JPH02263896A - Method for improving sunlight stability of lubricating oil base product - Google Patents

Abstract

PURPOSE: To improve the sunlight stability of a lubricating oil base product, by subjecting liquid products produced by the isomerization of wax to hydrorefining in the presence of a specified catalyst under mild conditions.

CONSTITUTION: All liquid products produced by the isomerization of wax are subjected to hydrorefining in the presence of a catalyst selected from group VIII metals and carried on a refractory metal oxide under mild conditions, i.e., at a temperature of 170-270°C (preferably 180-220°C), a flow rate of 0.25-10 V/V/hr (preferably 1-4 V/V/hr), a pressure of 300-1,500 psiH₂ (preferably 500-1,000 psiH₂), and a hydrogen gas flow rate of 500-10,000 SCF/B (preferably 1,000-5,000 SCF/B).

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Oils in the boiling range in lubricating oils obtained by hydroisomerization of waxes are suitable for use as lubricating oil base stocks or compounding stocks. Neither daytime stability nor oxidative stability is shown. Such oils may have improved intra-day stability and oxidative stability by treatment under mild conditions over a catalyst having Group I on a support or Group I on a halogenated support. I understand. Preferably, the metal component of Group Ⅰ is platinum. The sampled catalyst is a material containing halogenated alumina or an alumina support, preferably a material in which alumina or alumina catalyst is predominant (e.g. greater than 50%), more preferably a fluorinated or chlorinated material. even more preferably fluorinated alumina on the supported support.
It is selected from platinum on a support, and most preferably platinum on a fluorinated gamma alumina catalyst. These preferred catalysts are preferred hydroisomer catalysts that are used under mild to severe operating conditions.

Sludge waxes containing 0% to 25% oil from conventional petroleum crude dewaxing are hydrotreated over conventional hydrotreating catalysts to reduce the levels of sulfur and nitrogen content in the wax. be done. This hydrogen treatment
This is necessary in order to avoid inactivation of the typical group I on the isomerization catalyst of halogenated refractory metal oxides. Other materials that are less sensitive to isomerization catalysts are used, such as combinations of Group II metals on refractory metal oxide catalysts, because such catalysts are usually sulfurized prior to use. This reduces, if not eliminates, the need for pre-hydrogen treatment. However, in such instances, the condensate from the isomer unit utilizing such catalysts will not be as halogenated as used in the present invention during the mild hydro-refining step following isomerization. Prior to contacting the Group I metal on the refractory metal oxide catalyst or the Group I on the refractory metal oxide catalyst, it must be treated to remove sulfur, nitrogen, or both.

Isomerized sura from the isomerization unit.

The entire liquid wax product is then refined under mild hydrorefining conditions with a Group II metal over a halogenated refractory metal oxide catalyst or a Group II metal over a refractory metal oxide catalyst. This step is followed by fractionation into different cut boiling ranges in different lubricating oil paces, dewaxing and final fractionation. Although these steps can be carried out in different sequences, it is desirable to subject the total liquid product from the isomerization unit to the gradual hydrorefining described here; The reason for this was that in the past,
This is because such a hydrogen finishing procedure needed to be performed on fractionated oil rather than simply canted oil.

It has been found that it is possible to hydrofine fractionated and isomerized wax products, but in the case of non-fractionated isomerized wax products, from the isomerization unit It has also unexpectedly been found that the total liquid product of can be hydrofined under mild conditions to produce materials with improved daytime stability.

[Contents of the invention]

In the present invention, the lubricating oil base stock or formulated stock oil obtained by isomerization of sludge wax is halogenated by converting the total liquid product from the isomerization unit under mild conditions. significantly improve its sunlight stability by a process comprising contacting a metal from Group VIB to Group II on a hydrogen isomeric refractory catalyst of a refractory metal oxide or a metal of Group II on a refractory metal oxide supported catalyst. It is known that this is possible.

Hydrogen finishing under this mild condition is at a temperature of about 170°C to 270°C, preferably 180°C to 220°C, and from 0.25 to IOV/V/hr, preferably from 1 to 4 V/V/hr. With a flow rate of 300 to 1500
psi Hz preferably 500 to 1000 psi H
At a pressure of z, and from 500 to 10.0OO3CF/b
bl preferred, shi< is 1000 to 500QSCF/bbl
is carried out at a hydrogen gas flow rate of . Temperatures at the upper end of the range should only be used if pressures are similarly employed at the upper end of the ranges mentioned. Temperatures above these listed temperatures should be employed at pressures above 1500p.
Although pressures above si may be used, such pressures are neither practical nor economical.

In conjunction with the isomerization step, any necessary hydrotreatment of the sludge wax condensation can be performed using commercially available catalysts such as Co/Mo on alumina, e.g.
Under standard commercial conditions such as temperatures from 0.1 to 2. At a space velocity of OV/V/hr, 50
at pressures from 0 to 3000 psi lit, and 500
to 500 OSCF/B (7) gas flow rates.

The isomers are typically numbered from ■ to ■, more preferably ■
The catalyst is carried out on a catalyst comprising a hydrogenated metal component of a noble metal group, most preferably platinum on a halogenated refractory metal oxide support. The catalyst is typically 0.
1 to 5°0wt1 metal preferably 0.1 to 1.0
wtχ metal, most preferably 0.2 to 0.6 wtχ
The refractory metal oxide support is typically a transition material, such as gamma alumina or eta alumina, and the halogen is most commonly fluorine. Isomerization is carried out from 270°C to 400°C, preferably at 300°C.
The process is completed under moderate to high temperature conditions of 360°C to 360°C. The space velocity range is 0. lO to IOV
/V/hz? Yes, but 1.0 to 2. Preferably it is OV/V/hr. Pressure range is from 500 to 300
0psi Hz but 1000 to 1500p3i
The hydrogen flow rate range, preferably Hz, is 1
000 to 10,0OO3CF/B. Conversion of waxes to isomers is preferably carried out at moderate levels. The conversion is at such a level that 25% to 40% unconverted wax, and preferably 25% to 35% unconverted wax, remains in the 370°C full distillate delivered to the dewaxer. It is preferable that there be.

As already mentioned, if the isomerization catalyst is of the group that is normally presulfided before use, the prehydrogen treatment step can be omitted, but the isomerized wax product still , H2 and NH before being contacted with the second stage catalyst.

must be removed. This operation involves flushing to remove H2 and NH.
g) or by stripping.

Preferred catalysts used in the present process include a hydrogenation metal component that is a Group II noble metal or a mixture thereof, more preferably a Group II noble metal;
Most preferred is an alumina-containing material or platinum on fluorinated alumina, more preferred is a predominantly (i.e., greater than 50%) alumina-containing material or alumina, and most preferred is gamma alumina. or eta-alumina, in which the waxy condensate-derived catalyst mentioned above is a processing feature.
(1) When the hydration level is below 60, when the hydration level is 100, the fluorine is at a high concentration of HF, i.e. above 10-t%, preferably from 10 to 15-tχ, and the substance is 1
XRD peak height of a standard consisting of 150 mg gamma alumina 0.6 wt χ platinum containing 7,2 Ht, X-ray diffraction (X RD
) is 10 to 60 as a value determined as the relative amount of hydrate represented by the peak in the pattern, and (2) the surface nitrogen content @N/Al ratio is XPS (X
-ray photoelectyron 5pecl
(3) the bulk concentration of fluorine is about 2 to 10-tχ, and (4) the surface The surface concentration of fluorine is 3wt as the amount of fluorine present in a layer extending to a depth of 1/100 inch from! preferably less than Iwtχ, and most preferably less than 0.5 svtχ if the surface concentration of fluoride is less than the bulk concentration of fluoride.

There are many ways to measure the fluoride content of a catalyst.

One technique, well described in the literature, uses oxy-combustion methods to analyze fluorinated catalysts. Approximately 8
A sample of lOag from the 300th floor! Mix with 0.1 g of benzene and 1.2 g of mineral oil in a stainless steel explosion capsule fitted inside. Then explode the oxygen salt incendiary bullet. The "sample" is deoxygenated and then combusted under a pressure of 30 Atm of pure oxygen. The combustion product is non-ionized 5I
collected in 1 liter of water. Once the reaction is complete (approximately 15 minutes), the absorption solution is transferred quantitatively to a fixed volume.

The fluoride concentration in the sample is determined by ionizing the combustion product solution.
Determined by chromatographic analysis. A calibration curve was drawn by burning an ethanol KF standard (in the same way as for the samples) at several temperatures, resulting in a calibration range of 0 to 10 ppm. The fluoride concentration of the catalyst is calculated on a no-ignition loss basis by comparing the response of the calibration curve and the response of the sample solution. Ignition loss is at least 2
Measured on individual samples heated to 800'F for hours.

In the second method, the fluoride is distilled off by titration. Fluoride is converted to fluoride silicon salt (HzSi F &) by reaction with phosphate in the medium and thus distilled by ultra-hot steam.

This is William-1+1interTanana
CV distillation. It should be noted here that the use of very hot dry (not wet) steam is essential to obtain accurate results.

Using a wet steam generator results in a fractional fraction of 10% to 2.
It was 0% lower. The collected fluoride silicon salt is titrated with a standardized solution of sodium hydroxide. A modification is also carried out on the phosphoric acid transferred to the steam. Data regarding fluoride is reported on the basis of no-ignition loss after measuring ignition loss on a sample heated to 400° C. for one hour.

A third preferred catalyst is a material containing a support of alumina or the precipitation of hydrogenated metals on alumina, wherein said metal-loaded support is typically heated between 350 and 500°C.
calcining preferably at 450 to 500° C. for about 1 to 5 hours, more preferably about 1 to 3 hours, and fluoridating the metal loading support using a high pH fluorine source solution to about 8 wt. %, preferably less than about 7 wt2, of a mixture of NH4I or HF with a pH value of 3.5 to 4.5 and preferably produced before rapid drying/heating in a thin bed or rotary kettle. By this, by heating in air, about 350 to 45
At 0° C. for 3 hours and if necessary holding the final relief for a period sufficient to reduce the hydrate content to the aforementioned levels (e.g. 1 to 5 hours) in an oxygen-containing atmosphere and nitrogen atmosphere. Ensure an active atmosphere, or use an aqueous solution of HF or a suitable mixture of HF and NH,F with a low pH fluorine source solution of no more than about 10 wt%, but preferably no more than about 8 wt% followed by about 35 wt%
Drying/heating is carried out in a thin bed or rotating oven at temperatures of 0 to 450°C, preferably in air, provided by a process of treatment in an oxygen-containing atmosphere for 1 to 5 hours. The alumina or alumina-containing support material is preferably extruded in shape and preferably has a longest cross-sectional dimension of at least about 1732 inches across. low pH
Once the catalyst given the value is initially charged to a certain unit, the catalyst must be held at the final temperature for more than 5 hours, preferably for more than 10 hours and preferably at a temperature of 400 to 450°C. No.

The above catalysts typically range from 0.1 to 5. Owtχ, preferably 0.1 to 1.0 wt% metal, and most preferably 0.2 to 0. Contains Owtχ metal.

The dried/heated catalyst is
photo-electron 5 pectrosco
py ), the surface nitrogen content NEAl is 0.01 or less, more preferably N/AI is 0.004 or less.

Following the heating step described above, the catalyst is charged and rapidly brought into operation in the isomerization reactor. Instead of doing this,
Following the heating step described above, p)I from 3.5 to pH 4
The catalyst presented using the solution technique of . Care should be taken that 24 hours, preferably 2 to 10 hours, is sufficient. For comparison, the pH is 3.5.
Catalysts provided using less than 100 ml of solution can be activated in pure or factory hydrogen at 350 to 500° C. for from 1 to 48 hours or more. In fact, the pH value is 3.5
If the catalyst provided using a solution of less than , if heated first, milder activation conditions similar to those used in the case of catalysts presented in high pFl solution techniques are sufficient.

Typical activation profile is 100°C for 0 to 2 hours
For a catalyst held at Hold at final temperature for a period of time. Instead of this, the catalyst can be heated from room temperature to a final temperature of 350 to 4
It can also be given by heating to 50° C. for 2 to 7 hours and holding at that final temperature for 0 to 4 hours.

A similar activation can be completed by increasing the temperature from room temperature to the final temperature in 1 hour.

If the catalyst is first heated in air, it is possible to dispense with a separate activation step completely. In these examples, the calcined catalyst is simply charged up to the reactor, heated to a temperature just above the melting point of the wax condensate, and the condensate and hydrogen introduced onto the catalyst; The unit then rapidly comes into operating condition.

A fourth preferred catalyst is to precipitate the hydrogenated metal onto the support and to evaporate the metal-loaded support with fluorine chloride, such as 1, HF, by any conventional technique such as spraying, soaking, minor moisture, etc. material containing a support of alumina or fluorinated alumina, whereby between 2% and 10% F, preferably between 2% and 8% F. Precipitate. After halogenation, the catalyst is typically dried at 120° C. and then crushed to expose the internal surfaces, and the crushed catalyst is double sieved to remove fines and uncrushed particles. This uniformly sized catalyst is less than 1732 inches and typically has a maximum cross-sectional width of 1/64 to 1/32 inches across.

The initial particles or extrudates may be of any physical configuration, so particles such as cylinders, trilobes or quadrilobes may be used. Extrudates of any diameter may be used and their lengths may be from 1/32 inch to several inches; this length value is set by handling considerations only; is preferably a length smaller than the initial extrudate diameter.

After precipitation of the hydrogenated metal and fluorination of the particles or extrudates, the particles or extrudates are crushed or ground to expose the internal surfaces.

Tarafing is carried out on the particles or extrudates to a degree suitable to initiate operation. Thus, an extrudate 1 foot long and 1/16 inch in diameter will have dimensions ranging from 1764 to 1/32 inch across its longest cross section. Similarly, if the extrudate was initially only 1716 inches, it could simply be halved, for example, to give two 1/32 inch dimensions.

Alternatively, one may take a metal load support whose dimensions are already about 1732 inches or less and fertilize it using HF as described above.

Generally, therefore, the dimensions of the sized material are approximately 17
The value is between 64 inches and 1732 inches.

The uncalcined catalyst is prepared in a hydrogen atmosphere, such as factory hydrogen or pure hydrogen, containing 6Q to 70 vol. is activated in

Here, the hydrogen activation profile described above may be used.

This sized catalyst was unexpected but predominant for wax isomerization compared to crushed particle or extrudate starting material. The 10°C oil product is more effective than the 370+ oil given starting with waxed 0% oil (on the one hand) and about 20% oil (on the other hand) compared to about 5 to 10% waxed oil. To create a product that exhibits a high ■ value and therefore has the maximum ■ value,
A "sized" catalyst produced using HF will be used to isomerize waxes with 5 to 15% oil, preferably 7 to 10% oil.

To maximize the production of lubricating oils with viscosities in the range of 5.6 to 5.9 cst/100°C, the isomerization process must be carried out under conditions of low flow rates of the hydrotreating gas. That is, the flow rate of the processing gas is 500 to 5000S.
CF/bb1. H2, preferably 2000 to 400
0SCF/bb1.81, more preferably about 2000
It should be between 3000 SCF/bbl, o.

The isomerized wax material is then subjected to a second catalytic
Steps of processing are performed. In this treatment, a catalyst in which a group 1 metal is supported on a refractory metal oxide or a catalyst in which a group 1 metal is supported on a halogenated refractory metal oxide is used.

The halogenated catalyst may be the same as the Group I metal supported on the halogenated refractory metal oxide used in the preceding isomerization reactor, or may be different from this. If the same catalyst is used, the process can be carried out according to the sequence shown in the blocks.

That is, the reactor is initially operated under harsh conditions to produce isomers and compounds, which are then stored in a tank. Removes trace amounts of polynuclear aromatic components that may have an adverse effect on properties and oxidative stability. However, these mild conditions are insufficient to cause differential isomerization of the hydrocarbon components. This second stage is carried out at a temperature of about 170°C to 270°C, preferably 180°C to 220°C, a flow rate of 0.25 to 10V/V/hour, preferably 1 to 4V/V/hour, and a flow rate of 300 to 1500°C.
psiHx, preferably 500 to 1000psi)I
t pressure and 500 to 10. OOOSCF/B,
It is preferably carried out at a hydrogen flow rate of 1000 to 5000 SCF/H. Higher temperatures may be employed if the pressure exceeds 1500 psi, but such high pressures are impractical.

Following the isomerization and a second stage carried out under mild conditions, the isomerization products are fractionated into the lubricating oil cut and the fuel oil cut. Lubrication oil cut is 33
It is a component that boils in the 0°C range, preferably in the 370°C range. This lubricating oil component is dewaxed to a bore point of about -21°C or below. Since in the process of the present invention unconverted wax is recycled to the isomerization unit, dewaxing is carried out in a manner that allows recovery of unconverted wax. The recycled wax is preferably recycled to the main wax reservoir and passed through a hydrotreating unit to remove any dewaxing solvent contained therein and to remove any adverse effects thereof on the isomerization catalyst. Alternatively, a separate stripper may be used to remove dewaxing solvent and other foreign matter. In view of the loss of unconverted wax, dewaxing processes that destroy the wax, such as catalytic membrane waxing, are not recommended. Solvent dewaxing is performed and typical dewaxing solvents are used.

Solvents that may typically be used include, for example, CsCa ketones (e.g. methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof), C8C1° aromatic hydrocarbons (e.g. toluene), mixtures of ketones and aromatics (e.g. M
EK/) luene), self-freezing solvents such as propane, propylene, butane, butylene and mixtures thereof, which are usually gas phase liquefied, and the filter temperature is -25°C.
The temperature is between -30°C. The preferred solvent for isomerization, especially for isomerizations obtained from heavier waxes (e.g. bright stock waxes) under miscible conditions, which yields the highest yields at high filtration rates, is MEK. /MIBK (20/80 v/v) mixture, which is used in the range of -25°C to -30°C. Although it is possible to obtain a bore point below -21° C. by lowering the filter temperature and lowering the other proportions of the solvent, in this case the problem arises that the filtration rate is reduced.

Also, isomerization products obtained from microwaxes, such as Bright 5tock
) When deparaffinizing coarse wax, the portion of the isomerized product sent to the dewaxing equipment is about 330 to 60
Recognized as fractional boiling carried out at a temperature of 0°C, preferably about 370° to 580°.
It has been found desirable that the broad heart cut and, after such fractionation, the portion sent to the dewaxer have between 25 and 40 percent unchanged wax. The heavy bottom portion contains significant wax and can be recycled directly to the isomerization unit. However, if hydrotreating or deoiling is deemed necessary or desirable, the fractionated bottom portion is first sent to a fresh feed reservoir and then recycled by combining with the wax therein. Alternatively, the isomerization product from the second stage catalyst zone may be fractionated into narrow cuts and each cut individually dewaxed.

1 and 2 are schematic diagrams showing a preferred embodiment of the wax isomerization process.

In FIG. 1, a coarse wax feed derived from light oil, e.g. below 60 ON, is sent via line 2 from reservoir 1 to hydrotreater 3, where heteroatomic compounds are removed from the wax. Ru. This hydrotreated rough wax is sent to the isomerization device 5 via the pipe 4, and then
The entire liquid product is first sent via lines 6 and 6A to the cold relaxed state second stage treatment unit (unit 7) where the TL
P is contacted with an isomerization catalyst or simply with a Group 4 noble metal catalyst supported on aluminum. The resulting stream is sent via line 6B to the rectification column (device 8).

A stream of lubricating oil boiling above 370° C. is sent via line 9 to a solvent dewaxing device (device 10) in order to separate the wax content therefrom. The dewaxed oil fraction is recovered via line 11 and sent to other conventional processing steps normally used for blending feedstocks and blended oils. The recovered wax can be recycled directly into the coarse wax stream being sent to the isomerizer or can be passed through line L2b to the hydrotreater before being recycled to the isomerizer.
is recycled to Reservoir 1 via .

The wax processing flow in Figure 2 is very similar to that in Figure 1, with the main difference being that Figure 2 shows the diagram dealing with heavy waxes, such as wax feeds derived from bright stock oil. The point is that there is. In such a case, before transferring the wax from reservoir 1 to the isomerization unit (unit 5) via line 4, it is sent via line 2 to hydrogenation unit W3, and then via line 6 to 6A where it is heated under low temperature and mild conditions. It is sent to a second stage treatment unit (unit M 7 ) where the isomerization catalyst is further modified or simply contacted with a group 1 noble metal supported on alumina and then via line 6B to a fractionation column (unit i[8).
send to In the fractionation tower, the boiling point of the isomerized product (isoa+erate) produced using heavy wax is 370°C
- a light fraction with a boiling point in the range of 370°C and a residual fraction with a boiling point in the range of 580°C. The broad lubricating oil fraction with a boiling point between 370° C. and 580° C. is sent via line 9 to the dewaxing device (device 10) already mentioned. The residue at 580° C. contains a significant amount of wax and is recycled to the isomerization unit 5 via lines 13.13A, 13B. This residue is optionally combined with the wax in line 12 recovered from dewaxing unit 10 via lines 13 and 13C, in which case all recycle is transferred to line 12.1.
3B and 1 to an isomerizer or can be sent to a wax reservoir via line 12B for treatment in a hydrogenator prior to being sent to an isomerizer.

In the following examples, the catalyst is used as a first-stage isomerization catalyst and/or the second-stage mild conditions are used as a hydrogenation (hydrogenation) catalyst.
(finishing) catalyst.

It is made clear on each side which catalysts are used for which applications.

μ0!3: Contains 0.62% PT on gamma alumina and approximately 1% chlorine. This is a commercially available platinum catalyst supported on γ alumina.

Fu Gai Dan: Commercially available Pt/rAfzos base (
Platinum supported on T-fluoride alumina obtained by immersing catalyst A) in an NH4F/HF solution with a pH of about 4. The soaked material was washed, dried, and then heated in air at 400° C. for 2 hours. As a result of analyzing this catalyst, the total fluoride concentration was 7.0.
%, platinum temperature is 0.62% by weight, N1Al ratio on the surface (
(by X-ray spectroscopy) was 0.0037. The catalyst was activated by heating to 450° C. in hydrogen at a pressure of 3.51 kg/ct as follows. That is, heating from room temperature to 100°C over 2 hours and holding at 100°C for 1 hour; 3
Heat from 100°C to 400°C over time and hold at 450°C for 4 hours.

Catalyst C: Commercially available Pt/γAl1zOz base (catalyst A)
This is one piece of platinum supported on fluorinated alumina obtained by immersing it in an NH4F/HF solution with a pH of approximately 4. The soaked material was washed, dried, and then heated in air at 400° C. for 2 hours. As a result of analysis of this catalyst, the total fluoride concentration was 6.9%, the platinum concentration was 0.62 weight, and the NlAl ratio at the surface (according to XPS analysis) was 0.0040.

The catalyst was activated by heating to 350° C. in hydrogen at a pressure of 3.51 kg/ad as follows. That is, heating from room temperature to 100°C over 2 hours and holding at 100°C for 1 hour; heating from 100°C to 400°C over 2 hours, and holding at 350°C for 1 hour.
Time keeping.

Boiled: This is platinum supported on T-fluorinated alumina obtained by immersing the commercial Pt/γ8z, base (catalyst A) in an approximately 10% HF solution. The soaked items were washed and then dried in air. As a result of analyzing this catalyst, the total fluoride concentration was 8.0.
%, the platinum temperature was 0.62 wt%. The catalyst was dissolved in hydrogen at a pressure of 21.09 kg/c+a as follows:
It was activated by heating to 00°C.

That is, heating from room temperature to 100 °C at 35 °C per hour, 100 °C
Hold at ℃ for 6 hours; 100℃ to 250℃ at 10℃ per hour
℃ and held at 250℃ for 2 hours, 10℃ per hour.
Heat at 100°C to 400°C; hold at 400°C for 3 hours.

7UIfi: 0.5% pt held once with γ alumina
A commercially available platinum supported on γ alumina consisting of
The halogen was removed and activated by heating in hydrogen at a pressure of 2.81 kg/c+J as follows: heating from room temperature to 100°C in 2 hours;
Hold for 1 hour; heat to 350℃ for 2 hours;
Hold for 1 hour.

In the following example, raw sulfur rank wax obtained from the dewaxing of petroleum oil is hydrogenated to deactivate the fluorinated alumina-platinum hydroisomerization catalyst. Petroatom compounds (sulfur- and nitrogen-containing compounds) and polar substances are removed. Any conventional hydrogenation catalyst (e.g. Cy
anamia's HDN30: Katalco q
NM-506; Ketjen's XF-840, etc.) can also be used. The primary treatment goals for the hydrotreated material are approximately 10 ppm sulfur content and 1 ppm or less nitrogen content. In this example, a KetjenKF-840 in the form of a 1720-inch quadrilobe.
was used. As received from the manufacturer, this catalyst was alumina based with 4% NiO and 19.5% MO.
O3 and had a surface area of 180 rrf/duram, an average pore volume of 0.35 cc/g, and an average pore radius of 38. This 12 liter catalyst has a diameter of 9.9
cm, length 189c11 tubular fixed bed and sulfided by exposure to H,S in hydrogen and sulfur-containing vacuum distillate. The hydrotreating unit can operate in either upflow or downflow mode. Two different slack waxes were hydrogenated. That is, Hes
tarCanadian 600M slack wax socks and AugustaBright 5tock slack wax socks. Typical characteristics of each feed are shown in Table 1 below.

Table 1 Slack wax source gravity API Clay, 100°C cSr Sulfur, wppm Total nitrogen, wppm Basic nitrogen, wppm Asphaltenes (weight percentage) Dewaxing aid (weight percentage) GC distillation, initial temperature 1%, °C 5%, °C 50%, °C 93%, °C Oil content M (weight percentage) Aromatic content (weight percentage) 0O Neutral 36.2 6.93 19.6 Bright tock 31.5 18.25 0.14 0.17 12. 9 The above is a representative assay of identified slack wax standards.

In fact, significant changes, particularly in sulfur and nitrogen content, are seen in different samples of these slox waxes over time, reflecting variations in different crude samples and depending on the severity of processing. are doing.

600M Surasok wax at 0.5V/V/hr, hydrogen pressure 1000psig and gas processing rate 1500SCF
Hydrogenated in Ht/B in upflow mode. During the first 2080 hours of operation, the reaction temperature was kept at 320°C and thereafter at 330°C. The sulfur content of slack wax is approximately 0.073 percent to 0.1 percent by weight.
13 percent, nitrogen content - 12 to 17 hρ
It was ρm. Periodic analysis of the hydrogenated wax showed that the sulfur content was always below 4 wppm, while the nitrogen content was always below 2 wppm.

Bright 5tock slurry wax feeds with different oil contents are heated at 380℃ and hydrogen pressure 11000ps.
Hydrogenation was then performed in upflow mode at a processing gas rate of 1500 SCF Hz/Bte. The space velocity was varied from 0.42 to 0.5 to obtain the desired sulfur/nitrogen reduction. Testing of the hydrogenated wax feed used in the examples is shown in Table 2 below.

Table 2 Coarse wax Hydrogenation wax source 60ON Bright 8 gravity (8 PI @ 15℃) 36,3 35゜7 viscosity (1
00℃cst) 6.77 11.05 Sulfur (w
ppm) 2, 2 nitrogen (wpp
m) <1 <1 Asphalt (wt%) -0,05 Dewaxing agent (wt%)
0.00 Initial 6C distillation temperature (℃)
367 1891% (t”> 378
2115% (t) 412 31350%
(t) 482 36693% ('tl:
) 547 Oil content (wt%') 19
．． 5 17゜1 Aromatic content Jl (wt%) 24 Stock 34.1 10,52 1 23.6 Hydroisomerization treatment The rough wax from the hydrogenation treatment agent liberated from hydrogen sulfide and nitric acid contains the various types of Pt mentioned above. -F/8 to 80. It is isomerized by treatment with a catalyst. The yield of dewaxed oil at 370° C. and 100° C. described below is the standard test for petroleum wax extraction solvents of ASTM Law 3235-73 (effective in 1983).

(8) Hydrotreated bright stock wax (B) is 320
°C, 0.89V/V10r space velocity, 100 ps i
() I z) Pressure and 5000 SCF/bbl, l
Isomerization was carried out at a gas flow rate of 200 cc and a catalyst B charge of 200 cc. Hydroxylation was carried out in upflow mode and the mass rate was run at 160 hr/ft (low mass rate).

The total isomerized liquid production (TLP) was 37.5 wt% at 370°C conversion when the standard 370°C ten-dewaxing yield was 48°5t% (depending on feed).

B) Hydrotreated bright stock wax (B) low mass rate 325-330°C 1.89 V/V/h.

1000 psigSHz, 5000 SCF Hz/
bbl, isomerized with 11,200 cc of catalyst input.

The total isomerized liquid production (TLP) was 370°C-conversion of 20.6wt% when the standard 370°C ten-dewaxed oil yield was 41.7wt% (depending on the feed).

(C) Hydrotreated bright stock roughing wax (A) was subjected to six consecutive high mass rate conditions (2000 bonds/hr/5QI
IARE PQOT) 17) Reactor charging 135 Q
Isomerization was carried out over an Occ catalyst under the following isomerization conditions for 2&Il. (i) 313°C, 0.5 V/V/Hr
, 1000psi, 5000SCF H2/bb
l and (ii) 325°C, 1, OV/V/Hr, 10
00psig, 5000SCF H! /bb 1 mixed isomer production rate (ii/i = 80/20).

Conversion (mixture) was 25.1 wt% at 370°C. Under standard conditions, the dewaxing oil yield (mixture ratio) at 370° C. was 50.0 wt%.

(D) 600 N hydrogenated rough wax, 6 series (6)
High mass rate of 2000 lb/hr/sq-ft-32
6℃, l 000psi 15000SCF Hz/b
bl, 1. Reactor input of OV/V/rr 35
Isomerization was carried out over 00 cc of catalyst. Conversion to 370°C was 25.8. 370′c” Dewaxed oil yield is 5
It was 1.0 wt% (depending on the feed).

The base oil was prepared from the total liquid product resulting from the isomerization zone by fractionating the TLP into various lubricating components and dewaxing the lubricating components to a pour point of -21°C.

1. A 60ON coarse waxy compound (D) is obtained by dewaxing the filter at -26°C in a wet state using 100% MIBK solvent at a dilution ratio of 4 parts solvent to 1 part oil.
The TLP of the sample showed a maximum value of 370°C, and this lubricating component was dewaxed to a pour point of -21°C.

2. Bright stock isomerized product (B
) showed a maximum value of 370°C and was dewaxed at -21'C.

3. Bridestock isomer (C) is 370-58 using 15/85 MBK/old BK solvent 4 per l oil
Fractionated to give a heart-cut split at 2°C -2,7
It was dewaxed at a flow rate of -21°C. This dewaxed oil is then placed at the front and rear ends of the desired heart cut at two
% fraction is vacuum fractionated.

4. Similar to 3 (above), but the increasing fraction was mixed to a final dewaxed oil viscosity of 8.0 to 8.3 at 100°C.

5. Same as 3 (above), but the increasing fraction of bright stock isomerization product (A) from distillation component (A) is 100°C
The viscosity of the final dewaxed oil was mixed at .

In the following example, the sunlight stability of Products 1 to 5 (above) was determined by using a 5 tel sample with a Sunbrite Electric "Efthera Fluorene End Tube" that corresponds to the intensity and period of actual solar irradiation. It was placed in a nose box device where air was always present. Samples were classified according to the degree of haze, block and sludge formation on a daily basis during air and light exposure.

The dewaxed base oil stocks 1 to 5 above were evaluated for sunlight stability and exhibited the following properties.

Table 3 Slight haze at 48 hours Noticeable haze at 49 hours Haze/stuff 2524 hours Haze/stuff 2524 hours Haze/stuff 2524 hours Haze/stuff 2524 hours Hydrofinishing. When the sunlight stability of this hydrogenated base oil was investigated, it was found that although the sunlight stability was slightly improved as shown below, it was still insufficient.

Table 4 KF-840 Hydrorefining Sun Stable Debased Oil 3 Haze/Sludge 50 Hours 4
Haze/Sludge 100 hours It can be said that all of the above dewaxed and isomerized base oil products exhibited sufficient sunlight stability since conventional lubricating base oils exhibit sunlight stability of 10 days or more. There were quite a lot of things.

■1 KF840 which is sulfurized wax base oil base oil 3 and 4
(Ni-MO/A180s) at 500psi, 5
00SCF Pt/F-A1203 with dewaxed base oil 3.4.5 under conditions of uz/bbt and IV/V/h - Bare finish base oil (PL-F/Al, 0.0% catalyst)
Hydrofinishing was carried out using Catalyst B using several conditions shown in Table 4. When the sunlight stability of the hydrogenated product was investigated, the following results were obtained.

Table 5: Dewaxing base oil feed catalyst hydrofinishing conditions temperature t: 160 180 200 200
225 200 pressure ps+ H2100010001
000100010001000 Space velocity & V/V/hour 0.9 0.9 2.0 0.9 0.9 0.9 Gas flow rate SCF H,/B 2270227022702
27022705000 Time to Form 8 >60 *Feed 4 had already formed a sludge prior to hydrofinishing, and this sludge was filtered out prior to hydrotreating and evaluation.

It has been found that higher stability can be obtained in processing isomerized fractions by using higher processing gas flow rates.

In Examples 4-9 below, stabilized and unfractionated all-liquid isomerization products were hydrofinished using various catalysts under various conditions and sunlight stability was investigated.

The 60ON slack wax total liquid isomerization product (TLP) obtained by hydroisomerization (d3 treatment) using Teido Catalyst D (Ni-Mo/AJzOz) was subjected to KF-840 (conditions are shown below). Hydrogenated and finished.

The hydrofinished product was fractionated to give a 370°C fraction, which was heated to -21°C at a filter temperature of -26°C using 100% MIBK solvent at a solvent to oil diluent ratio of 4/1. I took my clothes off at ℃.

The sunlight stability of this dewaxed oil was investigated.

Table 1 Temperature °C Pressure psi Hz Gas flow rate, SCF/B, )lt Space flow rate, V/V/hr 2.0 2.0 As can be seen from the table above, all liquid products are The products obtained when treated with a finishing catalyst exhibited insufficient sunlight stability.

Charcoal 1 Feed 60ON slack wax isomeride (TLP) D
Also, bright stock sulfur wax isomeride (TLP) was used as Feed B, and these were hydrofinished using platinum/alumina and Catalyst E (as described above) under the following conditions. This was fractionated to obtain one fraction at 370°C, which was dewaxed to -21°C as shown in Example 4. The sunlight stability of the purified product after dewaxing was investigated. (Table 7) Hawk-Single Hydroisomerization (TLP) Feed Hydrofinishing Conditions: Temperature °C Pressure psi l (z Gas flow rate, SCF/B, H.

Space flow rate, V/V/hr2.0 2.0 0.9 By hydrofinishing the entire liquid product using platinum supported on alumina as a catalyst, hydrogen is produced using a conventional hydrofinishing catalyst. It has been found that improved sunlight stability is obtained compared to materials obtained from chemically finished TLPs.

Feed coalworks 60ON slack wax isomeride (TLP) D
Platinum (1% C1) held in alumina as
Hydrofinishing was carried out using a catalyst (Catalyst A described above) under the conditions shown below.

The hydrofinished isomerate was fractionated to give a 370°C fraction, which was segmented from -21°C with 100% MIBK solvent at a 4/1 solvent to oil dilution and a filter temperature of -26°C. Dewaxed and dewaxed as in Example 4. The sunlight stability of the fraction after dewaxing was investigated. (Table 8) Man-"L-Table.

Hydrofinishing conditions Temperature °C.

Pressure psi Hz Gas flow rate, SCF/B, Hl Space flow rate, V/V/hour 2.0 2.0 From this, TLP can be hydrogenated using platinum supported on halogenated alumina as an isomerization catalyst. It can be seen that the finishing results in a material exhibiting significant sunlight stability.

Mawari-60ON TLP (Feed D)
) to Pt/F Aj! Hydrofinishing was carried out using zOx (catalyst C) as a catalyst under the conditions described below.

The hydrofinished isomerate was fractionated to give a 370°C 0 fraction, which was desorbed with 100% MIBK solvent at a solvent to oil diluent ratio of 471 at a filter temperature of -26°C. Dewaxing was performed as shown in Example 4. The sunlight stability of the dewaxed fraction was investigated.

(Table 9) From the above results, it can be seen that there are certain regions in the hydrofinishing conditions that maximize the sunlight stability of the material obtained from the isomerized all-liquid product. Hydrogenated finish 180 to 300 to obtain sunlight stability.
It can be seen that it is sufficient to carry out the process within the temperature range of ℃.

Anal Bright Stock Coarse Eyes Melate (TLP),
Feed (a), pt/F-An! gos
Hydrorefining was carried out on (Catalyst B) under the conditions described below. TLP and hydrorefined materials that have not been hydrorefined are
A 460-450°C fraction was obtained by vacuum distillation, which was further dewaxed. These fractions were filtered using 5% toluene, 795% M I B-
I tried to take my clothes off. Afterwards, the daylight stability of each theory was evaluated.

, Table-1" - Feed Hydroitumerate fat water 11 Jl [1 item Temperature ('C) - 200270 Pressure (psi
Hz) -10001000 Gas flow rate (SC
P/B, )lx) -50005000 Space flow velocity, Si/
shi/hr O, 90, 9 shoes
Chestnut-stopping kimono made by Hyoseikaken (460-550℃ fraction) Viscosity at 100℃ (cst)? ,2 6.8
7.1 Time until obvious haze occurs ≦1 13 10 hours (days) As can be seen from this table, hydrorefining at temperatures below about 270°C produces daylight-stable base oils from TLP. preferred to occur.

■ Nibrite Stock Coarsely Waxed Aitsumerate TLP, Feed (a), under the following conditions pt/F-Aj! OzOz
Hydrorefining was carried out on (Catalyst B). The hydrorefined material was vacuum distilled to obtain an intermediate fraction boiling in the range of 370° to 380°C. These two parts have a solvent:oil ratio of 4:
1. Dewaxing was performed with 100% MIBK at a filtration temperature of -30°C. The dewaxed intermediate fraction was then fractionated into light (4,5 csL) and heavy (8,4 cst) dewaxed oil fractions as shown in Table 11, and their daylight stability was evaluated.

Table-m Temperature (℃) Pressure (psi Hz) Gas flow ft (SCF/B, HD Space flow rate (ν/v/hr) 0.9 2.0 Viscosity at 100℃ (cst) 4.5 8.4 4.5 8.5 Pour point ('C) Time until clear haze occurs 12 10 11 11
Time (number of days) As is clear from the above examples,
Hydrorefining of the entire liquid product from the isomerization unit using catalysts supported with Group metals or Group I metals supported on halogenated refractory metal oxides can be used to produce non-hydrorefined dewaxed base oils or yields a dewaxed base oil that exhibits reduced daylight stability compared to a dewaxed base oil that is hydrorefined using a hydrorefining catalyst.

Each side has a narrow temperature range, i.e., 170 to 270°C, preferably 1°C, in which the hydrorefining is carried out under conditions of constant and moderate pressure, process gas rate and flow rate.
This indicates that the process must be carried out at a temperature of 80 to 220°C.

The following example illustrates the effect of hydrorefining under mild conditions on fractionated lube oil hydrocracked products.

A hydrocracked lubricating oil base stock was prepared as follows.

The fuel hydrocracker was operated under the following conditions to extract recycled material.

Feeds Heavy Coker Gas New Feed Rate (KB/D) 11.2 Conversion (wt%) -90.6 Recycle Extraction (KB/D) 1.05 Reactor 1 Temperature (°C) 401.6 Reactor 2 temperature (psi) 376.5 pressure quadrat (psi)
) 2100 This recycled material is separated into 26
．． A 3LV% lubricating oil was obtained. The lubricating oil fraction was separated using a solvent; a 40/60 mixture of MEK/MIBK was used, the ratio of the four agents and oil was %, and the filter temperature was -22.
It was ℃. As a result, a dewaxed oil having the following properties was obtained.

Fuel at 40°C (cst) 13.44 Viscosity Index 109 Saturates (wt%) 96.0 This base stock has excellent viscosity properties. A sample of this base stock was incubated at 300°C, 2, OLH3V-35
0 psi It, 50 Q SCF/B t(z, under the conditions of treatment gas rate, Ni sulfurized to Al2O2
A similar sample of the fractionated hydrocracked product hydrotreated against a conventional catalyst (KF-840) equipped with /Mo was prepared according to the present invention at 200 °C, 1, OLHSV,
1000psi To and 5000SCF/bbl
Under the conditions of treatment gas rate, Pt/F/A l,
03 catalyst (catalyst B) was hydrorefined. These 3
Seed oil was tested in two ways for daylight stability. In Method 1, 5111 vials were filled three-quarters full with sample, loosely packed with cotton wool, exposed to sunlight in a north-facing window, and checked for appearance every day possible.

In method 2, the 5
ml vials were exposed continuously in a light box using a Sunburst Electric Fucera fluorescent lamp to simulate the intensity and frequency of actual shots. Samples were evaluated daily for turbidity, flocculation, and time required to sludge.

The results are shown in Table 12.

It is clear from this that by hydrofinishing the hydrocracked products, base oil materials exhibiting excellent daylight stability can be obtained.

An experiment was conducted to determine the effect of mild hydrocracking on the overall liquid hydrocracking product. In this example, the entire feed sample liquid hydrocracked product was recycled from the fuel hydrocracked product described in Comparative Example 1.

A portion of this flow is heated to 200°C without any sorting.
It was passed over the catalyst at 1.0' LHSV, 1000 psi To and 5000 SCF/bbl Hz. On the other hand, another part used KF-840 and was processed in a conventional manner under the conditions described in Comparative Example 1. These raw materials were then processed to obtain a lubricating oil product.
The fractionated and deparaffinized lubricating oil product obtained was evaluated by the light box method described in Comparative Example 1 for daylight stability. The results are shown in Table 13.

It can be seen that mild hydrorefining of TLP hydrogenated products improves the daylight stability of the base oil obtained from said feedstock to a certain extent compared to conventional hydroprocessing, but the degree of improvement is It is clear that this does not significantly alter the reaction properties of the oil.

However, this example shows that due to mild hydrogenation production,
It does show that the daylight stability is significantly and surprisingly improved for the paraffin isomerization product TLP.

[Brief explanation of drawings]

FIG. 1 schematically shows the entire wax isomerization process using a light slack wax feed and including hydrotreating as a second stage according to the present invention; FIG. 2 shows a heavy micro 1 schematically depicts an overall wax isomerization process using a crystalline wax feed and including fractionator bottom circulation and the present invention as a second stage with hydrotreating under mild conditions; FIG.

Claims (14)

[Claims] (1) A method for improving the sunlight stability of lubricating oil-based or blended products made by isomerization of wax, comprising the steps of hydrorefining any liquid product produced by said wax isomerization. a catalyst selected from Group VIII metals supported on a refractory metal oxide, and a catalyst selected from Group VIII metals supported on a halogenated refractory metal oxide. A method characterized by being carried out under mild conditions using 2. The method of claim 1, wherein the hydrorefined whole liquid product is fractionated under mild conditions to obtain a lubricating oil fraction and a dewaxed lubricating oil fraction. (3) Under the above-mentioned mild conditions, hydrorefining is carried out at a temperature of 170°C to 270°C, a flow rate of 0.25 to 10 V/V/hour, a pressure of 300 to 1500 psiH_2, and a hydrogen gas amount of 500 to 10,000 SCF/ A method according to any one of claims (1) and (2), characterized in that it is carried out in B. (4) Hydrorefining under the above-mentioned mild conditions is carried out at 180°C.
At a temperature of from 1 to 220°C, at a flow rate of from 1 to 4 V/V/hr, at a pressure of from 500 to 1000 psiH_2, and at a temperature of 100
The method according to claim 3, characterized in that it is carried out at a hydrogen gas flow rate of 0 to 5000 SCF/B. (5) A claim characterized in that the catalyst used in the hydrorefining under the mild conditions is platinum or palladium for a refractory metal oxide, and is platinum or palladium for a halogenated refractory metal oxide. The method according to any one of paragraphs (1) and (2). (6) A claim characterized in that the catalyst used in the hydrorefining under mild conditions is platinum or palladium for oxidation of refractory metals, or platinum or palladium for halogenated refractory metals. (3) The method described. (7) Claim (5) characterized in that the catalyst used in hydrorefining carried out under mild conditions is fluorinated or chlorinated silica, silica/alumina, or platinum or palladium for alumina.
) method described. (8) Claim (6) characterized in that the catalyst used in hydrorefining carried out under mild conditions is fluorinated or chlorinated silica/silica/alumina or platinum or palladium for alumina.
) method described. (9) A process according to claim 8, characterized in that the catalyst is platinum on fluorinated transition alumina. (10) A method for improving the sunlight stability of lubricating oil-based or blended products refined by isomerization of wax, comprising the step of hydrorefining a fraction of the isomerized lubricating oil boiling region. said hydrorefining using a catalyst selected from Group VIII metals for refractory metal oxides or a catalyst selected from Group VIII metals for halogenated refractory metal oxides. A method characterized by being carried out under mild conditions. (11) The temperature of the hydrorefining is 170 to 270°C,
Flow rate of 0.25-10V/V/hr, 300-150
00psiH_2 pressure and 500 to 10,000
The method according to claim 10, characterized in that it is carried out at a hydrogen flow rate of SCF/b. (12) A claim characterized in that the catalyst used in hydrorefining carried out under mild conditions is platinum or palladium for refractory metal oxides, or platinum or palladium for halogenated refractory metal oxides. The method according to any one of items (10) and (11). (13) A claim characterized in that the catalyst used in hydrorefining carried out under mild conditions is platinum or palladium for refractory metal oxides, or platinum or palladium for halogenated refractory metal oxides. The method described in item (12). (14) Process according to claim 13, characterized in that the catalyst is platinum on fluorinated alumina.