WO2020085832A1 - High-viscosity lubricant base oil manufacturing method - Google Patents

Abstract

The present invention relates to a lubricant base oil manufacturing method and can provide a lubricant base oil manufacturing method comprising the steps of: mixing an olefin mixture, comprising a branched alpha olefin and a branched internal olefin, with a linear alpha olefin so as to provide a feed; oligomerizing the feed so as for same to be converted to a substance having a kinematic viscosity of at least 20 cSt at 100°C; and hydrogenating the product obtained from the oligomerizing step.

Description

Manufacturing method of high viscosity lubricating base oil

The present invention relates to a method of manufacturing a high viscosity lubricating base oil, and more particularly, to a method of manufacturing a lubricating base oil having a high viscosity and a high viscosity index.

Lubricant refers to a substance used to reduce friction, and is expressed as a mixture of substances with various functions, or mainly a mixture of lubricant base oil and additives. Lubricating base oil is a material that corresponds to 80 ~ 90% of the majority of lubricant, and is the main material for determining the level of physical properties of lubricants. It is composed mostly of hydrocarbons, and the properties lacking lube base oil are corrected with the remaining 10 ~ 20% additive materials.

Lubricating base oil is composed of more than 98% of the total market using lubricating base oil composed of hydrocarbons, and is classified into API Group I ~ Group V according to the level of physical properties. Group V is Group I ~ Group containing oxygenated substances such as Ester. When defined as a substance other than IV, practically the highest quality base oil among hydrocarbon substances can be regarded as Group IV base oil, PAO.

PAO stands for Poly Alpha Olefin, and is a material obtained through oligomerization reaction and hydrogenation finishing reaction using C10 LAO (1-Decene) obtained through polymerization of ethylene. When using LAO raw materials of C8 or lower or C12 or higher, only C10 LAO is used as the raw material because it does not satisfy the main base oil properties such as viscosity index or pour point, and PA10 lubricating base oil derived from C10 LAO is compared to lubricating base oil derived from general oil It is incomparably high quality.

PAO is produced by mixing oligomers according to the degree of oligomerization after the oligomerization reaction of 1-Decene, and then mixing oligomers according to the kinematic viscosity, which has different uses in the market by kinematic viscosity, and generally the higher the average molecular weight, the higher the kinematic viscosity. It is recognized in the market as a product.

 Lubricating base oil products that exhibit characteristics of about 30 cSt or more based on kinematic viscosity (100 ° C) are collectively referred to as high-viscosity lube base oils, and these high-viscosity lube base oils have a smaller product volume than low-viscosity lube base oils, but the product price is high and mainly mixed with low-viscosity base oil Thus, it increases the thickness of the lubricating oil film during the friction driving process, thereby reducing friction, and consequently, it increases the raw material efficiency.

High-viscosity PAO is a high-quality lubricating base oil with a high price, and its application is clear, but the problem is that it is difficult to convert to a high-viscosity material, and thus the yield is low in the total quantity, and as a result, the quantity itself in the market is not large.

The market is compensating for this problem by using low-cost substitutes that can replace high-viscosity PAOs. There are currently two types of materials used as low-cost substitutes: one is a low-molecular-weight material generated in the polymer manufacturing process, and the other is a polyisobutene (PIB) produced by polymerizing isobuten generated in the cracking process of petroleum oil.

The low-molecular-weight material generated in the polymer manufacturing process can be applied as a high-viscosity PAO substitute material, but there is a disadvantage in that the yield is not high in the current polymer manufacturing technology. Of course, it is possible to increase the selectivity by targeting the low-molecular-weight material itself, but it is not preferred because it has low marketability (price, quantity, manufacturing economics, etc.) compared to the polymer, and only low-molecular-weight by-products generated during the polymer manufacturing process are applied as high-viscosity lubricants. It is doing.

In fact, the material used as a substitute for high-viscosity PAO on the market is PI I (Poly Isobutene). It is a polymer of isobutene generated from petroleum refining and petrochemical semi-finished products such as cracking process, and has a low product compared to PAO, and is widely used as a substitute for PAO. In order to further increase the economic efficiency of PIB products, in addition to isobutene, C4 low-cost olefins are mixed to produce high-viscosity PB (Poly Butene) and sold as products.

However, all of the low molecular weight by-products generated in the above-described polymer manufacturing process, or PIB or PB, include disadvantages in terms of product properties, which is that the viscosity index properties are relatively low.

Since heavy PAO is a material manufactured using C10 LAO as a raw material, the viscosity index of general products has a high viscosity index of 140 or higher. However, the low-molecular-weight material generated in the process of polymer production, but PIB does not exceed 100 because of the large number of twigs in the molecule. Particularly, in the case of PIB, due to the structural properties by polymerization of isobutene, there are many twigs, and due to these properties, the viscosity index of the product with a kinematic viscosity of 31 cSt (100 ° C) shows a low characteristic of 75.

High viscosity lubricating base oils with a kinematic viscosity (100 ° C) of about 30 cSt or more generally determine whether a product is available only with kinematic viscosity properties, but the viscosity index properties are very important. The viscosity index is a value obtained by converting the rate of change in dynamic viscosity between 40 ° C and 100 ° C through a calculation formula. The viscosity index indicates the rate of change of the kinematic viscosity of the lubricant base oil according to temperature, and the lubricant base oil having a small change in kinematic viscosity despite temperature changes is defined as a high-quality base oil, and the viscosity index is set high. It can be said that the smaller the difference in kinematic viscosity between 40 ℃ and 100 ℃, the larger the viscosity index is calculated.

High-viscosity lubricating base oils show high viscosity index properties, which means that the viscosity characteristics are small even with temperature changes, and considering the major lubricant base oil properties that determine price, such as CCS and volatility, are related to viscosity. It can be classified as lubricating base oil.

The alternatives of heavy PAOs currently on the market have a fatal problem that cannot replace the existing heavy PAOs in terms of viscosity index, which is a property of these important lubricant base oils.

In one aspect of the present invention, unlike conventional heavy PAO production methods or PIB production methods, a specific olefin mixture as a reaction raw material has a kinematic viscosity (100 ° C) of 20 cSt or more, more specifically 30 cSt or more, And it is intended to provide a method of manufacturing a lubricating base oil capable of producing a high viscosity and a high viscosity lubricating base oil having a viscosity index of 140 or more.

An aspect of the present invention comprises the steps of mixing an olefin mixture comprising a branched alpha olefin and a branched internal olefin, and a linear alpha olefin to provide a feed; Oligomerizing the feed to convert to a material with a kinematic viscosity at 100 ° C of 20 cSt or higher; And hydrogenating the product of the oligomerizing step.

The oligomerization step may be carried out at a temperature of 60 ℃ to 150 ℃.

The oligomerization step may be carried out at a temperature of 80 ℃ to 100 ℃.

In the step of providing the feed, 70% to 95% by weight of the olefin mixture including the branched alpha olefin and the branched internal olefin, and 5 to 30% by weight of the linear alpha olefin may be mixed. .

In the step of providing the feed, 85% to 90% by weight of the olefin mixture including the branched alpha olefin and the branched internal olefin, and 10 to 15% by weight of the linear alpha olefin may be mixed. .

The olefin mixture may contain 60% by weight or more of branched alpha olefins, based on 100% by weight.

The olefin mixture further includes a linear olefin, and the content of the branched internal olefin to the content of the linear olefin in the olefin mixture may be 1/1 or more.

The linear alpha olefin may include C12 or higher linear alpha olefin.

The linear alpha olefin may include C12 and C14 linear alpha olefins.

The lubricating base oil may have a viscosity index of 140 or more.

According to a method of manufacturing a lubricating base oil of one aspect of the present invention, a lubricating base oil having physical properties similar to that of a conventional Heavy PAO (kinematic viscosity (100 ° C) 20 cSt or more, more specifically 30 cSt or more, and 140 or more viscosity index) can be produced. You can.

Since the manufacturing raw material of the method for manufacturing a lubricating base oil of one aspect of the present invention is a process by-product or a low-cost material, it is possible to produce at a low cost, and is expected to replace the conventional high-viscosity lubricating base oil.

1 is a reaction scheme of a method of manufacturing a lubricating base oil in one aspect of the present invention.

2 is an exemplary process diagram of a method of manufacturing a lubricating base oil in one aspect of the present invention.

3 is a result of simdist analysis of the lubricant base oil prepared in Example 6.

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may be used as meanings commonly understood by a person having ordinary skill in the art to which the present invention pertains. When a part of the specification "includes" a certain component, this means that other components may be further included rather than excluding other components, unless specifically stated to the contrary. Also, the singular form includes the plural form unless otherwise specified in the phrase.

As used herein, "A to B" means "A or more and B or less" unless otherwise specified.

An aspect of the present invention comprises the steps of mixing an olefin mixture comprising a branched alpha olefin and a branched internal olefin, and a linear alpha olefin to provide a feed; Oligomerizing the feed to convert to a material with a kinematic viscosity at 100 ° C of 20 cSt or higher; And hydrogenating the product of the oligomerizing step.

Since lubricating base oil is a mixture, the quality of the product is determined based on the average physical properties in the mixture, so the properties that are insufficient depending on the degree of branching can be supplemented by mixing raw materials having two or more different degrees of branching. The present invention is to provide a method for preparing a high-viscosity and high-viscosity index lubricating base oil by mixing two or more different branching raw materials as a method for manufacturing a high-viscosity and high-viscosity index lubricant that has not been provided in the existing market.

In addition, according to the method of manufacturing a lubricating base oil according to an aspect of the present invention, main lubricating base oil properties such as viscosity index and pour point can be controlled by adjusting reaction conditions such as temperature and time during a polymerization reaction, and high viscosity and high viscosity index under specific conditions. Having, it can manufacture a high-viscosity lubricating base oil having a level of physical properties that can replace conventional PAO.

According to the method of manufacturing a lubricating base oil of one aspect of the present invention, a high viscosity (dynamic viscosity at 100 ° C. of 20 cSt or more, more specifically 30 cSt) from a mixture of an olefin mixture containing a branched alpha olefin and a branched internal olefin and a linear alpha olefin Or higher) and a high viscosity index (120 or higher, specifically 130 or higher, more specifically 140 or higher).

Lubricating base oils are usually classified by mechanical and chemical property standards prescribed by API as shown in Table 1 below, and according to the standards, the prepared base lubricants may correspond to API Group III or higher lubricant base oils.

In the conventional method for producing a high-viscosity lubricating base oil, a branched alpha olefin and a branched internal olefin and a linear alpha olefin are not mixed to control branching degree.

In the case of Heavy PAO, the existing product on the market is manufactured by using 1-decene (C10 LAO) material alone, and PIB (Poly Isobutene), which is easily applied as a substitute, was also used as Isobutene (iso-C4). In order to further increase the economic efficiency of PIB, polybutene is produced by using not only Isobutene, but also various C4 mixtures as raw materials, but in this case, it was difficult to be classified as a high-viscosity index lubricating base oil because the viscosity index did not exceed 100.

In one aspect of the present invention, by preparing a lubricating base oil from a raw material in which a linear alpha olefin is mixed with a branched alpha olefin and a branched internal olefin, a lubricating base oil having physical properties equivalent to a heavy PAO derived from C10 LAO as well as a kinematic viscosity is prepared. It provides a way to do it.

Provision of olefin mixtures comprising branched alpha olefins and branched internal olefins, and feeds comprising linear alpha olefins

According to one aspect of the present invention, branched alpha olefins, branched internal olefins, and linear alpha olefins can be obtained, for example, in a full range LAO process that converts ethylene into a linear alpha olefin as a raw material.

 Full range LAO is a process for producing linear alpha olefins by oligomerizing ethylene, and C4 to C40 linear alpha olefins are mainly produced depending on the polymerization degree of ethylene, C2. There are different uses depending on the size of the molecule. Mainly, C6 and C8 linear alpha olefins are used as copolymers for polymer production, and C10 linear alpha olefins are used as raw materials for high-quality lubricant base oil PAO. In addition, in the case of a linear alpha olefin having a relatively high molecular weight of C12 or more, it is difficult to convert to a lubricating base oil, and is mainly used for manufacturing a product having a relatively low consumption amount such as a solvent or wax and a low price.

In the method of manufacturing a lubricant base oil of one aspect of the present invention, the linear alpha olefin mixed as a raw material may be one containing C12 or higher linear alpha olefin. Specifically, it may include a C12 or more and C16 or less linear alpha olefin, and more specifically, a C12 or more and C14 or less linear alpha olefin. Preferably, it may be a mixture of C12 and C14 linear alpha olefins, but the present invention is not necessarily limited thereto.

By using such a linear alpha olefin as a raw material for manufacturing a lubricating base oil, the economic efficiency of manufacturing the lubricating base oil is improved according to the use of a low-cost raw material, and furthermore, it is possible to manufacture the lubricating base oil having the high viscosity and high viscosity index described above.

Olefin mixtures, including branched alpha olefins and branched internal olefins, occur as by-products in the full range LAO process, and usually less than 10 wt% of the material is produced as a by-product. Because it is a mixture of various olefins, not a single structured material, it is marketed as a low-cost material without special use.

On the other hand, in the cracking process, an olefin mixture including branched alpha olefin and branched internal olefin can be obtained. In the oil refining process, a large amount of olefin mixture can be recovered through the RFCC process. However, usually, C4-C20 branched alpha olefins and branched internal olefins can be obtained, and they contain a large amount of aromatics and naphthene, which limits their application to high-quality lubricant base oils.

As another example, an olefin mixture including branched alpha olefin and branched internal olefin may be recovered through the Fischer-Tropsch process. After converting the gas into a syngas mixture, its molecular weight is increased through its Fischer-Tropsch reaction. In this process, an olefin mixture including C6 to C20 branched alpha olefins and branched internal olefins is generated as a by-product.

By mixing the branched alpha olefin and the branched internal olefin and the linear alpha olefin, recovered in this way, it is possible to secure the raw materials for the method of manufacturing the lubricating base oil of one aspect of the present invention.

On the other hand, in the method of manufacturing a lubricant base oil of one aspect of the present invention, in the step of providing the feed, 70% to 95% by weight of the olefin mixture including the branched alpha olefin and the branched internal olefin, and the linear alpha olefin 5 It may be to be mixed by weight to 30% by weight.

More specifically, 80% to 90% by weight of the olefin mixture comprising the branched alpha olefin and the branched internal olefin, and 10% to 20% by weight of the linear alpha olefin, and more specifically the branched alpha olefin and The olefin mixture containing the branched internal olefin may be a mixture of 85% to 90% by weight and 10% to 15% by weight of the linear alpha olefin.

When mixing in such a range, it may be good to be able to manufacture a lubricating base oil having a viscosity index of 100 c kinematic viscosity of 30 cSt or higher and 140 or higher in high yield.

In addition, the olefin mixture comprising the branched alpha olefin and the branched internal olefin may contain 60% by weight or more of the branched alpha olefin relative to 100% by weight. When this range is satisfied, it may be good to be able to manufacture a lubricating base oil having a viscosity index of 30 cSt or higher and a viscosity index of 140 or higher at 100 ° C with high yield. More specifically, it may be 70% by weight or more, or 80% by weight or more.

Further, the olefin mixture further includes a linear olefin, and the content of the branched internal olefin (branched internal olefin / linear olefin) with respect to the content of the linear olefin in the olefin mixture may be 1/1 or more. If this range is satisfied, it may be good to be able to manufacture a lubricating base oil having a viscosity index of 30 cSt or higher and a viscosity index of 140 or higher at 100 ° C with high yield. More specifically, it may be 2/1 or more.

In addition, the olefin mixture may more specifically include a branched alpha olefin, a branched internal olefin, a linear alpha olefin, and a linear internal olefin, and these are 80% by weight or more, more than 100% by weight of the total olefin mixture Specifically, it may contain 90% by weight or more.

Meanwhile, the number of carbon atoms of the olefins included in the olefin mixture may be C4 to C30, specifically C8 to C20, and more specifically C12 to C18.

Oligomerization reaction

In the method for preparing a lubricating base oil of one aspect of the present invention, an oligomerization reaction may be applied to the feed described above to convert it into a high-viscosity olefin-based lubricating base oil containing a double bond.

In the method for preparing the lubricating base oil of one aspect of the present invention, as the catalyst used in the oligomerization reaction, a cationic polymerization catalyst, a metallocene catalyst, a homogeneous acid catalyst such as AlCl ₃ , BF ₃ , etc. may be used, and preferred For example, a metal halide catalyst such as AlCl ₃ can be used.

The oligomerization reaction generally proceeds at a temperature of 60 ° C. or lower, but in this case, due to the steric hindrance due to polymerization of the branched alpha olefin and the branched internal olefin and the linear alpha olefin, it is at a high viscosity material level. The transition becomes difficult. For this reason, in one aspect of the present invention, the reaction may be performed at a temperature of 60 ° C to 150 ° C. More specifically, the reaction may be performed at a temperature of 80 ° C to 120 ° C, 90 ° C to 110 ° C, 60 ° C to 100 ° C, or 80 ° C to 100 ° C.

When the reaction temperature is too low, a lubricating base oil having a kinematic viscosity of less than a high viscosity criterion with a kinematic viscosity (100 ° C) of 10 to 20 cSt is produced. In the reaction process, a high exothermic phenomenon occurs. In a condition in which the reaction temperature is too high, the amount of heat generated is too large, which makes it difficult to control the temperature and is very dangerous, and it may be difficult to produce a reproducible material due to the side reaction.

If the reaction temperature is too high, the viscosity index of the lubricating base oil to be produced may be lowered.

It is preferably performed at a temperature of 80 ° C. to 100 ° C., since it can produce a lubricating base oil having a high viscosity of 30 cSt or higher and a high viscosity index of 140 or higher.

The oligomerization reaction can be carried out for 1 minute to 24 hours, specifically 30 minutes to 5 hours, more specifically 1 hour to 3 hours.

In addition, the oligomerization reaction may be carried out in a continuous manner (for example, using a CSTR reactor), in which case the space velocity (WHSV) is 0.01hr ^-1 to 10hr ^-1 , specifically 0.1hr ^-1 to 5hr ^-1 Range.

After the oligomerization reaction, the catalyst cannot be regenerated and used, but in the case of a gas type catalyst such as BF ₃ , partial recovery is possible through condensation of the gas catalyst.

The recovered oligomerization reaction can be stirred with water to remove the AlCl ₃ catalyst component in the oligomer. Whether or not the catalyst component remains in the oligomer is confirmed by analyzing the chlorine component in the layered water layer after stirring, and can be washed with excess water until no chlorine component is detected.

The reactant from which the catalyst component has been removed may be placed in a dryer such as a desiccator or dried in an oven to remove residual water in the oligomer.

Hydrofinishing

In the method for preparing a lubricant base oil of one aspect of the present invention, the olefin-based lubricant base oil produced by the above-described oligomerization reaction contains a double bond in the molecular structure. When considering the oxidation stability of the final product, it may be desirable to remove the double bond. To this end, the double bond may be saturated and removed by a hydrogenation finishing reaction known in the art.

One of the important properties of lubricating base oil is oxidation stability. The oxidative stability may mean a degree of denaturation through bonding with oxygen present in air. When combined with oxygen, it should not only discolor, but also cause corrosion, so there should be no unsaturated double bond in the lubricating base oil.

However, since the olefin-based lubricating base oil is a material generated through the oligomerization reaction of the olefin, it inevitably contains an unsaturated double bond, and in order to apply it as a lubricating base oil, hydrogen (H ₂ ) saturates the unsaturated double bond inside the olefin. Can be removed.

In the hydrogenation finishing reaction, a catalyst used for the hydrogenation finishing reaction in a normal oil refinery process may be used without particular limitation. Specifically, as a hydrogenated metal, a metal selected from Groups 8, 9, 10, 11 and 12 on the periodic table, more specifically platinum (Pt), palladium (Pd), nickel (Ni), iron (Fe), One or more metals selected from copper (Cu), chromium (Cr), vanadium (V) and cobalt (Co) can be used. More specifically, platinum (Pt), palladium (Pd) or alloys thereof can be used.

In addition, inorganic oxide supports, specifically alumina, silica, silica-alumina, zirconia, ceria, titania, zeolite (e.g., Y zeolite (specifically, SAR of about 12 or more)), clay, SAPO and AlPO, etc. The above selected support can be used by supporting the metal.

The hydrogenation finishing reaction conditions are, for example, a reaction temperature of 150 ° C to 500 ° C (specifically, 180 ° C to 350 ° C, more specifically 200 ° C to 350 ° C), and a hydrogen (H ₂ ) pressure of about 5 bar to 200 bar (more specifically As 20bar to 180bar), GOR (H ₂ / feed ratio) may be in the range of about 300N㎥ / ㎥ to 2000N㎥ / ㎥ (more specifically 500N㎥ / ㎥ to 1500N㎥ / ㎥).

In addition, in the continuous mode (for example, using a CSTR reactor), the space velocity of 0.1hr ^-1 to 5hr ^-1 , specifically 0.1hr ^-1 to 3hr ^-1 , and more specifically 0.1hr ^-1 to 1hr ^-1 (WHSV).

As described above, the kinematic viscosity (100 ° C) of 20 cSt or higher, more specifically 30 cSt or higher, and a viscosity index of 140 or higher from the mixture of olefin mixtures containing branched or internal olefins and a mixture of linear alpha olefins by the above method And a high viscosity index lubricating base oil.

Hereinafter, preferred embodiments are provided to help understanding of the present invention, but the following examples are provided only to more easily understand the present invention and the present invention is not limited thereto.

[Production Example 1]

A by-product of the LAO manufacturing process for use as a lubricant base oil manufacturing material was secured. Specifically, the obtained olefin by-products were subjected to component analysis through GC-FID and 2D-GC analysis, and the component ratios according to the number of carbons and olefin types are summarized in Table 2.

In addition, C10 and C12 components of the by-products were classified into branched alpha olefin, branched internal olefin, linear alpha olefin, and linear internal olefin, Table 3 shows the analyzed results. C10 and C12 components consist of about 80 to 90% by weight of branched olefins, 4 to 12% by weight of linear olefins, and 2 to 7% by weight of naphthene and paraffin components And it was found.

[Comparative Example 1]

Lubricated base oil was prepared as a by-product obtained in the step of Preparation Example 1.

Specifically, 100 g of a by-product of Preparation Example 1 was added to an autoclave of 250 cc, and the temperature was raised to 40 ° C by raising the temperature. After that, an additional oligomerization catalyst, AlCl ₃ (Aldrich) 10g, was added to proceed with the oligomerization reaction. After the catalyst was added, the autoclave was automatically temperature controlled through a chiller so that the accelerated reaction due to rapid reaction heat did not proceed.

The stirring speed was gradually increased so that the reaction temperature could be maintained at 40 ° C, and the stirring speed was increased to a final 800 rpm. The reaction was maintained for 3 hours after the start of the reaction.

After the reaction was completed, 50 cc of water was introduced through the inlet, and the stirring speed was changed to 300 rpm and maintained for 30 minutes. After that, the autoclave reactor was opened to recover a mixture of reactants and water, and then the remaining material on the reactor wall was washed with n-heptane and recovered together.

The recovered material was separated by separating the organic layer and the water layer through a separatory funnel and then selectively removing the chlorine concentration in the water layer. Then, after adding 50 cc of water and stirring at 300 rpm, the water layer is selectively separated through a separatory funnel, the internal chlorine concentration is analyzed by ICP, and then the process is repeated until the chlorine concentration is 1 ppm or less. Was removed.

The reactant of the organic layer recovered through this was distilled under reduced pressure to selectively remove n-heptane in the organic material. The reduced pressure was reduced to 10 mbar at room temperature to selectively remove n-heptane in the organic layer. The amount of reactants recovered through this was 93.7 g.

The hydrogenation finishing reaction was carried out in a CSTR reactor using a PtPd / SiO ₂ -Al ₂ O ₃ catalyst. The reaction was performed under reaction conditions of 200 ° C, H ₂ pressure 30 bar, space velocity (WHSV) 0.5 hr ^-1 and GOR (H ₂ / feed ratio) 1000 Nm ³ / m ³ , to selectively remove double bonds in the reaction product Did.

Then, distillation under reduced pressure was performed to remove unreacted raw materials. The distillation under reduced pressure was performed at 176 ° C and 3 mbar operating conditions, and the weight of the material recovered after distillation under reduced pressure was measured to derive a final yield.

The final recovered product was checked for the boiling point distribution of the mixture through a high temperature simdist (HT-750). In order to check the properties as a lubricating base oil, the kinematic viscosity at 40 ° C and 100 ° C was checked and the viscosity index was calculated through this, and the pour point was measured to check the low-temperature lubrication properties. This is summarized in Table 4. To compare the properties of the lubricating base oil, the properties of commercial PAO products and PIB products were compared.

[Comparative Example 2]

The oligomerization reaction was the same as in Comparative Example 1, except that the reaction temperature was performed at 50 ° C.

[Comparative Example 3]

The oligomerization reaction was the same as in Comparative Example 1, except that the reaction temperature was performed at 60 ° C.

[Comparative Example 4]

The oligomerization reaction was the same as in Comparative Example 1, except that the reaction temperature was performed at 100 ° C.

As can be seen from Table 4 above, it was confirmed that when the catalyst was introduced at an excess of 10 wt%, a high viscosity material having a kinematic viscosity (100 ° C) of 30 cSt or higher was generated at a reaction temperature of 60 ° C or higher. When the reaction temperature was as low as 40 ° C, it was confirmed that 30 wt% of unreacted raw materials remained and the kinematic viscosity (100 ° C) was low at 12.7 cSt even though it was an AlCl ₃ catalyst having a very high reaction activity and proceeding in a batch reactor.

The prepared material is a material having a viscosity index of 112 to 119 level, a base oil of API Group II level, and confirmed that the pour point is lower than -50 ℃.

In the case of Comparative Example 3 and Comparative Example 4, the kinematic viscosity (100 ° C.) is 30 cSt or more, and it is expected to be applicable as a high-viscosity lubricating base oil because the viscosity index is superior when compared with commercial PIB products.

However, in order to be classified into a general high-viscosity and high-viscosity index lubricating base oil, properties of a lubricating base oil having a viscosity index of 140 or higher are required.

[Example 1]

In the step of Preparation Example 1, a lubricating base oil was prepared using a mixture of by-products and a linear alpha olefin.

Specifically, a by-product of Preparation Example 1, C14 linear alpha olefin, and 100 g of a mixture were added to an autoclave of 250 cc. The C14 linear alpha olefin mixing ratio was 5 wt%, and was prepared by mixing 95 g of a by-product of Preparation Example 1 and 5 g of C14 linear alpha olefin.

After that, the temperature was raised and the temperature was raised to 60 ° C. After that, an additional oligomerization catalyst, AlCl ₃ (Aldrich), 10 g was added, and a lubricating base oil was prepared in the same manner as in Comparative Example 1. The results of the yield and physical properties analysis through the experiment are shown in Table 5 below.

[Example 2]

The same as in Example 1, except that the C14 linear alpha olefin mixing ratio of Example 1 was increased to 10 wt%.

[Example 3]

The C14 linear alpha olefin mixing ratio of Example 1 is increased to 10 wt%, and is the same as in Example 1, except that the reaction temperature is performed at 80 ° C.

[Example 4]

The C14 linear alpha olefin mixing ratio of Example 1 is increased to 15 wt%, and is the same as in Example 1, except that the reaction temperature is 80 ° C.

[Example 5]

The C14 linear alpha olefin mixing ratio of Example 1 is increased to 20 wt%, and is the same as in Example 1, except that the reaction temperature is performed at 80 ° C.

[Example 6]

It was the same as in Example 3, except that the reaction temperature was 100 ° C.

[Example 7]

It was the same as in Example 3, except that the reaction temperature was 120 ° C.

[Example 8]

The same as in Example 1, except that the linear alpha olefin of Example 1 was replaced with a linear alpha olefin mixture of C12 and C14 (wt: wt = 1: 1).

As can be seen in Table 5 above, when a small amount of C14 linear alpha olefin mixture was introduced in a small amount of about 5 wt% (Example 1), it was confirmed that the viscosity index rose to 125 from the existing 120 or lower level. When the mixing ratio of the C14 linear alpha olefin was increased to 10 wt% (Example 2), the viscosity index increased significantly to a similar level of 140. However, as the C14 linear alpha olefin mixing ratio increased, the molecular weight increase reaction activity was lowered to the high-viscosity lubricating base oil, and the kinematic viscosity was significantly lowered to 22.2 level, and the yield was lowered.

When the C14 linear alpha olefin is mixed at 10 wt% or more, if the reaction temperature is 80 ° C or higher (Examples 3 to 6), the kinematic viscosity (100 ° C) and viscosity index are about 30 cSt, 140 or higher, respectively, and high viscosity and It was confirmed that the high-viscosity index lubricating base oil conditions were met.

It was confirmed that the pour point and the yield decreased as the C14 linear alpha olefin mixing ratio increased, thereby increasing the reaction temperature to compensate.

When the reaction temperature is increased to 100 ° C. under a C14 linear alpha olefin mixing ratio of 10 wt% (Example 6), the kinematic viscosity is 30 cSt or higher, and the viscosity index is 140 or higher, and the lubricating base oil having a pour point of −20 ° C. or lower is satisfied. Was confirmed. As a result of Simdist analysis, it was confirmed that a substance having a temperature of 500 ° C. or higher based on a boiling point was 95% or higher, and the detailed pattern was expressed in FIG.

On the other hand, when the C14 linear alpha olefin mixing ratio is 10wt% to 15wt%, and the reaction temperature is 80 ° C to 100 ° C (Example 3, Example 4, and Example 6), a high viscosity of 30 cSt or higher and 140 or higher It was possible to prepare a lubricating base oil having a viscosity index.

On the other hand, when the reaction temperature is increased to 120 ° C, the kinematic viscosity at 100 ° C is about 20 cSt, the viscosity index is about 120, and a high viscosity and high viscosity index lubricating base oil cannot be prepared.

All simple modifications or changes of the present invention belong to the scope of the present invention, and the specific protection scope of the present invention will be clarified by the appended claims.

Claims (10)

Mixing an olefin mixture comprising a branched alpha olefin and a branched internal olefin, and a linear alpha olefin to provide a feed; Oligomerizing the feed to convert to a material with a kinematic viscosity at 100 ° C of 20 cSt or higher; And Hydrogenating the product of the oligomerization step; lubricating base oil production method comprising a. In claim 1, The step of oligomerization, A method of manufacturing a lubricating base oil, performed at a temperature of 60 ° C to 150 ° C. In claim 2, The step of oligomerization, A method of manufacturing a lubricating base oil, performed at a temperature of 80 ° C to 100 ° C. In claim 1, In the step of providing the feed, 70% to 95% by weight of an olefin mixture comprising the branched alpha olefin and the branched internal olefin, and The linear alpha olefin 5 to 30% by weight of the mixture, lubricating base oil production method. In claim 3, In the step of providing the feed, 85% to 90% by weight of an olefin mixture comprising the branched alpha olefin and the branched internal olefin, and The linear alpha olefin is 10 to 15% by weight of the mixture, the lubricating base oil production method. In claim 1, The olefin mixture, A method of manufacturing a lubricating base oil that contains 60% by weight or more of a branched alpha olefin based on 100% by weight. In claim 1, The olefin mixture further comprises a linear olefin, the content of the branched internal olefin relative to the content of the linear olefin in the olefin mixture is 1/1 or more, the method of manufacturing a lubricating base oil. In claim 1, The linear alpha olefin, A method of manufacturing a lubricating base oil comprising C12 or higher linear alpha olefin. In claim 8, The linear alpha olefin, A method of manufacturing a lubricating base oil comprising linear alpha olefins of C12 and C14. In claim 1, The lubricant base oil, A method of manufacturing a lubricating base oil having a viscosity index of 140 or more.

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