KR102721492B1 - Method for manufacturing high performance lube base oil having high viscosity index and low kinematic viscosity - Google Patents

Abstract

A method for producing a lubricating base oil may be provided, comprising the steps of: a) supplying a linear alpha-olefin of C14 or more or a mixture thereof; b) subjecting the linear alpha-olefin of C14 or more or the mixture thereof to an oligomerization reaction to produce an olefin-based oligomer having 28 or more carbon atoms and a boiling point of 330 to 500°C; and c) subjecting the olefin-based oligomer having 28 or more carbon atoms and a boiling point of 330 to 500°C to a hydroisomerization reaction to produce a branched hydrocarbon having 28 or more carbon atoms.

Description

METHOD FOR MANUFACTURING HIGH PERFORMANCE LUBE BASE OIL HAVING HIGH VISCOSITY INDEX AND LOW KINEMATIC VISCOSITY

The present invention relates to a method for selectively producing a high-quality low-viscosity, high-viscosity index lubricating oil using a linear alpha-olefin (LAO) having a content of C14 or higher as a reaction raw material.

The American Petroleum Institute (API) classifies lubricating oils according to quality as shown in Table 1 below.

Viscosity index Sulfur content (weight%) Pour point(℃) Saturated (wt%) Group Ⅰ 80 to 119 greater than 0.03 -5 to 15 less than 90 Group Ⅱ 80 to 119 0.03 or less -20 to -10 90 and above Group Ⅲ 120 or more 0.03 or less -25 to -10 90 and above Group Ⅳ poly alpha olefin (PAO)

Among these, demand for high-quality lubricating oils of Group Ⅲ or higher is increasing, and in reality, the highest-quality lubricating oil can be considered to be PAO, which is Group IV oil.

PAO is a material obtained through oligomerization reaction and hydrogenation finishing reaction using C10 LAO (1-Decene) obtained through polymerization of ethylene as a raw material. When LAO raw material of C8 or less or C12 or more is used, major base oil properties such as viscosity index or pour point are not satisfied, so only C10 LAO is used as a raw material, and PAO lubricating oil derived from C10 LAO is of incomparably high quality compared to lubricating oil derived from general petroleum. However, since PAO lubricating oil derived from C10 LAO is a high-quality lubricating oil with a high price, there is a problem that the quantity itself in the market is not large.

In response to the above problems with PAO lubricating oils, the market is supplementing the insufficient quantity by using low-cost substitutes that can replace PAO lubricating oils. However, in terms of the important properties of lubricating oils, the low-cost substitutes of PAO lubricating oils currently on the market have the problem that they cannot satisfactorily replace existing PAO lubricating oils.

Meanwhile, a technology for producing a chemical substance (e.g., drilling fluid) with improved properties by shifting the double bond existing in the alpha position of LAO to the inside of the carbon chain and converting it into a linear internal olefin (LIO) (olefin shift reaction) is also known (e.g., U.S. Patent No. 6,281,404). However, the above prior art not only targets a wide range of LAOs having C4 to C50, but also mainly discloses the double bond shift reaction for 1-pentene, etc., and therefore cannot be regarded as a technology for utilizing inexpensive LAOs having C14 or higher.

Therefore, there is a need for a method to develop a low-cost substitute that can effectively replace existing expensive, high-quality lubricating oils.

One aspect of the present invention provides a method for producing a lubricating oil, which can produce a low-viscosity, high-viscosity index lubricating oil having properties equivalent to or higher than those of conventional PAO lubricating oils, by using an inexpensive C14 or higher linear alpha-olefin (LAO) as a reaction raw material, thereby aiming to increase the added value of inexpensive C14 or higher linear alpha-olefins.

One aspect of the present invention provides a method for producing a lubricating oil including a branched hydrocarbon having at least 28 carbon atoms, the method comprising the steps of: a) supplying a linear alpha-olefin having at least C14 carbon atoms or a mixture thereof; b) subjecting the linear alpha-olefin having at least C14 carbon atoms or the mixture thereof to an oligomerization reaction to produce an olefin-based oligomer having at least 28 carbon atoms and a boiling point of 330 to 500°C; and c) subjecting the olefin-based oligomer having at least 28 carbon atoms and a boiling point of 330 to 500°C to a hydroisomerization reaction to produce a branched hydrocarbon having at least 28 carbon atoms.

The oligomerization reaction of step b) above can be performed under a catalyst, and the catalyst can be zeolite or clay.

The oligomerization reaction of step b) above can be performed under temperature conditions of 140 to 300°C.

The oligomerization reaction of step b) above can be performed using a batch reactor.

The above zeolite may be Y-zeolite having a SAR (Si/Al ratio) of 3 to 150, and the clay may be at least one selected from the group consisting of montmorillonite, illite, vermiculite, smectite, and kaolin.

The hydroisomerization reaction of step c) above can use a catalyst in the form of one or more metals selected from platinum (Pt), palladium (Pd), nickel (Ni), iron (Fe), copper (Cu), chromium (Cr), vanadium (V), and cobalt (Co) supported on one or more supports selected from alumina, silica, silica-alumina, zirconia, ceria, titania, zeolite, and clay.

The hydrogenation reaction of step c) above can be performed using a batch reactor or a fixed bed reactor.

The hydrogenation reaction of step c) above can be performed under conditions of a temperature of 140 to 400°C and a H ₂ pressure of 20 to 200 bar.

The lubricating oil containing the branched hydrocarbon having 28 or more carbon atoms may have a kinematic viscosity at 100°C of 3.3 cSt to 4.9 cSt, a viscosity index of 120 or more, a pour point of -30°C or less, a CCS (Cold Crank Simulation) viscosity at -35°C of 1700 cP or less, and a Noack volatility of 13.5 wt% or less.

According to the method for manufacturing a lubricating oil of one embodiment of the present invention, a low-viscosity, high-viscosity index lubricating oil having properties equivalent to or higher than those of conventional PAO lubricating oil can be manufactured at a high yield.

The method for manufacturing a lubricating oil according to one embodiment of the present invention uses an inexpensive linear alpha-olefin (LAO) having a C14 or higher content as a reaction raw material, so that an inexpensive linear alpha-olefin having a C14 or higher content can be increased in value.

Figure 1 exemplarily shows the mechanism of oligomerization reaction and hydroisomerization reaction in a method for producing lubricating oil according to one embodiment of the present invention.
Figure 2 shows the Simdist pattern (HT 750) of C14 LAO, C16 LAO, and C18 LAO used as raw materials in oligomerization example 1.
Figure 3 shows the simdist pattern of the product recovered through the oligomerization reaction of Oligomerization Example 1.
Figure 4 shows the XRD analysis results for the Y-zeolite of the faujasite type in oligomerization example 2.
Figure 5 shows the simdist pattern of the oligomerization product according to the SAR of the Y-zeolite of the faujasite type of oligomerization example 2.
Figure 6 shows the simdist pattern of the oligomerization product of Oligomerization Example 3.
Figure 7 shows the simdist pattern of the oligomerization product of Comparative Example 1.
Figure 8 shows the simdist pattern of a material that underwent the hydrogenation treatment of Example 2.

Throughout this specification, whenever a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated. Also, the singular includes the plural unless specifically stated otherwise in the phrase.

In this specification, “A to B” means “A or more and B or less” unless otherwise specifically defined.

In this specification, “lubricating oil” may typically mean a hydrocarbon having a boiling point of about 300° C. or higher (specifically, about 340 to 700° C.) and a viscosity of about 2 cSt or higher at 100° C.

The present invention relates to a method for producing a high-quality low-viscosity, high-viscosity index lubricating oil using a linear alpha-olefin (LAO) having a content of C14 or higher as a reaction raw material.

Specifically, one aspect of the present invention provides a method for producing a lubricating oil including a branched hydrocarbon having at least 28 carbon atoms, the method comprising the steps of: a) supplying a linear alpha-olefin having at least C14 carbon atoms or a mixture thereof; b) subjecting the linear alpha-olefin having at least C14 carbon atoms or the mixture thereof to an oligomerization reaction to produce an olefin-based oligomer having at least 28 carbon atoms and a boiling point of 330 to 500°C; and c) subjecting the olefin-based oligomer having at least 28 carbon atoms and a boiling point of 330 to 500°C to a hydroisomerization reaction to produce a branched hydrocarbon having at least 28 carbon atoms.

Step a): Supply of linear alpha-olefin (LAO) of C14 or higher or a mixture thereof

As the above C14 or higher LAO, specifically, one or more of C14 to C36 LAOs can be used, and more specifically, at least one selected from C14 LAO (1-tetradecene), C16 LAO (1-hexadecene), and C18 LAO (1-octadecene) can be used.

There is no particular limitation on the method for obtaining the LAO of C14 or higher as long as a method known to those skilled in the art is adopted, and it can also be purchased as a commercial product.

In particular, typically, C14 or higher LAO can be obtained from a full range LAO process which converts ethylene as a raw material into LAO, and branched and/or internal olefins can be generated as by-products of the full range LAO process. Known processes for manufacturing such full range LAO include the Chevron Phillips (or Gulf) process, the SHOP process, the INEOS process, and the Etyl process. Accordingly, C14 or higher LAO derived from the above-mentioned full range LAO can be supplied alone as a reaction raw material, but an embodiment in which the by-product branched and/or internal olefins are supplied in a mixture with C14 or higher LAO is also possible.

On the other hand, LAO can also be produced by (i) cracking of paraffin, (ii) dehydrogenation of paraffin, (iii) dehydration of alcohol, (iv) Fischer-Tropsch reaction, etc. Therefore, in some cases, LAO having a carbon content of C14 or higher or a mixture thereof derived from at least one of the reaction routes (i) to (iv) may be supplied as a reaction raw material.

Step b): Oligomerization Reaction

In step b) of the method for manufacturing a lubricating oil according to one embodiment of the present invention, an olefin oligomer having 28 or more carbon atoms and a boiling point of 330 to 500°C is produced by subjecting a C14 or higher LAO or a mixture thereof, which is a reaction raw material, to an oligomerization reaction.

Through the above oligomerization reaction, one or more of the above olefin oligomers containing double bonds can be produced.

The above olefin oligomer mainly includes dimers, and may additionally include a small amount of trimer or higher oligomers depending on the oligomerization reaction conditions. At this time, the dimer included in the olefin oligomer may specifically have an X-shaped structure, and for example, may have an X-type dimer structure having 28 or more carbon atoms represented by the following chemical formula 1, but is not limited thereto.

[Chemical Formula 1]

(In the above chemical formula 1, n is an integer greater than or equal to 1.)

The above olefin oligomer can ultimately provide improved low-temperature stability to the target lubricating oil due to its physical and chemical properties.

When applying LAO or a mixture thereof having C14 or higher as a reaction raw material to an oligomerization reaction, the position and number of double bonds in the reaction product can be controlled by controlling the reaction conditions. However, in the method for producing a lubricating oil according to one embodiment of the present invention, the reaction conditions such as the reaction catalyst, reaction temperature, and reaction time can be appropriately controlled so that the olefin oligomer can be produced in a high yield.

In producing the olefin-based oligomer through the oligomerization reaction in step b), the oligomerization reaction may be performed under a catalyst. The catalyst may specifically be zeolite or clay, and the use of such a catalyst may be advantageous in further improving the yield and selectivity of the olefin-based oligomer.

The above zeolite may be at least one selected from the group consisting of Y-zeolite, ZSM-5, and beta-zeolite, but is not necessarily limited thereto. The Y-zeolite may be specifically a Y-zeolite having a SAR (Si/Al ratio) of 3 to 150, more specifically a Y-zeolite having a SAR of 30 to 150, and even more specifically a Y-zeolite having a SAR of 50 to 150. In particular, when the SAR of the Y-zeolite is 50 to 150, it may be more advantageous in significantly improving the yield and selectivity of the olefin-based oligomer. In addition, the Y-zeolite may be a USY (ultra stable Y) zeolite or a Faujasite type Y-zeolite having a SAR in the above-described range, but is not limited thereto.

The above clay may be at least one selected from the group consisting of montmorillonite, illite, vermiculite, smectite, and kaolin, but is not necessarily limited thereto.

The amount of the above oligomerization reaction catalyst to be used may be 0.1 to 30 parts by weight per 100 parts by weight of LAO having C14 or higher or a mixture thereof, but is not necessarily limited thereto.

The oligomerization reaction of step b) can be performed under a temperature condition of 140 to 300°C, and specifically, can be performed under a temperature condition of 170 to 230°C. By performing the oligomerization reaction under the above temperature conditions, it may be advantageous to further improve the yield and selectivity of the olefin-based oligomer.

The oligomerization reaction time of step b) may be from 1 minute to 24 hours, specifically from 30 minutes to 10 hours, and more specifically from 1 hour to 6 hours.

The oligomerization reaction of step b) can be performed using a batch reactor.

Among the total oligomers of the oligomerization reaction of step b), the content of the olefin-based oligomer may be 10 to 100 wt%. In addition, the mole ratio of the olefin-based oligomer and other oligomers may be 1:0.5 to 1:0.001.

By the oligomerization reaction of step b), the yield of the olefin oligomer may be specifically 40% or more, more specifically 50% or more, and even more specifically 60% or more.

After the oligomerization reaction of step b), a step of selectively separating the olefin-based oligomer from the entire oligomer produced may be further included. There is no particular limitation on the separation method as long as a means known to those skilled in the art is adopted. For example, since the boiling point (bp) of the produced olefin-based oligomer is 330 to 500°C, it can be selectively separated by vacuum separation or fractional distillation.

Step c): Hydrogen isomerization ( Watershed branching ) reaction

In step c) of the method for producing a lubricating oil according to one embodiment of the present invention, the olefin oligomer produced in step b) is subjected to a hydroisomerization (hydrobranching) reaction to produce a branched hydrocarbon having 28 or more carbon atoms.

Through the above hydroisomerization reaction, the above branched hydrocarbon can be produced into one or more.

One of the important properties of lubricating oil is oxidation stability. The oxidation stability may refer to the degree of denaturation through combination with oxygen present in the air. Since combination with oxygen may cause discoloration and corrosion, the lubricating oil should not contain unsaturated double bonds. However, since olefin-based lubricating oil such as the above olefin-based oligomer is a substance produced through an oligomerization reaction of olefin, it inevitably contains unsaturated double bonds, and in order to be applied as a lubricating oil, the unsaturated double bonds inside the olefin can be saturated and eliminated with hydrogen ( _H2 ).

In the case of the above olefin oligomer, a double bond is contained in the molecular structure. Therefore, considering the oxidation stability of the final product, it is desirable to remove the double bond. To this end, the double bond can be saturated and removed by a hydrogenation reaction known to those skilled in the art.

However, in the method for manufacturing a lubricating oil according to one embodiment of the present invention, the unsaturated double bond is removed by a hydroisomerization reaction without carrying out a general hydrogenation reaction to remove the unsaturated double bond, and molecular branching (molecular lipidization) is also carried out at the same time.

In addition, the above olefin oligomer containing a double bond basically has high low-temperature stability, but since a molecular branching reaction is effective in improving the CCS properties, which are the main property criteria of high-quality lubricating base oil, a reaction is performed to improve the CCS properties of the lubricating base oil through a hydroisomerization reaction and simultaneously remove unsaturated double bonds.

The hydroisomerization reaction of step c) can use a catalyst used for a hydroisomerization reaction in a typical oil refining process without any particular limitation. For example, a catalyst in which at least one metal selected from platinum (Pt), palladium (Pd), nickel (Ni), iron (Fe), copper (Cu), chromium (Cr), vanadium (V), and cobalt (Co) is supported on a support selected from at least one of alumina, silica, silica-alumina, zirconia, ceria, titania, zeolite, and clay can be used. The zeolite can be, for example, a mesopore zeolite (for example, EU-1, ZSM-35, ZSM-11, ZSM-57, NU-87, ZSM-22, EU-2, EU-11, ZBM-30, ZSM-48, ZSM-23 or a combination thereof), but is not limited thereto. Additionally, the content of the metal component in the catalyst may be, for example, in a range of about 0.1 to 3 wt%, specifically about 0.3 to 1.5 wt%, and more specifically about 0.3 to 1 wt%.

Depending on the reaction temperature of the hydroisomerization reaction, the residual amount of unsaturated double bonds in the generated branched hydrocarbons may be high. Even if the residual amount of unsaturated double bonds is high, the "Saybolt color 30", which is a property standard of major lubricating base oils, can be satisfied, but if unsaturated double bonds remain, the basic properties such as CCS properties and oxidation stability deteriorate, so if necessary, a hydrogenation reaction commonly used can be added to remove the residual unsaturated double bonds.

The hydroisomerization reaction of step c) can be performed using a batch reactor or a fixed bed reactor, and preferably can be performed using a fixed bed reactor with high productivity. Specifically, the hydroisomerization reaction of step c) can be performed using a fixed bed reactor, and thus can be operated in a continuous manner. In this way, when a fixed bed reactor is used, the reaction can be performed under the supply of hydrogen gas, and an inert gas such as nitrogen, argon, and helium can be mixed and used to increase the reaction stability.

The flow rate of hydrogen gas introduced into the above-mentioned fixed bed reactor can be considered as one of the factors controlling the reaction activity. Specifically, since the reaction is carried out by contact between the catalyst and the reactant, the retention time can be considered in order to control the reaction. Meanwhile, the space velocity (WHSV) during the reaction using the fixed bed reactor can be controlled in the range of, for example, 0.01 to 50 hr ^-1 , specifically 0.1 to 3 hr ^-1 , and more specifically 0.5 to 1.5 hr ^-1 .

The hydroisomerization reaction of step c) can be performed under the conditions of a temperature of 140 to 400° C., and a H ₂ pressure of 20 to 200 bar. Specifically, the hydroisomerization reaction of step c) can be performed under the conditions of a temperature of 150 to 350° C., and a H ₂ pressure of 30 to 160 bar. By performing the hydroisomerization reaction under the above temperature and pressure conditions, it may be advantageous to further improve the yield of the branched hydrocarbon.

The branched hydrocarbon having 28 or more carbon atoms derived from the above olefin oligomer may have an X-shaped branched hydrocarbon structure represented by the following chemical formula 2, but is not limited thereto.

[Chemical formula 2]

(In the above chemical formula 2, n is an integer greater than or equal to 1.)

Carbon number Containing 28 or more branched hydrocarbons Lubricating oil

By the method for producing a lubricating oil according to one embodiment of the present invention, a lubricating oil containing a branched hydrocarbon having 28 or more carbon atoms is produced.

The above-mentioned lubricating oil may be composed solely of the branched hydrocarbon having a carbon number of 28 or more, or may contain the branched hydrocarbon having a carbon number of 28 or more and other substances together.

Since the branched hydrocarbon having 28 or more carbon atoms has a branched structure with higher steric hindrance in its chemical structure, it can exhibit improved stability against side reactions depending on the application compared to conventional lubricating oil materials with relatively low steric hindrance.

The lubricating oil containing the branched hydrocarbon having 28 or more carbon atoms may have a kinematic viscosity at 100°C of 3.3 cSt to 4.9 cSt, a viscosity index of 120 or more, a pour point of -30°C or less, a CCS (Cold Crank Simulation) viscosity at -35°C of 1700 cP or less, and a Noack volatility of 13.5 wt% or less.

Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are provided only to make it easier to understand the present invention and the present invention is not limited thereto.

[Oligomerization Example 1]

The raw materials, C14 LAO (1-tetradecene), C16 LAO (1-hexadecene), and C18 LAO (1-octadecene), were purchased as commercial products and used. To confirm the purity of the raw materials, GC-Simdist, GC-FID, and GC-MS analyses were performed, and it was confirmed that the purity was 95 wt% or higher.

Figure 2 shows the Simdist pattern (HT 750) of C14 LAO, C16 LAO, and C18 LAO used as raw materials.

Through the GC-FID (gas-chromatography flame-ionization-detector) analysis results of C14 LAO, the GC-area% of C14 LAO and byproducts is shown in Table 2 below. It was confirmed that the remaining impurities other than the C14 LAO raw material were isomers of C12 or C16 LAO.

C16 LAO and C18 LAO also contained adjacent LAO and branched olefins as byproducts, and the LAO purity was confirmed to be over 95%.

division GC-Area% (GC-FID) C12 LAO 0.41 C12 olefin isomer 0.74 C14 n-paraffin 0.28 C14 olefin isomer 2.12 C14 LAO 95.49 C16 olefin isomer 0.04 C16 LAO 0.91

160 g of C14 LAO and 640 g of C16 LAO were introduced into a 2 L 3-neck flask, and the oligomerization catalyst was sequentially introduced. The mixture was heated to the reaction temperature, stabilized at the reaction temperature, and maintained for the operation time. After completion of the reaction, the spent catalyst and oligomers (①) were separated and recovered through filtering. After that, the spent catalyst remaining in the filtering funnel was washed with n-heptane to recover the residual oligomers existing between the catalysts, and n-heptane and the residual oligomers (②) were separated through a rotary evaporator. The total oligomers (① + ②) were confirmed to confirm the recovery rate at the oligomer stage, and the selectivity was confirmed through Simdist analysis of the recovered oligomers to confirm the final oligomer yield.

Table 3 below shows the oligomerization catalytic activity in USY zeolite or clay. The middle product recovered in the range of 330-500℃ based on the boiling point includes an olefin dimer applicable to low-viscosity lubricating oil, and when 5 wt% of USY zeolite (SAR 86) was introduced, a middle product yield of 84 wt% was confirmed under the reaction conditions of 200℃ and 3 hours. When USY zeolite of SAR 12, which has a relatively low SAR (Si/Al ratio) and high catalytic acid point, was applied, the heavy product (bp>500℃) mainly including trimers or higher was confirmed to be relatively high even though a relatively small amount of catalyst was introduced, and it was confirmed that the yield of the target middle product (bp 330-500℃) rather decreased to 69 wt%.

As a clay catalyst, Montmorillonite 10K was purchased from Samsung Chemical and used. Although the conversion rate of the clay catalyst is lower than that of Y-zeolite, it was confirmed that more heavy products than trimers were generated and the yield of middle products was actually reduced, confirming that the characteristics of Y-zeolite were more advantageous.

The simdist pattern of the product recovered through the oligomerization reaction in Table 3 below is shown in Figure 3.

number
catalyst
Reaction conditions Yield (wt%) temperature
(℃) hour
(hr) Catalytic amount
(wt%) Middle
(bp 330-500℃) Heavy
(bp>500℃) Light
(bp<330℃) 1 USY Zeolite
(SAR 86) 180 3 3.5 57 37 6 2 200 3 3.5 69 20 11 3 200 3 5 84 11 5 4 USY Zeolite
(SAR 12) 200 3 3.5 69 20 11 5 USY Zeolite (SAR 6.2) 200 3 3.5 60 34 6 6 Clay 200 3 3.5 62 18 20

[Oligomerization Example 2]

In order to confirm the influence of SAR of Y-zeolite of Faujasite type, the oligomerization reaction activity was confirmed using Y-zeolite manufactured according to a specific SAR. 80 g of C14 LAO and 320 g of C16 LAO were introduced into a 1 L three-necked flask, and 20 g of Y-zeolite was introduced sequentially. The reaction temperature was then increased to 220°C and maintained for 3 hours after stabilization. After completion of the reaction, the recovery and analysis of the oligomerization product were carried out in the same manner as in Oligomerization Example 1.

The Y-zeolite catalyst used was confirmed to have a SAR (Silica Alumina ratio) through XRF analysis, and was confirmed to be a faujasite type Y-zeolite through XRD analysis, as shown in Fig. 4. The detailed properties of the catalyst used were confirmed through BET (Brunauer-Emmett-Teller) analysis, and are shown in Table 4 below.

SAR Surface area(m ² /g) Pore volume
(cc/g) Average pore diameter (Å) Total Micro- Meso/Macro 6.0 695.5 616.1 79.4 0.40 23.2 11.9 765.8 654.3 111.5 0.44 23.2 35.7 882.7 788.1 94.6 0.54 24.4 56.2 864.1 635.9 228.2 0.52 24.4 86.7 865.7 756.9 108.8 0.53 24.5

Through the following Table 5 and Figure 5, the oligomerization activity and the simdist pattern of the product according to the SAR of the Y-zeolite of the faujasite type are shown. As a result of the evaluation, it was confirmed that the higher the SAR of the Y-zeolite catalyst, the higher the yield of the middle product (bp 330-500℃) among the oligomerization products.

SAR Yield (wt%) Middle
(bp 330-500℃) Heavy
(bp>500℃) Light
(bp<330℃) 6.0 42 9 49 11.9 46 11 43 35.7 53 11 36 56.2 57 11 32 86.7 60 12 28

[Oligomerization Example 3]

C14 LAO (80 g) and C16 LAO (320 g) were introduced into a 1 L three-necked flask, and 20 g of USY zeolite (SAR 86) was sequentially introduced. The temperature was then increased to the reaction temperature, and after stabilization, it was maintained for 3 hours. After completion of the reaction, the recovery and analysis of the oligomer were performed in the same manner as in Oligomerization Example 1. Through simdist analysis of the recovered sample, the yield pattern of the product is expressed in Table 6 and Fig. 6 below. Through this, it was confirmed that the temperature range with the highest yield of the middle product (bp 330-500℃) that can be exclusively used as a low-viscosity lubricating oil was around 175℃ when USY zeolite (SAR 86) was applied.

Reaction temperature (℃) Yield (wt%) Middle
(bp 330-500℃) Heavy
(bp>500℃) Light
(bp<330℃) 170 70 15 15 175 74 13 13 180 71 13 16 200 66 16 18 220 56 15 29 240 50 14 36 260 50 14 36 280 49 12 39

[Comparative Example 1]

To confirm the effect of hydroisomerization treatment of olefin oligomers, the properties of lubricating oils manufactured by simply hydrofinishing the oligomers were confirmed using the following method.

C16 LAO 800g was introduced into a 2L autoclave, and USY zeolite (SAR 56.2) 40g was sequentially introduced, and then connected to the reactor. Thereafter, the mixture was stirred at 500 rpm, raised to a reaction temperature of 200℃ at a rate of 1℃/min, and then stabilized and maintained for 3 hours. After completion of the reaction, the product was allowed to settle, and only the upper oligomers were selectively recovered. Subsequently, in order to recover the oligomers present in the catalyst layer, the catalyst and oligomers were further separated through centrifugation, and the oligomers recovered through centrifugation and the oligomers recovered previously were combined to confirm the recovery rate. A total of 776.5 g of the oligomers recovered in this manner were recovered, and the recovery rate was confirmed to be 97 wt%. In order to confirm the conversion rate of the recovered oligomers and the yield of the middle product, simdist analysis was performed, and the results are shown in Fig. 7 and Table 7 below.

Yield (wt%) Middle
(bp 330-500℃) Heavy
(bp>500℃) Light
(bp<330℃) 71 16 13

The previously manufactured oligomers were classified by boiling point range through vacuum separation, and classified into Light (bp<330℃)/Middle (330-500℃)/Heavy (>500℃). Among these, the middle distillate was used as a raw material for the hydrogenation finishing reaction, and the catalyst used for the hydrogenation finishing reaction was OleMax 453 (containing 0.3 wt% of Pt and 0.6 wt% of Pd, a Clariant product).

Silica beads were filled in a fixed bed reactor, then wool was added, and 12 g of a catalyst was introduced on top of it. The catalyst was introduced by sieving (sieve no. 16-40) to be limited to a catalyst with an average diameter of about 1 mm. The catalyst was introduced into the center of the fixed bed reactor where the external temperature sensor and the internal temperature sensor were located. After the introduction of the catalyst, wool was similarly introduced on the catalyst layer, and then silica beads were filled. The reactor with the catalyst introduced was connected to the reaction system, and 192 sccm of H ₂ was introduced under the condition of H ₂ 50 psig, the temperature was increased at a rate of 1°C/min to 170°C, and then maintained at 170°C for 1 hour. Thereafter, the H ₂ pressure was increased to 50 bar, the temperature was increased at a rate of 1°C/min to 300°C, and then maintained for 2 hours. After that, the H ₂ pressure was lowered to 30 bar and 170℃, and the H ₂ flow rate was lowered to 129 sccm, and the previously recovered Middle product was introduced at a rate of 0.24 sccm. The samples from the first two days when the reactor stabilization was not complete were discarded, and the samples recovered after two days were collected to analyze the properties of the lubricating oil. The total yield was 99%, and there was almost no loss due to side reactions. The results of the property analysis of the lubricating oil are shown in Table 8 below.

Lubricating oil Comparative Example 1
PAO base oil GTL base oil Group Ⅲ Oil Lubricant oil properties Analysis method Tie point
(@100 ^o C, cSt) ASTM D445 4.26 4.1 4.08 4.25 Viscosity index ASTM D2270 134 126 130 124 CCS(@-35 ^o C, cP) ASTM D5293 1980 1426 1900 2900 Noak volatility, wt% ASTM D5800 7.9 14.0 12.1 14.5 Flow point, ^o C ASTM D97 -15 -66 -30 -15 Saybolt color. ASTM D156 30 30 30 30

The manufactured lubricating oil is superior to Group III base oil and can be considered a high-quality base oil at a level similar to GTL (gas to liquid) base oil. However, it is superior to PAO base oil only in terms of Noak volatility and inferior in terms of pour point and important properties such as CCS properties.

[Example 1]

The final lubricating oil was manufactured through a hydroisomerization (hydrobranching) reaction rather than a hydrofinishing reaction of an olefin oligomer, and its properties were confirmed. The catalyst used in the hydroisomerization reaction was a Pt/ZSM-48 catalyst (Exxonmobile HDW (hydrodewaxing) catalyst) containing 0.6 wt% of Pt.

The oligomer manufactured through No. 3 of Oligomerization Example 1 was classified by boiling point range through vacuum separation and classified into Light (bp<330℃)/Middle (330-500℃)/Heavy (>500℃). Among these, the middle product was used as a raw material to perform hydroisomerization (hydrobranching) reaction.

The hydroisomerization reaction treatment through the fixed bed reactor was carried out in the same manner as in Comparative Example 1, except that the catalyst was changed to a hydroisomerization catalyst and the reaction temperature was carried out at 260°C or higher. Similarly, the samples from the first two days when the reactor stabilization was not completed were discarded, and the samples recovered after two days were collected to perform a property analysis of the lubricating oil. The results of the property analysis of the lubricating oil are shown in Table 9 below.

Hydrogenation reaction temperature ( ^o C) 290 330 Yield (wt%) 90 55 Lubricant oil properties Analysis method Viscosity (@100 ^o C, cSt) ASTM D445 4.13 4.06 Viscosity index ASTM D2270 129 124 CCS(@-35 ^o C, cP) ASTM D5293 1560 1650 Noak volatility, wt% ASTM D5800 12.7 13.4 Flow point, ^o C ASTM D97 -39 -54 Saybolt color. ASTM D156 30 30

When the hydroisomerization reaction temperature was treated at 290℃, the kinematic viscosity was confirmed to be a low-viscosity lubricating oil of 4.13 cSt, and the viscosity index was 129 and the Saybolt color was 30, confirming that it had good properties for application as a lubricating oil. Furthermore, the Noack volatility was 12.7 wt%, and considering that the Noack volatility value of equivalent PAO is 13.5 wt%, it was confirmed that it had better lubricating oil properties. The CCS was 1560 cP, which was slightly inferior to the CCS of general PAO of 1450-1500 cP, but it was confirmed that there was no significant difference. The pour point was -39℃, which was inferior to the pour point of "-54℃ or less" of PAO with equivalent kinematic viscosity. However, the pour point of -39℃ is a relatively high property considering that the general lubricating oil property is "below -20℃", and it was confirmed that there is no problem in applying it as a high-quality lubricating oil. Through Table 10 below, the properties of the lubricating oil manufactured through Example 1 were compared with the properties of Comparative Example 1 and the conventional lubricating oil.

Lubricating oil Example 1 Comparative Example 1
PAO base oil GTL base oil Group Ⅲ Oil Lubricant oil properties Analysis method Tie point
(@100 ^o C, cSt) ASTM D445 4.13 4.26 4.1 4.08 4.25 Viscosity index ASTM D2270 129 134 126 130 124 CCS(@-35 ^o C, cP) ASTM D5293 1560 1980 1426 1900 2900 Noak volatility, wt% ASTM D5800 12.7 7.9 14.0 12.1 14.5 Flow point, ^o C ASTM D97 -39 -15 -66 -30 -15 Saybolt color. ASTM D156 30 30 30 30 30

It can be confirmed that the lubricating base oil manufactured through Example 1 has significantly improved CCS properties and pour point, which are important lubricating base oil properties, compared to Comparative Example 1, and in particular, it can be confirmed that the CCS properties are improved to a level similar to that of PAO base oil. In addition, although the pour point was inferior to that of PAO base oil, the Noack volatility was superior to that of PAO base oil, and the other properties were at similar levels. That is, it is confirmed that according to the method for manufacturing the lubricating base oil of Example 1, a high-quality lubricating base oil having properties equivalent to or higher than those of conventional PAO base oil can be manufactured at a high yield.

[Example 2]

A lubricating oil was manufactured using a mixture of C14 LAO and C18 LAO, and the properties of the lubricating oil were confirmed. For two raw materials, a mixture of 400 g of C14 LAO and 400 g of C18 LAO and a mixture of 440 g of C14 LAO and 360 g of C18 LAO, lubricating oils were manufactured and the properties were confirmed, respectively. The mixture of C14 LAO and C18 LAO was introduced into an autoclave, and 20 g of USY zeolite (SAR 86) was sequentially introduced. The manufacture and separation of the oligomerization product were carried out in the same manner as in Oligomerization Example 1, and the subsequent hydroisomerization treatment and confirmation of the properties of the lubricating oil were carried out in the same manner as in Example 1. At this time, for the middle product separated from the oligomerization product, the simdist pattern of the material that underwent hydroisomerization treatment at 290°C is as shown in Fig. 8. In addition, through Table 11 below, the properties of the lubricating oil manufactured through Example 2 were compared with the properties of the conventional lubricating oil.

Example 2 PAO base oil C14:C18 LAO ratio (wt%:wt%) 50:50 55:45 Total yield (wt%) 72 72 Lubricant oil properties Analysis method Tie point
(@100 ^o C, cSt) ASTM D445 4.31 4.15 4.1 Viscosity index ASTM D2270 131 120 126 CCS(@-35 ^o C, cP) ASTM D5293 1580 1470 1426 Noak volatility, wt% ASTM D5800 8.7 9.1 14.0 Flow point, ^o C ASTM D97 -37 -35 -66 Saybolt color. ASTM D156 30 30 30

It was confirmed that the lubricating oil manufactured through Example 2 did not differ significantly from the PAO base oil. The viscosity index was 120 or higher and the Saybolt color was 30, which satisfied the product standards, and the CCS property, which is the most important property, was at a similar level to the PAO base oil. The pour point was at the level of -37℃ to -35℃, which was inferior to the PAO base oil, but the Noack volatility was at the level of 8.7-9.1 wt%, which was superior to the PAO base oil. That is, it was confirmed that according to the method for manufacturing the lubricating oil of Example 2, a high-quality lubricating oil having properties equivalent to or higher than those of the conventional PAO base oil can be manufactured at a high yield.

Claims (9)

a) a step of supplying a linear alpha-olefin of C14 or higher or a mixture thereof;
b) a step of oligomerizing the linear alpha-olefin of C14 or more or a mixture thereof to produce an olefin oligomer having 28 or more carbon atoms and a boiling point of 330 to 500°C; and
c) a step of hydroisomerizing an olefin oligomer having 28 or more carbon atoms and a boiling point of 330 to 500°C to produce a branched hydrocarbon having 28 or more carbon atoms; a method for producing a lubricating oil containing a branched hydrocarbon having 28 or more carbon atoms,
A method wherein the oligomerization reaction of step b) is carried out under a catalyst, wherein the catalyst is Y-zeolite, ZSM-5, beta-zeolite or clay.
delete In the first paragraph,
A method in which the oligomerization reaction of step b) is performed under temperature conditions of 140 to 300°C. In the first paragraph,
A method in which the oligomerization reaction of step b) above is performed using a batch reactor. In the first paragraph,
A method wherein the above Y-zeolite is a Y-zeolite having a SAR (Si/Al ratio) of 3 to 150, and the clay is at least one selected from the group consisting of montmorillonite, illite, vermiculite, smectite, and kaolin. In the first paragraph,
The hydroisomerization reaction of step c) above is a method using a catalyst in the form of a support supported on at least one metal selected from platinum (Pt), palladium (Pd), nickel (Ni), iron (Fe), copper (Cu), chromium (Cr), vanadium (V), and cobalt (Co) selected from alumina, silica, silica-alumina, zirconia, ceria, titania, zeolite, and clay. In the first paragraph,
A method in which the hydrogenation reaction of step c) above is performed using a batch reactor or a fixed bed reactor. In the first paragraph,
A method in which the hydrogenation reaction of step c) is performed at a temperature of 140 to 400°C and a H ₂ pressure of 20 to 200 bar. In the first paragraph,
A method of producing a lubricating oil containing a branched hydrocarbon having 28 or more carbon atoms, wherein the lubricating oil has a kinematic viscosity of 3.3 cSt to 4.9 cSt at 100°C, a viscosity index of 120 or higher, a pour point of -30°C or lower, a CCS (Cold Crank Simulation) viscosity of 1700 cP or lower at -35°C, and a Noack volatility of 13.5 wt% or lower.