the activity can be remarkably accelerated. For example, it was confirmed that by raising the temperature immediately after switching from the predetermined reaction temperature by 10 to 30 ° C., poisoning substances were removed early and the isomerization activity was recovered within 24 hours. Therefore, when the feedstock oil type is switched from hydrofinishing to isomerization, 10 to 30
It is preferable to carry out the operation for 12 to 24 hours to recover the isomerization activity at an elevated temperature of 0 ° C. Then, by returning the temperature to a predetermined temperature, a lubricating base oil having desired properties can be obtained.

[0016] Then, also when switching the hydrofinishing hydrogenation activity (desulfurization, denitrification) Since reduction of not occur, and an object is set to a predetermined reaction temperature
Hydrofinishing oil is immediately available. Normal,
Since the hydrogenation activity decreases as the treatment amount increases, that is, as the treatment time elapses, it is necessary to gradually raise the reaction temperature in order to maintain the hydrogenation activity. However, when the isomerization of the wax of the present invention is carried out alternately, the carbonaceous matter on the catalyst, which causes the catalyst deterioration, is reduced, and the long-term operation becomes possible.

The hydrofinishing and isomerization reaction are
Although the reaction is carried out under the same reaction conditions as described above, in order to carry out the same reactor, the hydrogen pressure and hydrogen / oil ratio should remain the same, and only the liquid hourly space velocity and reaction temperature should be changed as described above. Above all preferred. Further, in the hydrofinishing and isomerization reactions, a conversion to a light fraction occurs due to a cracking reaction which is a side reaction, and it is necessary to perform vacuum distillation in order to remove the light fraction which is not desirable as this lubricating base oil. a common fractionator can be used in both hydrofinishing <br/> and isomerization also distillation for.
Further, usually, vacuum distillation residues of this hydrofinishing product and isomerization products are both but subjected to dewaxing unit, the dewaxing conditions also commonly be used for much there is no difference in both.

[0018]

Example 1 In a fixed bed flow reactor, 12% by weight of molybdenum, 3% by weight of nickel and 2.5% by weight of phosphorus were supported on an alumina carrier, specific surface area 180 m ² / g, pores. Volume 0.42
After the catalyst having a volume of ml / g was filled and the catalyst was sulfided, the feedstock I and the feedstock II having the properties shown in Table 1 were passed alternately in the presence of hydrogen. First, the raw material oil I is set to a hydrogen pressure of 80
kg / cm ² , hydrogen / oil ratio 500 l / l, LHSV 0.
Oil was passed for 72 hours at 5 hr ⁻¹ and a reaction temperature of 400 ° C. Next, the feedstock oil II was passed for 72 hours under the same conditions as above except that the LHSV was 1.0 hr ⁻¹ and the reaction temperature was 330 ° C. After that, the feed oil was switched to the feed oil I, the LHSV was changed to 0.5 hr ⁻¹ , and the reaction temperature was changed to 420 ° C. After passing oil under the same conditions as above for 20 hours, only the reaction temperature was changed to 4
The temperature was returned to 00 ° C and oil was passed for 50 hours. Then, the LHSV was changed to 1.0 hr ⁻¹ and the reaction temperature was changed to 330 ° C., and the stock oil II was passed again for 72 hours. Table 2 shows the time after switching the feedstock and the properties of the produced oil in each case.

[0019]

[Table 1]

[0020]

[Table 2] The generated oil is sampled for 2 hours, and the time after switching in the table indicates the time at the end of sampling. N in the table
The P conversion is the reduction rate of n-paraffin, and the decomposition rate is 3 for the boiling point.
The yield of fractions lighter than 30 ° C is shown.

NP conversion, decomposition rate and feedstock of feedstock I
With regard to the desulfurization rate of II, satisfactory results were already obtained at 32 hours after the feedstock was changed, and were comparable to the case where separate catalysts and devices were used.

Example 2 Using the same catalyst and reactor as in Example 1, feed oil I and feed oil II were passed alternately in the presence of hydrogen. The stock oil I was oiled at a hydrogen pressure of 80 kg / cm ² , a hydrogen / oil ratio of 500 l / l, LHSV of 0.5 hr ⁻¹ and a reaction temperature of 400 ° C. for 72 hours. Next, LHSV 1.0h
After setting r ⁻¹ and the reaction temperature to 330 ° C., the raw material oil II was passed for 72 hours. Then, switch the feedstock oil to feedstock oil I, and
Oil was passed for 169 hours at an SV of 0.5 hr ⁻¹ and a reaction temperature of 400 ° C. Table 3 shows the time after switching the feedstock oil in each case and the properties of the produced oil at that time.

[0023]

[Table 3] The generated oil is sampled for 2 hours, and the time after switching in the table indicates the time at the end of sampling.

By comparing Tables 2 and 3, the high
It is clear that increasing the temperature during the switch from Dolofinishing to isomerization leads to an early recovery of the isomerization activity of the wax.

Example 3 A fixed bed flow reactor was charged with the same catalyst as in Example 1,
After sulphidation, the feedstock oil II in the presence of hydrogen, hydrogen pressure 80 kg / cm ² , hydrogen / oil ratio 500 l / l, LHSV
Oil was passed for 120 hours at 1.0 hr ⁻¹ and a temperature of 330 ° C. The sulfur content in the produced oil was 0.11 wt%. After that, the feedstock oil was switched to the feedstock oil I, and oil was passed for 24 hours at LHSV 0.5 hr ⁻¹ and a reaction temperature of 420 ° C. The NP conversion of the produced oil 12 hours after the switching was 55.0%,
The NP conversion of the produced oil after 8 hours was 82.0%. Table 4 shows the composition, surface area, pore volume, and median pore diameter of this used catalyst.

Comparative Example 1 A fixed bed flow type reactor was charged with the same catalyst as in Example 1,
After sulfurization, the feedstock oil II was passed under the same conditions as in Example 3 . The sulfur content in the produced oil was 0.12 wt%. Table 4 shows the composition, surface area, pore volume, and median pore diameter of this used catalyst.

[0027]

[Table 4]

From Table 4, the amount of carbon,
It can be seen that the amount of nitrogen is greatly reduced and the surface area and pore volume are recovered.

Example 4 The catalyst of Example 1 was charged into a fixed bed flow reactor and after sulfiding, the feed oil II was added in the presence of hydrogen at a hydrogen pressure of 80 kg.
/ Cm ² , hydrogen / oil ratio 500l / l, LHSV 1.0h
Oil was passed for 240 hours at r ⁻¹ and a temperature of 330 ° C. Next, the feedstock oil was switched to the feedstock oil I, passed through LHSV 0.5 hr ⁻¹ and a reaction temperature of 420 ° C. for 20 hours, and then the reaction temperature was set to 400.
It was made to be 40 ° C. and oiled for 240 hours. After that, the stock oil II and the stock oil I were alternately passed under the above conditions, and each stock oil was passed 12 times in total to complete the experiment. Transition of Sulfur Content in Product Oil from Feed Oil II, N in Product Oil from Feed Oil I
Table 5 shows changes in P conversion rate and decomposition rate.

[0030]

[Table 5]

From Table 5, it can be seen that by alternately passing the stock oil II and the stock oil I, it is possible to operate for a long time without lowering the catalytic activity.

Reference Example The produced oil 6 in Table 2 in Example 1 was distilled under reduced pressure to remove light components, and a residue having a boiling point of 327 ° C. at the initial boiling point was obtained. Then, this was subjected to a dewaxing treatment using methyl ethyl ketone / toluene (1/1 volume ratio) as a solvent under the conditions shown in Table 6 to obtain a lubricating base oil A. The properties of this base oil are shown in Table 6.

In addition, the product oil 8 in Table 2 in Example 1
Was dewaxed under the conditions shown in Table 6 using methyl ethyl ketone / toluene (1/1 volume ratio) as a solvent to obtain a lubricating base oil B. The properties of this base oil are shown in Table 6.

[0034]

[Table 6] The yield in the table is based on the residue having a boiling point of 327 ° C. as the initial boiling point.

[0035]

INDUSTRIAL APPLICABILITY The present invention provides a single reactor with a hydro
It is possible to produce a general-purpose finished lubricating base oil and a lubricating base oil having a high viscosity index by isomerizing wax.
The existing reactor can be effectively used, and the reactor can be operated for a long time without lowering the catalytic activity, which is an economical method for producing a lubricating base oil.

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Claims (3)

(57) [Claims] [Claim 1] with a refractory oxide support in the catalyst carrying at least one metal component selected from the Periodic Table Group VIA and Group VIII elements of the fourth period as essential components, the original
Alternate between sulfur-containing lubricating base oil production intermediate and wax
Supplied, 50 to 100 and sulfur-containing lubricating base oil production intermediate
/ Cm ² hydrogen pressure, at a temperature of 250 ~ 380 ℃
Idro finishing operation and wax 50 to 15
Temperature of 320-450 ° C. under hydrogen pressure of 0 kg / cm ^2.
A method for producing a lubricating base oil, characterized in that the isomerization operation below is alternately performed in the same reactor. 2. The catalyst is alumina or an alumina carrier containing silica therein, and the catalyst is group VIA or VI of the periodic table.
The method for producing a lubricating base oil according to claim 1, which is a catalyst supporting an element of Group II, Fourth period. 3. The method for producing a lubricating base oil according to claim 1, wherein the catalyst is a catalyst in which molybdenum, nickel and phosphorus are supported on an alumina carrier.