TW201930575A - Lubricant compositions having improved low temperature performance - Google Patents

Abstract

Disclosed are lubricant compositions prepared with Group III base stocks comprising greater than or equal to about 90 wt. % saturated hydrocarbons (saturates); a viscosity index from 120 to 145; a unique ratio of molecules with multi-ring naphthenes to single ring naphthenes (2R+N/1RN); and a unique ratio of branched carbons to straight chain (BC/SC) carbons; a unique ratio of branched carbons to terminal carbons (BC/TC); and unique MRV behavior as a function of base stock naphthene ratio (2R+N/1RN).

Description

Lubricant composition with improved low temperature performance

This disclosure relates to a lubricant composition formulated with a unique Group III base oil and these base oil mixtures.

The base oil is the main component of the finished lubricant and contributes greatly to the properties of the lubricant. For example, engine oil is a finished crankcase lubricant used in automobile engines and diesel engines, and contains two general ingredients, namely base stock (base stock or base oil) (a base oil or a mixture of base oils) And additives. Generally, some lubricating base oils are used to make various engine oils by changing the mixture of individual lubricating base oils and individual additives.

According to the American Petroleum Institute (API) classification, base oils are divided into five categories based on their saturated hydrocarbon content, sulfur content, and viscosity index (Table 1). Lubricating oil base oils are typically manufactured on a large scale from non-renewable petroleum sources. Group I, II, and III base oils are all derived from crude oil and undergo extensive processing, such as solvent extraction, solvent or catalytic dewaxing, and hydroisomerization. Group III base oils can also be manufactured from synthetic hydrocarbon liquids derived from natural gas, coal, or other fossil resources. Group IV base oils are polyalphaolefins (PAO) and are derived from It is produced by oligomerization of alkene). Group V base oils include all base oils that do not belong to Groups I-IV, such as naphthenic, polyalkylene glycols (PAG), and esters.

Base oils are usually prepared from higher boiling fractions recovered from vacuum distillation operations. They can be prepared from petroleum-derived or syncrude-derived raw materials or from the synthesis of lower molecular weight molecules. Additives are chemicals added to base oils to improve certain properties of finished lubricants so that they meet the minimum performance standards for finished lubricant grades. For example, additives added to the engine oil can be used to improve the oxidative stability of the lubricant, increase its viscosity, increase the viscosity index, and control deposits. Additives are expensive and may cause miscibility issues in the finished lubricant. For these reasons, it is often desirable to optimize the additive content of motor oil to the minimum amount required to meet appropriate requirements.

Due to the need to improve quality, the formula is being changed. For example, regulatory organizations (such as the American Petroleum Institute) help define the specifications of motor oil. More and more engine oil specifications require products with excellent low temperature properties and high oxidation stability. Currently, only a small portion of the base oil mixed into the engine oil meets the most demanding engine oil specifications. Currently, formulators are using a series of base oils, including Group I, II, III, IV, and V base oils, to formulate their products.

Industrial oils are also required to improve the oxidative stability, cleanliness, interface properties and quality of sediment control.

Despite advances in the technology of lubricating base oils and lubricant formulations, there is still a need to improve the oxidation performance of formulated oils (for example, for engine oils and industrial oils with longer life) and low temperature performance. In particular, there is a need to improve the oxidation performance and low temperature performance of formulated oils without adding more additives to the lubricant formulation.

This disclosure is about a formulated lubricant composition containing a unique Group III base oil and mixture.

This disclosure part relates to a lubricating composition prepared with a Group III base oil having a Kinematic Viscosity at 100 ° C of greater than 2 cSt, such as from 2 cSt to 14 cSt or more, such as from 2 cSt to 12 cSt and from 4 cSt to 7cSt. These base oils are also referred to as lube base oils or products in this disclosure. In one embodiment, the present disclosure provides a lubricating composition, which includes a Group III base oil having: at least 90 wt% saturated hydrocarbons; a kinematic viscosity at 100 ° C (KV100) of 4.0 cSt to 12.0 cSt; viscosity index 120 to 133; ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.43; and an effective amount of one or more lubricant additives.

In another embodiment, the present disclosure provides a passenger car engine oil composition, which includes a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbons; the kinematic viscosity at 100 ° C is as high as 4.0 cSt Up to 5.0 cSt; viscosity index from 120 to less than 140; ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) less than 0.45; and an effective amount of one or more lubricant additives.

In another embodiment, the present disclosure provides a heavy-duty diesel engine lubricating oil composition, which includes a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbon; the kinematic viscosity at 100 ° C is from 5.5cSt up to 7.0cSt; viscosity index from 120 to less than 144; ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) less than 0.56; and effective amount of one or more lubricant additives.

In another embodiment, the present disclosure provides a lubricating composition including a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbon; a kinematic viscosity at 100 ° C of 4.0 cSt to 5.0 cSt ; The viscosity index is 120 to 140; the ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.52; the ratio of branched carbon to linear carbon (BC / SC) is less than or equal to 0.23; and effective Amount of one or more lubricant additives.

In another embodiment, the present disclosure provides a lubricating composition including a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbon; a kinematic viscosity at 100 ° C of 5.0 cSt to 12.0 cSt ; The viscosity index is 120 to 140; the ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.59; the ratio of branched carbon to linear carbon (BC / SC) is less than or equal to 0.26; Amount of one or more lubricant additives.

In another embodiment, the present disclosure provides a lubricating composition prepared with a base oil having a ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) less than 0.59 and branched carbon to the terminal The ratio of carbon is less than 2.6.

In another embodiment, the present disclosure provides a lubricating composition including a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbon; a kinematic viscosity (KV100) at 100 ° C of 5.0 cSt To 12.0 cSt; viscosity index 120 to 144; ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) less than 0.56; and effective amount of one or more lubricant additives.

A method of manufacturing diesel fuel and a Group III base oil can be used to obtain a Group III base oil used to prepare the lubricant composition of the present disclosure. Generally, through the first stage (which is mainly a hydrogen treatment unit that raises the viscosity index (VI) and removes sulfur and nitrogen), the raw materials (eg, oil-fed viscosity index (solvent with solvent dewaxing) are fed dewaxed oil feed viscosity index) is from about 45 to about 150 heavy vacuum gas oil feed stock (heavy vacuum gas oil feed stock) or mixed feedstock with solvent dewaxing oil feed viscosity from about 45 to about 150. The next part is the stripping part, where the light end and diesel are removed. Then the heavier lubricating oil fraction enters the second stage, in which hydrocracking, dewaxing and hydrofinishing are carried out. This combination of treatment methods produces base oils with unique compositional characteristics. These unique compositional characteristics are observed in the low, medium and high viscosity base oils produced.

From the following detailed description, other purposes and advantages of the present disclosure will become apparent.

All numerical values in the detailed description and patent application in this article are modified to "approximately" or "approximately" indication values, and consider experimental errors and variations known to those skilled in the art.

As used herein, the term "main ingredient" refers to an amount of an ingredient (eg, base oil) present in the lubricating oil of the present disclosure that is greater than 50 weight percent (wt%).

As used herein, the term "secondary component" refers to the amount of components (eg, one or more lubricating oil additives) present in the lubricating oil of the present disclosure that is less than 50 weight percent.

As used herein, the term "monocyclic cycloalkane" refers to a saturated hydrocarbon having the general formula C _n H _2n, which is arranged in the form of a single closed loop, where n is the number of carbon atoms. It is also referred to as 1RN in this article.

As used herein, the term "polycyclic cycloalkane" refers to a saturated hydrocarbon group _{H 2 (n + 1-r} ) having the formula C _n, a plurality of which are arrayed in the form of a closed loop, where n is the number of carbon atoms, and r Is the number of rings (in this article, r> 1). It is also referred to herein as 2 + RN.

As used herein, the term "kinematic viscosity at 100 ° C" will be used interchangeably with "KV100", and "kinematic viscosity at 40 ° C" will be used interchangeably with "KV40". The two terms should be considered equal.

As used herein, the term "linear carbon" refers to the sum of α, β, γ, δ, and ε peaks measured by ¹³ C nuclear magnetic resonance (NMR) spectroscopy.

As used herein, the term “branched carbon” refers to the sum of pendant methyl, pendant ethyl, and pendant propyl measured by ¹³ C NMR.

As used herein, the term "terminal carbon" refers to a terminal methyl group, a terminal ethyl group, and a terminal propyl group measured by ¹³ C NMR.

Lubricating base oil

According to the present disclosure, a lubricating composition (eg, engine lubricating oil composition) having certain kinds of paraffin molecules is provided. The inventor of the present invention was surprised to find that a lubricant composition prepared by a method described herein using a base oil having a low ratio of 2R + N / 1RN and / or less branched carbon, such as those manufactured, shows an improvement Low temperature viscosity properties. Lower levels of 2R + N molecules and branched carbon materials are ideal in lubricant compositions because high levels of 2R + N molecules and branched carbon materials can impede the low-temperature performance of formulated oils, such as low-temperature viscosity. In particular, the lubricating composition of the present disclosure has improved oxidation performance compared to conventional lubricants, especially at low temperatures. For example, the oxidative performance of the formulated base oil of the present disclosure (using CEC-L-85 or ASTM D6186) shows an improvement of 10-100 times compared to lubricants prepared with base oils that are currently commercially available. For example 20-50 times, for example 30-40 times.

According to various embodiments of the present disclosure, the base oil used in the lubricating composition of the present disclosure is API Group III base oil. The Group III base oil of the present disclosure can be manufactured by an advanced hydrocracking process using the following raw materials: for example, the oil feed viscosity index with solvent dewaxing is at least 45 (for example at least 55, for example at least 60 up to 150 , Or 60 to 90) of vacuum gas oil feedstock) or oil feed with solvent dewaxing viscosity index of at least 45 (such as at least 55, such as at least 60 to about 150, or 60 to 90) heavy vacuum gas oil and heavy Heavier atmospheric gas oil mixed feed stock. Group III is at least 45, such as at least 55, such as at least 60 to 150, or 60 to 90. The Group III base oil of the present disclosure may have Kinematic viscosity is greater than 2cSt, such as from 2cSt to 14cSt, such as from 2cSt to 12cSt and from 4cSt to 12cSt. The disclosed third base oil may have a ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) Less than about 0.59 and the ratio of branched carbon to linear carbon is less than or equal to 0.23. The disclosed Group III base oil may also have a ratio of branched carbon to terminal carbon of less than 2.6.

For a base oil having a kinematic viscosity of 4-12 cSt at 100 ° C, the API Group III base oil used in the lubricant composition of the present disclosure may have a ratio of polycyclic naphthenes to monocyclic naphthenes of less than 0.59, for example Less than 0.52, such as less than 0.46, such as less than 0.45 or less than 0.43. The base oil may have a ratio of branched carbon to terminal carbon (BC / TC), where BC / TC ≤ 2.3. The light neutral base oil may have a viscosity index from 102 to 133 and be less than or equal to 142 * (1-0.0025 exp (8 * (2R + N / 1RN))). Medium and heavy neutral base oils may have a viscosity index of 120 to 133 and be less than or equal to 150.07 * (1-0.0106 * exp (4.5 * (2R + N / 1RN))). In addition, the amount of naphthenic hydrocarbons in the base oil of the present disclosure may be lower compared to the commercially known base oils in the viscosity range. The naphthenic content may be 30 wt% to 70 wt%.

The disclosed Group III base oil may have less than 0.03 wt% sulfur, pour point is -10 ° C to -30 ° C, Noack volatility is 0.5 wt% to 20 wt%, and CCS at -35 ° C (Cold crank simulator (CCS) value is 100 cP up to 70,000 cP, and naphthenic content is 30 wt% to 70 wt%. Light neutral Group III base oil, that is, with KV100 is 2cSt to 5cSt base oils may have a Noack volatility of 8 wt% to 20 wt%, a CCS value at -35 ° C of 100 cP to 6,000 cP, a pour point of -10 ° C to -30 ° C and a naphthenic content of 30 wt% to 60 wt%. The disclosed medium-neutral Group III base oils, ie those with KV100 of 5 cSt to 7 cSt, may have a Noack volatility of 2 wt% to 10 wt% at -35 The CCS value at ℃ is 3,500 cP to 20,000 cP, the pour point is -10 ℃ to -30 ℃ and the naphthene content is 30 wt% to 60 wt%. The heavy-duty neutral Group III base oil disclosed in this disclosure has Those base oils with a KV100 of 7 cSt to 12 cSt can have a Noack volatility of 0.5 wt% to 4 wt%, a CCS value of 10,000 cP to 70,000 cP at -35 ° C, a pour point of -10 ° C to -30 ° C and Naphthenic content is 3 0 wt% to 70 wt%. According to various embodiments of the present invention, the Group III base oil includes 30 wt% to 70% alkane, or 31 wt% to 69 wt% alkane, or 32 wt% to 68 wt% alkane. According to various embodiments of the present invention, the light neutral Group III base oil may contain 40 wt% to 70 wt%, or 45 wt% to 70 wt%, or 45 wt% to 65 wt% alkane According to various embodiments of the present invention, the medium neutral Group III base oil may contain 35 wt% to 65 wt%, or 40 wt% to 65 wt%, or 40 wt% to 60 wt% alkane. According to the present invention In various embodiments, the heavy-duty neutral Group III base oil may contain 30 wt% to 60 wt%, or 30 wt% to 55 wt%, or 30 wt% to 50 wt%, or 30 wt% to 45 wt%, Or 30 wt% to 40 wt% alkane.

Process

The processes described below can be used to make Group III base oils that are compositionally favorable according to the present disclosure. Generally, the feedstock (e.g., the oil feed viscosity index with solvent dewaxing) is processed through the first stage (which is mainly a hydrogen processing unit that increases the viscosity index (VI) and removes sulfur and nitrogen) A heavy vacuum gas oil feedstock of at least 45 (preferably at least 55, and more preferably at least 60 up to about 150) or an oil feed viscosity index with solvent dewaxing is from at least 45 (preferably at least 55, and More preferably, it is a mixed raw material of at least 60 up to about 150). Next is the stripping section, where the light end and diesel are removed. The heavier lubricating oil fraction then enters the second stage, in which hydrocracking, dewaxing and hydrofinishing are carried out. This combination of raw materials and processing methods produces base oils with unique compositional characteristics. These unique compositional characteristics are observed in the low, medium and high viscosity base oils produced.

Compared with the conventional Group III base oils, the disclosed process structure manufactures high-quality Group III base oils with unique composition characteristics. The compositional advantage can be obtained from the ratio of polycyclic naphthenes to monocyclic naphthenes in the composition.

The disclosed process can produce a base oil having a kinematic viscosity (KV100) at 100 ° C of greater than or equal to 2 cSt, or greater than or equal to 4 cSt (eg, from 4 cSt to 7 cSt), or greater than or equal to 6 cSt, or greater than Equal to 8cSt, or greater than or equal to 10cSt, or greater than or equal to 12cSt, or greater than or equal to 14cSt. Base oils manufactured using the disclosed process can produce base oils with a VI of at least 120 up to about 145 (eg, 120 to 140 or 120 to 133).

As used herein, a stage may correspond to a single reactor or multiple reactors. Optionally, multiple parallel reactors can be used for one or more processes, or multiple parallel reactors can be used for all processes in one stage. Each stage and / or reactor may contain one or more catalyst beds containing hydrogen treatment catalysts or dewaxing catalysts. It should be noted that the "bed" of the catalyst may refer to a part of the physical catalytic bed. For example, the catalyst bed in the reactor may be partially filled with hydrocracking catalyst and partially dewaxed catalyst. For ease of explanation, even though the two catalysts can be stacked together in a single catalyst bed, the hydrocracking catalyst and the dewaxing catalyst can still be individually called individual catalyst beds in concept.

Architecture example

FIG. 1 shows an example of a processing structure suitable for manufacturing the base oil of the present disclosure. Figure 2 shows an example of a general processing architecture suitable for processing raw materials to make the base oil of the present disclosure. It should be noted that R1 corresponds to 110 in FIG. 2; furthermore, R2, R3, R4, and R5 correspond to 120, 130, 140, and 150 in FIG. 2, respectively. Details of the processing architecture can be found in US Patent Application Publication No. 2015 / 715,555. In FIG. 2, the raw material 105 can be introduced into the first reactor 110. The reactor (eg, the first reactor 110) may include a feed inlet and an effluent outlet. The first reactor 110 may correspond to a hydrogen treatment reactor, a hydrocracking reactor, or a combination thereof. Optionally, a plurality of reactors can be used to allow selection of different conditions. For example, if both the first reactor 110 and the optional second reactor 120 are included in the reaction system, the first reactor 110 may correspond to a hydrogen treatment reactor, and the second reactor 120 may correspond to hydrocracking reactor. Other options may also be used, which are used to configure the reactor and / or catalyst in the reactor for initial hydrogen treatment and / or hydrocracking of the feedstock. Optionally, if the architecture includes multiple reactors in the initial stage, gas-liquid separation can be performed between the reactors to allow the removal of light ends and contaminant gases. In the case where the initial stage includes a hydrocracking reactor, the hydrocracking reactor in the initial stage may be referred to as an additional hydrocracking reactor.

Then, the hydrogen-treated effluent 125 from the final reactor (eg, reactor 120) in the initial stage may enter the fractionator 130 or enter another separation stage. Fractionator 130 (or other separation stage) may separate the hydrogen-treated effluent to form one or more fuel boiling range fraction 137, light-end fraction 132, and lubricant boiling range fraction 135. The lubricant boiling range fraction 135 may generally correspond to the bottom fraction from the fractionator 130. The lubricant boiling range fraction 135 may be further hydrocracked in the second stage hydrocracking reactor 140. Then, the effluent 145 from the second stage hydrocracking reactor 140 can enter the dewaxing / hydrofining reactor 150 to further improve the properties of the final lubricant boiling range product. In the architecture shown in FIG. 2, the effluent 155 from the second stage dewaxing / hydrofining reactor 150 can be subjected to fractionation 160 to separate the light end 152 from one or more desired lubricant boiling range fractions 155 / Or fuel boiling range fraction 157.

The architecture in FIG. 2 allows the second stage hydrocracking reactor 140 and the dewaxing / hydrofining reactor 150 to be in sweet processing conditions (equivalent to a feed (to the second stage) sulfur content of 100 wppm Or lower equivalent). Under this "sweet" processing condition, the architecture in Figure 2 combined with a high surface area, low acidity catalyst can be used to produce hydrocracked effluents with reduced or minimized aromatic content.

In the architecture shown in FIG. 2, the final reactor in the initial stage (eg, reactor 120) can be said to be in direct fluid communication with the inlet of fractionator 130 (or the inlet of another separation stage). Based on the indirect fluid communication provided by the final reactor in the initial stage, the other reactors in the initial stage may be referred to as indirect fluid communication with the inlet of the separation stage. Based on direct fluid communication or indirect fluid communication, the reactor in the initial stage may generally be referred to as fluid communication with the separation stage. In some optional aspects, one or more recycle loops may be included as part of the reaction system architecture. The recovery loop can quench the effluent between reactors / stages as well as within the reactors / stages.

In one embodiment, the feedstock is introduced into the reactor under hydrogen treatment conditions. Then, the hydrogen-treated effluent enters the fractionator, where the effluent is separated into a fuel boiling range fraction and a lubricant boiling range fraction. Then, the boiling range fraction of the lubricant enters the second stage, in which the steps of hydrocracking, dewaxing and hydrofinishing are carried out. Then, the effluent from the second stage enters the fractionator, where the Group III base oil of the present disclosure is recovered.

raw material

According to the present invention, a wide range of petroleum and chemical raw materials can be hydrogen treated. Suitable raw materials include whole crude oil and reduced crude oil, such as Arab Light, extra Light, Midland Sweet, Delaware Basin, West Texas Intermediate, Eagle Ford, Murban and Mars crude oil, atmospheric oil, circulating oil, gas oil (including vacuum gas oil) And coking gas oil), light to heavy distillate (including the original initial distillate), hydrocracking products, hydrogenated oil, petroleum-derived wax (including loose wax), Fischer-Tropsch wax, raffinate , Deasphalted oil, and mixtures of these substances.

One way to define raw materials is based on the boiling range of the feed. One option to define the boiling range is to use the initial boiling point of the feed and / or the final boiling point of the feed. Another option is to characterize the feed based on the amount of feed boiling at one or more temperatures. For example, the "T5" boiling point / distillation point of the feed is defined as the temperature at which 5 wt% of the feed will boil. Similarly, the temperature at which the "T95" boiling point / distillation point of the feed at 95 wt% will boil. Appropriate ASTM test methods (such as those described in ASTM D2887, D2892, D6352, D7129, and / or D86) can be used to determine the boiling point (including fractional weight boiling point).

A typical feed contains, for example, a feed having an initial boiling point of at least 600 ° F (~ 316 ° C); similarly, the T5 and / or T10 boiling point of the feed may be at least 600 ° F (~ 316 ° C). Additionally or alternatively, the final boiling point of the feed may be 1100 ° F (~ 593 ° C) or lower; similarly, the T95 boiling point and / or T90 boiling point of the feed may also be 1100 ° F (~ 593 ° C) or lower. As a non-limiting example, a typical feed may have a T5 boiling point of at least 600 ° F (~ 316 ° C) and a T95 boiling point of 1100 ° F (~ 593 ° C) or lower. Optionally, if hydrogen treatment is also used to form the fuel, the feed may contain a lower boiling range portion. For example, this feed may have an initial boiling point of at least 350 ° F (~ 177 ° C) and a final boiling point of 1100 ° F (~ 593 ° C) or lower.

In some aspects, the aromatic content of the feed may be at least 20 wt%, or at least 25 wt%, or at least 30 wt%, determined by the UV-Vis absorption or equalization method (eg, ASTM D7419 or ASTM D2007 or equalization method) , Or at least 40 wt%, or at least 50 wt%, or at least 60 wt%, for example 15 to 75 wt% or up to 90 wt%. In particular, the aromatic content may be 25 wt% to 75 wt%, or 25 wt% to 90 wt%, or 35 wt% to 75 wt%, or 35 wt% to 90 wt%. In other aspects, the feed may have a lower aromatic content, such as an aromatic content of 35 wt% or less, or 25 wt% or less, such as as low as 0 wt%. In particular, the aromatic content may be 0 wt% to 35 wt%, or 0 wt% to 25 wt%, or 5.0 wt% to 35 wt%, or 5.0 wt% to 25 wt%.

Particular raw material components useful in the process of the present disclosure include vacuum gas oil raw materials (eg, medium vacuum gas oil feeds (MVGO)), which have solvent dewaxing oil feed viscosity index from at least 45. At least 50, at least 55, or at least 60 to 150, for example from 65 to 125, at least 65 to 110, from 65 to 100 or 65 to 90.

Other special raw material components useful in the process of the present disclosure include base oils with mixed vacuum gas oil feeds (eg, medium vacuum gas oil feeds (MVGO)) and heavy atmospheric gas oil feeds, where the mixed raw materials have solvents The dewaxed oil feed viscosity index is from at least 45, at least 55, at least 60 to 150, for example from 65 to 145, from 65 to 125, from 65 to 100 or 65 to 90.

Where the hydrogen treatment includes a hydrogen treatment process and / or an acid hydrocracking process, the feed may have a sulfur content of 500 wppm to 20,000 wppm or more, or 500 wppm to 10000 wppm, or 500 wppm to 5000 wppm. Additionally or alternatively, the nitrogen content of this feed may be 20 wppm to 4000 wppm, or 50 wppm to 2000 wppm. In some aspects, the feed can be quite a "sweet" feed, so the feed has a sulfur content of 25 wppm to 500 wppm and / or a nitrogen content of 1 wppm to 100 wppm.

The first hydrogen treatment stage-hydrogen treatment and / or hydrocracking

In various aspects, the first hydrogen treatment stage can be used to improve one or more qualities of the raw materials for lubricant base oil manufacture. Examples of raw material improvements include, but are not limited to, reducing the heteroatom content of the feed, converting on the feed to provide a viscosity index increase, and / or aromatic saturation on the feed.

Regarding the removal of heteroatoms, the conditions in the initial hydrogen treatment stage (hydroprocessing and / or hydrocracking) may be sufficient to reduce the sulfur content of the hydrogen treatment effluent to 250 wppm or less, or 200 wppm or less, Or 150 wppm or less, or 100 wppm or less, or 50 wppm or less, or 25 wppm or less, or 10 wppm or less. In particular, the sulfur content of the effluent from the hydrogen treatment may be 1 wppm to 250 wppm, or 1 wppm to 50 wppm, or 1 wppm to 10 wppm. Additionally or alternatively, the conditions in the initial hydrogen treatment stage may be sufficient to reduce the nitrogen content to 100 wppm or less, or 50 wppm or less, or 25 wppm or less, or 10 wppm or less. In particular, the nitrogen content may be 1 wppm to 100 wppm, or 1 wppm to 25 wppm, or 1 wppm to 10 wppm.

In terms of including hydrogen treatment as part of the initial hydrogen treatment stage, the hydrogen treatment catalyst may include any suitable hydrogen treatment catalyst, including, for example, at least one Group 8-10 non-noble metal (eg, selected from Ni, Co, and combinations thereof) and at least A Group 6 metal catalyst (e.g. selected from Mo, W, and combinations thereof), optionally containing suitable support and / or filler materials (e.g., including alumina, silica, titania, zirconia, or combinations thereof) . The hydrogen treatment catalyst according to aspects of the present invention may be a bulk catalyst or a supported catalyst. The technique of making supported catalysts is widely known in the art. Techniques for making bulk metal catalyst particles are known and have been previously described, for example in US Patent No. 6,162,350, which is incorporated herein by reference. It may be through the method that all metal catalyst precursors are in solution, or through at least one of these precursors is at least partially in solid form, optionally but preferably at least one of these precursors It is a method provided only in the form of a solution to produce massive metal catalyst particles. For example, the provision of the metal precursor can be achieved at least partially in solid form by providing a solution of the metal precursor (which also includes solids and / or precipitated metals in the solution) (eg, in the form of suspended particles). As an illustration, U.S. Patent Nos. 6,156,695, 6,162,350, 6,299,760, 6,582,590, 6,712,955, 6,783,663, 6,863,803, 6,929,738, 7,229,548, 7,288,182, 7,410,924, and 7,544,632 and 8,294,255, U.S. Patent Application Publication No. 2005/0277545, 2006/0060502, 2007/0084754 and 2008/0132407, and International Patent Application Publications WO 04/007646, WO 2007 One or more of / 084437, WO 2007/084438, WO 2007/084439 and WO 2007/084471 describe some examples of suitable hydrogen treatment catalysts. Preferred metal catalysts include cobalt / molybdenum on alumina (1-10% Co for oxide, 10-40% Mo for oxide), nickel / molybdenum (1-10% Ni for oxide, 10-40 % Co is oxide), or nickel / tungsten (1-10% Ni is oxide, 10-40% W is oxide).

In various aspects, hydrogen treatment conditions may include temperatures ranging from 200 ° C to 450 ° C, or 315 ° C to 425 ° C; pressures ranging from 250 psig (~ 1.8 MPag) to 5000 psig (~ 34.6 MPag) or 500 psig (~ 3.4 MPag) to 3000 psig (~ 20.8 MPag), or 800 psig (~ 5.5 MPag) to 2500 psig (~ 17.2 MPag); Liquid Hourly Space Velocities (LHSV) is 0.2-10 hr ^-1 ; and hydrogen treatment rate is 200 scf / B (35.6 m ³ / m ³ ) to 10,000 scf / B (1781 m ³ / m ³ ), or 500 (89 m ³ / m ³ ) to 10,000 scf / B (1781 m ³ / m ³ ).

Hydrogenation catalysts are generally catalysts containing Group 6 metals and Group 8-10 non-noble metals (ie, iron, cobalt, and nickel) and mixtures thereof. These metals or mixtures of metals are usually present on refractory metal oxide supports as oxides or sulfides. Suitable metal oxide supports include low acid oxides, such as silicon dioxide, aluminum oxide or titanium dioxide, preferably aluminum oxide. In some aspects, the preferred alumina may be equivalent to porous alumina, such as γ or η, which has an average pore size of 50 to 200 Å, or 75 to 150 Å; the surface area is from 100 to 300 m ² / g, or 150 To 250 m ² / g; and / or pore volume is from 0.25 to 1.0 cm cm ³ / g, or 0.35 to 0.8 cm ³ / g. It is preferable not to promote the support with halogen (for example, fluorine), because this usually increases the acidity of the support.

The external surface area and micropore surface area are a way of specifying the total surface area of the catalyst. These surface areas were calculated based on the analysis of nitrogen porosimetry data using the BET method of measuring surface area. See, for example, Johnson, M. F. L., Jour. Catal., 52, 425 (1978). The micropore surface area refers to the surface area due to the one-dimensional pores of the zeolite in the catalyst. Only zeolite in the catalyst will contribute this part of the surface area. The external surface area can be attributed to the zeolite or binder within the catalyst.

Alternatively, the hydrogen treatment catalyst may be a bulk metal catalyst, or a combination of supported and stacked bed of bulk metal catalyst. By bulk metal, it refers to an unsupported catalyst, where the bulk catalyst particles include 30-100 wt% of at least one Group 8-10 based on the total weight of the bulk catalyst particles (calculated as metal oxides) Non-noble metals and at least one Group 6 metal, and wherein the bulk catalyst particles have a surface area of at least 10 m ² / g. Furthermore, based on the total weight of the bulk catalyst particles (calculated as metal oxides), it is preferred that the bulk metal hydrogen treatment catalyst used herein includes 50 to 100 wt%, and even preferably 70 to 100 wt% At least one Group 8-10 non-noble metal and at least one Group 6 metal. The amount of Group 6 and Group 8-10 non-noble metals can be determined via TEM-EDX.

It is preferably a bulk catalyst composition comprising one Group 8-10 non-noble metal and two Group 6 metals. It has been found that in this case, the bulk catalyst particles are sintering-resistant. Therefore, the active surface area of the massive catalyst particles is maintained during use. The molar ratio of Group 6 to Group 8-10 non-precious metals generally ranges from 10: 1 to 1:10, and preferably from 3: 1 to 1: 3. In the case of core-shell particles, these ratios are of course applicable to the metals contained in the shell. If the bulk catalyst particles contain more than one Group 6 metal, the ratio of the different Group 6 metals is usually not critical. The same applies when more than one Group 8-10 non-noble metal is used. When molybdenum and tungsten exist as Group 6 metals, the molybdenum: tungsten ratio range is preferably 9: 1 to 1: 9. Preferably, the Group 8-10 non-noble metals include nickel and / or cobalt. More preferably, the Group 6 metal includes a combination of molybdenum and tungsten. Preferably, a combination of nickel / molybdenum / tungsten and cobalt / molybdenum / tungsten and nickel / cobalt / molybdenum / tungsten is used. These kinds of precipitates are obviously resistant to sintering. Therefore, the active surface area of the precipitate is maintained during use. Such metals preferably exist as oxidized compounds of the corresponding metals, or if the catalyst composition has been sulfided, as the sulfided compounds of the corresponding metals.

In some optional aspects, the bulk metal hydrogenation catalyst used herein has a surface area of at least 50 m ² / g and preferably at least 100 m ² / g. In these respects, it is also desirable that the pore size of the bulk metal hydrogen treatment catalyst is almost the same as that of the conventional hydrogen treatment catalyst. The bulk metal hydrogenation catalyst determined by nitrogen adsorption may have a mark with a pore volume of 0.05-5 ml / g, or 0.1-4 ml / g, or 0.1-3 ml / g or 0.1-2. Preferably, there are no holes smaller than 1 nm. The bulk metal hydrogen treatment catalyst may have a median diameter of at least 50 nm, or at least 100 nm. The bulk metal hydrogenation catalyst may have a median diameter of no more than 5000 μm, or no more than 3000 μm. In one embodiment, the median particle diameter ranges from 0.1-50 μm and the optimal range is from 0.5-50 μm.

Examples of suitable hydrogen treatment catalysts include, but are not limited to, Albemarle KF 848, KF 860, KF 868, KF 870, KF 880, KF 861, KF 905, KF 907, and Nebula; Criterion LH-21, LH-22 and DN-3552; Haldor-Topsøe TK-560 BRIM, TK-562 HyBRIM, TK-565 HyBRIM, TK-569 HyBRIM, TK-907, TK-911 and TK-951; Axens HR 504, HR 508, HR 526 and HR 544. The hydrogen treatment can be performed by one of the catalysts listed above or a combination thereof.

Second stage treatment-hydrocracking or conversion conditions

In various aspects, instead of using conventional hydrocracking catalysts in the second (sweet) reaction stage of the shift feed, the reaction system can include a high surface area, low acidity shift catalyst as described herein. Where the lubricant boiling range feed (e.g. feed equivalent to a "sweet" feed) has a sufficiently low content of heteroatoms, the feed can be exposed to a high surface area, low acidity conversion catalyst as described herein without the need Previous hydrogen treatment to remove heteroatoms.

In various aspects, the conditions selected for conversion of lubricant base oil manufacturing may depend on the amount of conversion desired, the amount of contaminants input to the conversion stage, and potentially other factors. For example, the conditions of hydrocracking and / or conversion in the first stage and / or second stage of a single stage or in a multi-stage system can be selected to achieve the desired conversion amount in the reaction system. The hydrocracking and / or conversion conditions may be referred to as sour conditions or sweet conditions, depending on the amount of sulfur and / or nitrogen present in the feed and / or in the gas phase in which the reaction environment is present. For example, a feed with 100 wppm or less sulfur and 50 wppm or less nitrogen (preferably less than 25 wppm sulfur and / or less than 10 wppm nitrogen) represents a hydrogenation under sweet conditions Feed for cracking and / or conversion. Feeds with a sulfur content of 250 wppm or more can be processed under acid conditions. Feeds with intermediate amounts of sulfur can be processed under sweet or acid conditions.

In terms of including hydrocracking as part of the initial hydrogen treatment stage under acid conditions, the initial stage hydrocracking catalyst may include any suitable or standard hydrocracking catalyst, for example selected from zeolite beta, zeolite X, zeolite Y, Zeolite substrates of faujasite, ultrastable Y (USY), dealuminated Y (Deal Y), mordenite (Mordenite), ZSM-3, ZSM-4, ZSM-18, ZSM-20, ZSM-48, and combinations thereof ( zeolitic base), the zeolite substrate can advantageously support 20 one or more active metals (such as (i) Group 8-10 noble metals such as platinum and / or palladium or (ii) Group 8-10 non-noble metals such as nickel , Cobalt, iron, and combinations thereof, and Group 6 metals, such as molybdenum and / or tungsten). In this discussion, zeolite materials are defined as comprising framework structures with approved zeolites, such as those approved by the International Zeolite Association. These zeolite materials can be equivalent to silicoaluminate, silicoaluminophosphate, aluminophosphate and / or other combinations of atoms that can be used to form the framework structure of the zeolite. In addition to zeolite materials, other types of crystalline acidic support materials may also be suitable. Optionally, the zeolite material and / or other crystalline acidic materials can be mixed or combined with other metal oxides (such as alumina, titania, and / or silica). Details of suitable hydrocracking catalysts are available in US2015 / 715555.

In some optional aspects, the high surface area, low acidity conversion catalyst described herein can optionally be used as part of the catalyst in the initial stage.

Available at temperatures from 200 ° C to 450 ° C, hydrogen partial pressure from 250 psig to 5000 psig (~ 1.8 MPag to ~ 34.6 MPag), liquid space velocity from 0.2 hr ^-1 to 10 hr ^-1 and hydrogen treatment gas rate is The hydrocracking process in the first stage (or under acidic conditions) is carried out from 35.6 m ³ / m ³ to 1781 m ³ / m ³ (~ 200 SCF / B to ~ 10,000 SCF / B). Generally, in most cases, the conditions may include a temperature range of 300 ° C to 450 ° C, a partial pressure of hydrogen from 500 psig to 2000 psig (~ 3.5 MPag to ~ 13.9 MPag), and a liquid space velocity from 0.3 hr ^-1 To 5 hr ^-1 and the hydrogen treatment gas rate is from 213 m ³ / m ³ to 1068 m ³ / m ³ (~ 1200 SCF / B to ~ 6000 SCF / B).

In a multi-stage reaction system, the first reaction stage of the hydrocracking reaction system may include one or more hydrogen treatment and / or hydrocracking catalysts. Then, a separator can be used between the first and second stages of the reaction system to remove gaseous sulfur and nitrogen pollutants. One option for the separator is to simply perform gas-liquid separation to remove contaminants. Another option is to use a separator, such as a flash separator, which can be separated at a higher temperature. For example, this high temperature separator can be used to separate the feed into a portion with a boiling point below the temperature cut-off point (e.g., about 350 ° F (177 ° C) or about 400 ° F (204 ° C)), and a portion with a boiling point above the temperature cut-off point . In this separation, the portion of the naphtha boiling range of the effluent from the first reaction stage can also be removed, thereby reducing the volume of the effluent processed in the second or other subsequent stages. Of course, any low-boiling contaminants in the effluent from the first stage are also separated into parts with boiling points below the temperature cut-off point. If sufficient pollutant removal is performed in the first stage, the second stage can be operated as a "sweet" or low pollutant stage.

Another option may be to use a separator between the first and second stages of the hydrogen treatment reaction system, which may also perform fractional distillation of at least a portion of the effluent from the first stage. In this aspect, the effluent from the first hydrogen treatment stage may be separated into at least a portion of the boiling range below the distillate (e.g. diesel) fuel range, a portion boiling within the distillate fuel range, and a boiling point above the distillation range Part of the fuel range. Based on the known diesel boiling range, a distillate fuel range can be defined, for example, having a lower cut point temperature of at least about 350 ° F (177 ° C) or at least about 400 ° F (204 ° C) to having an upper cut point temperature of about 700 ° F (371 ° C) or lower, or 650 ° F (343 ° C) or lower. Optionally, the distillate fuel range can be extended to include additional kerosene, for example, by selecting the lower cut point temperature to be at least about 300 ° F (149 ° C).

Where the interstage separator is also used to produce distillate fuel fractions, the fraction with a boiling point lower than the distillate fuel fraction contains naphtha boiling range molecules, light ends, and contaminants such as H ₂ S. These different products can be separated from each other by any convenient method. Likewise, if desired, one or more distillate fuel fractions can be formed from the distillate boiling range fractions. The portion with a boiling point higher than the distillate fuel range represents a potential lubricant base oil. In these respects, the portion having a boiling point higher than the boiling range of the distillate fuel is used for further hydrogen treatment in the second hydrogen treatment stage. The portion having a boiling point higher than the boiling range of the distillate fuel may correspond to a lubricant boiling range fraction, for example, a fraction having a T5 or T10 boiling point of at least about 343 ° C. Optionally, the lighter lubricating oil fraction can be distilled and operated in the catalyst dewaxing portion of the closed operation, where the conditions are adjusted to maximize the yield and properties of each lube oil cut.

The conversion method under sweet conditions may be carried out under conditions similar to those used in acid hydrocracking processes, or the conditions may be different. In one embodiment, the conditions in the sweet conversion stage may have less stringent conditions than hydrocracking in the acid stage. Suitable switching conditions for the non-acid stage may include, but are not limited to, conditions similar to the first or acid stage. Suitable conversion conditions may include a temperature of about 550 ° F (288ºC) to about 840 ° F (449 ° C), a partial pressure of hydrogen from about 1000 psia to about 5000 psia (~ 6.9 MPa-a to 34.6 MPa-a), liquid space The speed per hour is from 0.05 hr ^-1 to 10 hr ^-1 and the hydrogen treatment gas rate is from 35.6 m ³ / m ³ to 1781 m ³ / m ³ (200 SCF / B to 10,000 SCF / B). In other embodiments, the conditions may include a temperature ranging from about 600 ° F (343 ° C) to about 815 ° F (435 ° C), and a hydrogen partial pressure from about 1000 psia to about 3000 psia (~ 6.9 MPa-a to 20.9 MPa- a), and the hydrogen treatment gas rate is from about 213 m ³ / m ³ to 1068 m ³ / m ³ (1200 SCF / B to 6,000 SCF / B). The LHSV may be from about 0.25 hr ^-1 to about 50 hr ^-1 , or from about 0.5 hr ^-1 to about 20 hr ^-1 , and preferably from about 1.0 hr ^-1 to about 4.0 hr ^-1 .

On the other hand, the same conditions can be used for hydrogen treatment, hydrocracking and / or switching beds or stages, for example using hydrogen treatment conditions for all beds or stages, using hydrocracking conditions for all beds or stages, And / or use transition conditions for all beds or stages. In another embodiment, the pressure used for hydrogen treatment, hydrocracking, and / or shift bed or stage may be the same.

In another aspect, the hydrogen treatment reaction system may include more than one hydrocracking and / or conversion stage. If there are multiple hydrocracking and / or conversion stages, at least one hydrocracking stage may have the effective hydrocracking conditions described above, including a hydrogen partial pressure of at least about 1000 psia (~ 6.9 MPa-a). In this regard, other (subsequent) conversion processes can be performed under conditions that can include a lower hydrogen partial pressure. Suitable conversion conditions for other conversion stages may include (but are not limited to) a temperature of about 550 ° F (288 ° C) to about 840 ° F (449 ° C), and a hydrogen partial pressure of from about 250 psia to about 5000 psia (1.8 MPa- a to 34.6 MPa-a), liquid space hourly speed from 0.05 hr ^-1 to 10 hr ^-1 , and hydrogen treatment gas rate from 35.6 m ³ / m ³ to 1781 m ³ / m ³ (200 SCF / 5 B to 10,000 SCF / B). In other embodiments, the conditions for other conversion stages may include a temperature range of about 600 ° F (343ºC) to about 815 ° F (435 ° C), and a partial pressure of hydrogen from about 500 psia to about 3000 psia (3.5 MPa-a To 20.9 MPa-a), and the hydrogen treatment gas rate is from about 213 m ³ / m ³ to about 1068 m ³ / m ³ (1200 SCF / B to 6000 SCF / B). The LHSV may be from about 0.25 hr ^-1 to about 50 hr ^-1 , or from about 0.5 hr ^-1 to about 20 hr ^-1 , and preferably from about 1.0 hr ^-1 to about 4.0 hr ^-1 .

Additional second stage treatment-dewaxing and hydrorefining / aromatic saturation (Aromatic Saturation)

In various aspects, catalytic dewaxing can be included as part of the second and / or sweet and / or subsequent processing stage (eg, also included in the conversion stage where a high surface area, low acid catalyst is present). Preferably, the dewaxing catalyst is zeolite (and / or zeolite crystals), which is mainly dewaxed by isomerizing hydrocarbon feedstock. More preferably, the catalyst is a zeolite with a one-dimensional pore structure. Suitable catalysts include 10-membered ring pore zeolites, such as EU-1, ZSM-35 (or ferrierite), ZSM-11, ZSM-57, NU-87, SAPO-11, and ZSM-22. Preferred materials are EU-2, EU-11, ZBM-30, ZSM-48, or ZSM-23. ZSM-48 is the best. It should be noted that zeolites having a ZSM-23 structure with a silica to alumina ratio of 20: 1 to 40: 1 are sometimes referred to as SSZ-32. Other zeolite crystals having the same structure as the above materials include Theta-1, NU-10, EU-13, KZ-1, and NU-23. U.S. Patent Nos. 7,625,478, 7,482,300, 5,075,269, and 4,585,747 further disclose that the dewaxing catalyst is useful in the process of this disclosure, and the above-mentioned U.S. patent cases are all incorporated herein by reference.

In various embodiments, the dewaxing catalyst may further include a metal hydrogenation component. The metal hydrogenation component is usually a Group 6 and / or Group 8-10 metal. Preferably, the metal hydrogenation component is a Group 8-10 noble metal. Preferably, the metal hydrogenation component is Pt, Pd or a mixture thereof. In another preferred embodiment, the metal hydrogenation component may be a combination of non-precious Group 8-10 metals and Group 6 metals. Suitable combinations may include Ni, Co or Fe and Mo or W, preferably Ni and Mo or W.

The metal hydrogenation component can be added to the dewaxing catalyst by any convenient method. One technique for adding metal hydrogenation components is by incipient wetness. For example, after combining the zeolite and the binding agent, the combined zeolite and the binding agent can be extruded into the catalyst particles. These catalyst particles can then be exposed to a solution containing suitable metal precursors. Alternatively, the metal can be added to the catalyst by ion exchange, where the metal precursor is added to the mixture of zeolite (or zeolite and binder) before extrusion.

The amount of metal in the dewaxing catalyst can be at least 0.1 wt%, or at least 0.15 wt%, or at least 0.2 wt%, or at least 0.25 wt%, or at least 0.3 wt%, or at least 0.5 wt% based on the catalyst. The amount of metal in the catalyst may be 20 wt% or less, or 10 wt% or less, or 5 wt% or less, or 2.5 wt% or less, or 1 wt% or less based on the catalyst. For the metal is Pt, Pd, another Group 8-10 noble metal, or a combination thereof, the amount of metal may be from 0.1 to 5 wt%, preferably from 0.1 to 2 wt%, or 0.25 to 1.8 wt% , Or 0.4 to 1.5 wt%. For aspects where the metal is a combination of non-precious Group 8-10 metals and Group 6 metals, the combined amount of metals may be from 0.5 wt% to 20 wt%, or 1 wt% to 15 wt%, or 2.5 wt% Up to 10 wt%.

Preferably, the dewaxing catalyst may be a catalyst having a low ratio of silica to alumina. For example, for ZSM-48, the ratio of silica to alumina in the zeolite can be less than 200: 1, or less than 110: 1, or less than 100: 1, or less than 90: 1, or less than 80: 1. In particular, the ratio of silica to alumina may be from 30: 1 to 200: 1, or 60: 1 to 110: 1, or 70: 1 to 100: 1.

The dewaxing catalyst may also contain a binder. In some embodiments, a low surface area binder is used to formulate the dewaxing catalyst used in the process according to the present invention, the low surface area binder means having a surface area of 100 m ² / g or less, or 80 m ² / g or more Small, or 70 m ² / g or less, for example as low as 40 m ² / g or even smaller binder.

Alternatively, the binder and zeolite particle sizes can be selected to provide a catalyst with a desired ratio of micropore surface area to total surface area. In the dewaxing catalyst used according to the invention, the micropore surface area corresponds to the surface area of the one-dimensional pores of the zeolite in the dewaxing catalyst. The total surface area corresponds to the micropore surface area plus the external surface area. Any binder used in the catalyst will not contribute to the micropore surface area and will not significantly increase the total surface area of the catalyst. The external surface area represents the balance of the total catalyst surface area minus the micropore surface area. Both the binder and the zeolite can contribute to the value of the external surface area. Preferably, the ratio of the micropore surface area of the dewaxing catalyst to the total surface area will be equal to or greater than 25%.

The zeolite (or other zeolite material) can be combined with the binding agent in any convenient way. For example, a bound catalyst can be made by starting with a powder of both zeolite and binder, combining the powder with added water and grinding to form a mixture, and then extruding the mixture to produce a bound catalyst of the desired size . An extrusion aid can also be used to modify the properties of the extrusion fluid of the mixture of zeolite and binder. Optionally, a binder composed of two or more metal oxides can also be used.

The processing conditions in the catalytic dewaxing zone may include a temperature from 200 to 450 ° C (preferably 270 to 400 ° C) and a hydrogen partial pressure from 1.8 to 34.6 MPag (~ 250 to ~ 5000 psi) (preferably 4.8 To 20.8 MPag), liquid space velocity from 0.2 to 10 hr ^-1 (preferably 0.5 to 3.0 hr ^-1 ), and hydrogen circulation rate from 35.6 to 1781 m ³ / m ³ (~ 200 to ~ 10,000 SCF / B) (preferably 178 to 890.6 m ³ / m ³ (~ 1000 to ~ 5000 scf / B)). Additionally or alternatively, the conditions may include a temperature range of 600 ° F (~ 343ºC) to 815 ° F (~ 435 ° C), a partial pressure of hydrogen from 500 psig to 3000 psig (~ 3.5 MPag to ~ 20.9 MPag), and hydrogen treatment gas The rate is from 213 m ³ / m ³ to 1068 m ³ / m ³ (~ 1200 SCF / B to ~ 6000 SCF / B).

In various aspects, hydrofinishing and / or aromatic saturation processes can also be provided. The hydrogen refining and / or aromatic saturation process may occur before and / or after dewaxing. The hydrogen refining and / or aromatic saturation process can occur before or after fractional distillation. If the hydrofinishing and / or aromatic saturation process occurs after fractionation, the hydrofinishing can be performed on one or more parts of the fractionated product, for example, on one or more lubricant base oil parts. Alternatively, the entire effluent from the final conversion or dewaxing process can be hydrorefined and / or aromatically saturated.

In some cases, the hydrofinishing process and the aromatic saturation process may refer to a single process using the same catalyst. Alternatively, a catalyst or catalyst system may be provided for aromatic saturation, and a second catalyst or catalyst system may be used for hydrofinishing. Typically, for practical reasons, such as facilitating the use of lower temperatures in hydrofinishing or aromatic saturation processes, the hydrofinishing and / or aromatic saturation processes will be dewaxing or hydrocracking processes in individual reactors. However, after the hydrocracking or dewaxing process but before the fractionation, it is conceptually possible to consider another hydrofinishing reaction as part of the second stage of the reaction system.

The hydrofinishing and / or aromatic saturation catalyst may include a catalyst having a Group 6 metal, Group 8-10 metal, and mixtures thereof. In one embodiment, the preferred metal includes at least one metal sulfide with a strong hydrogenation function. In another embodiment, the hydrorefining catalyst may include Group 8-10 noble metals, such as Pt, Pd, or a combination thereof. The mixture of metals may also be present as a bulk metal catalyst, where the amount of metal is 30 wt% or greater based on the catalyst. Suitable metal oxide supports include low acid oxides, such as silica, alumina, silica-alumina, or titania, preferably alumina. The preferred hydrofinishing for aromatic saturation will include at least one metal, which has a relatively strong hydrogenation function on the porous support. Typical support materials include amorphous or crystalline oxide materials, such as alumina, dioxide, and silica-alumina. The support material can also be modified, for example by halogenation, or in particular fluorination. For non-noble metals, the metal content of the catalyst is usually as high as 20 weight percent. In one embodiment, the preferred hydrofinishing may include crystalline materials belonging to the M41S family or family of catalysts. The M41S family of catalysts are mesoporous materials with high silica content. Examples include MCM-41, MCM-48 and MCM-50. The preferred member of this class is MCM-41. If individual catalysts are used for aromatic saturation and hydrofinishing, the aromatic saturation catalyst can be selected based on the activity and / or selectivity of the aromatic saturation, and can be based on the product specifications used to improve (e.g. product color and polynuclear aromatic For the activity of polynuclear aromatic reduction, a hydrofinishing catalyst is selected. U.S. Patent Nos. 7,686,949, 7,682,502, and 8,425,762 further disclose catalysts that can be used in the disclosed process, and these patents are incorporated herein by reference.

Hydrofining conditions may include temperatures from 125 ° C to 425 ° C (preferably 180 ° C to 280 ° C), and total pressures from 500 psig (~ 3.4 MPag) to 3000 psig (~ 20.7 MPag) (preferably 1500 psig (~ 10.3 MPag) to 2500 psig (~ 17.2 MPag)), and liquid space velocity (LHSV) from 0.1 hr ^-1 to 5 hr ^-1 (preferably 0.5 hr ^-1 to 1.5 hr ^-1 ).

After the second or subsequent stage, a second fractionation or separation can be performed at one or more locations. In some aspects, under sweet conditions, in the presence of a USY catalyst, after hydrocracking in the second stage, fractional distillation can be performed. Thereafter, at least one lubricant boiling range portion of the second stage hydrocracking effluent may be transferred to the dewaxing and / or hydrofinishing reactor for further processing. In some aspects, hydrocracking and dewaxing can be performed before the second fractionation. In some aspects, hydrocracking, dewaxing, and aromatic saturation can be performed before the second fractionation. Optionally, aromatic saturation and / or hydrofinishing may be performed before the second fractionation, after the second fractionation, or before and after the second fractionation.

If the lubricant base oil product is desired, the lubricant base oil product can be further fractionated to form a plurality of products. For example, the lubricant base oil product may be manufactured to correspond to a 2cSt cut point, a 4cSt cut point, a 6cSt cut point, and / or a cut point having a viscosity greater than 6cSt. For example, a lubricant base oil fraction having a viscosity of at least 2 cSt may be suitable for low pour point applications (such as transformer oil, low temperature hydraulic oil, or automatic transmission fluid) ) Fraction. The lubricant base oil fraction having a viscosity of at least 4 cSt may be a fraction with controlled volatility and low pour point, so the fraction is suitable for engine oils manufactured according to SAE J300 in 0W- or 5W- or 10W grades. This fractional distillation may occur when the diesel (or other fuel) product is separated from the lubricant base oil product in the second stage, or the fractional distillation may occur afterwards. Any hydrofinishing and / or aromatic saturation can occur before or after fractional distillation. After fractionation, the lubricant base oil product fraction can be combined with appropriate additives to serve as engine oil or another lubricant. U.S. Patent Nos. 8,992,764, 8,394,255, U.S. Patent Application Publication No. 2013/0264246 and U.S. Patent Application Publication No. 2015 / 715,555 reveal the illustrative process flow schemes that can be used in this disclosure, and such disclosures The full text of the content is incorporated into this article for reference.

Lubricating oil additives

The base oil constitutes the main component of the oil lubricant composition of the engine or other mechanical components disclosed herein, and is usually present in an amount of from about 50 to about 99 weight percent based on the total weight of the composition, preferably from about 70 to about 95 The weight percent, and more preferably from about 85 to about 95 weight percent. As described herein, the additive constitutes a minor component of the oil lubricant composition of the engine or other mechanical components of the present disclosure, and is generally present in an amount ranging from about less than 50 weight percent based on the total weight of the composition, preferably less than About 30% by weight, and more preferably less than about 15% by weight.

If desired, a mixture of base oils can be used, for example, base oil components and co-base stock components. In the lubricating oil of the present disclosure, based on the total weight of the composition, the amount of the base oil component is from about 1 to about 99 weight percent, preferably from about 5 to about 95 weight percent, and more preferably from about 10 Up to about 90 weight percent. In a preferred aspect of the present disclosure, a low-viscosity and high-viscosity base oil is used in the form of a base oil mixture, which includes from 5 to 95 wt% of low-viscosity base oil and from 5 to 95 wt% of high-viscosity base oil. The preferred range includes from 10 to 90 wt% of low viscosity base oil and from 10 to 90 wt% of high viscosity base oil. Based on the total weight of the oil lubricant composition, in the engine or other mechanical component oil lubricant composition, the base oil mixture may be present from 15 to 85% by weight of low viscosity base oil and from 15 to 85% by weight of high viscosity base Oil, preferably from 20 to 80 wt% of low viscosity base oil and from 20 to 80 wt% of high viscosity base oil, and more preferably from 25 to 75 wt% of low viscosity base oil and from 25 to 75 wt % High viscosity base oil.

In one aspect of the present disclosure, based on the total weight of the composition, in the engine or other mechanical component oil lubricant composition, the low viscosity, medium viscosity, and / or high viscosity base oil is present in an amount of from about 50 to about 99 weight percent , Preferably from about 70 to about 95 weight percent, and more preferably from about 85 to about 95 weight percent.

The formulated lubricating oil that can be used in the present disclosure may contain one or more other commonly used lubricating oil performance additives, including but not limited to anti-wear additives, cleaning agents, dispersants, viscosity modifiers, corrosion inhibitors, Rust agents, metal deactivators, extreme pressure additives, antiepileptic agents, wax modifiers, other viscosity modifiers, fluid-loss additives, sealing compatibilizers, lubricants, antifouling agents, color development Chromophoric agent, defoamer, demulsifier, emulsifier, thickener, wetting agent, gelling agent, tackiness agent, colorant, etc. For comments on many commonly used additives, see "Lubricant Additives, Chemistry and Applications", Ed. LR Rudnick, Marcel Dekker, Inc. 270 Madison Ave. New York, NJ 10016, 2003, and Klamann in Lubricants and Related Products, Verlag Chemie , Deerfield Beach, FL; ISBN 0-89573-177-0. Reference is also made to "Lubricant Additives" by M. W. Ranney, published by Noyes Data Corporation of Parkridge, NJ (1973); see also U.S. Patent No. 7,704,930, the entire disclosure of which is incorporated herein by reference. These additives are usually delivered with different amounts of diluent oil, and the amount of diluent oil can range from 5 weight percent to greater than 90 weight percent.

The additives that can be used in this disclosure are not necessarily soluble in lubricating oil. Insoluble additives (such as zinc stearate in oil) can be dispersed in the lubricating oil of the present disclosure.

When the lubricating oil composition contains one or more additives, the additives are mixed into the composition in an amount sufficient to allow it to perform its proper function. As mentioned above, the additives are usually present in the lubricating oil composition as a minor component, the usual amount of which is less than 50 weight percent based on the total weight of the composition, preferably less than about 30 weight percent, and more preferably less than about 15 Weight percentage. The amount of additives most often added to the lubricating oil composition is at least 0.1 weight percent, preferably at least 1 weight percent, and more preferably at least 5 weight percent. The usual amounts of these additives that can be used in this disclosure are shown in Table 1 below.

It should be noted that many of the additives are shipped by the additive manufacturer as a concentrate, containing one or more additives and certain amounts of base oil diluent. Accordingly, the weight content in Table 1 below and other amounts mentioned herein refer to the amount of active ingredient (ie, the non-diluent portion of the ingredient). The weight percentages (wt%) indicated below are based on the total weight of the lubricating oil composition.
Table 2
The usual amount of other lubricant components

The aforementioned additives are all commercially available materials. These additives can be added separately, but these additives are usually pre-combined in the packaging, which is available from lubricant oil additive suppliers. Additive packaging with various ingredients, ratios and characteristics is available, and selecting the appropriate packaging will take into account the necessary use of the final composition.

The lubricant composition containing the base oil of the present disclosure has improved oxidation stability relative to the conventional lubricant composition containing the Group III base oil. The low-temperature and oxidation performance of the lubricating base oil in the formulated lubricant is measured by MRV (Miniature Rotating Viscometer), used for low-temperature performance measured by ASTM D4684 or used by differential pressure scanning calorimetry (CEC-L -85, which is equivalent to the oxidation efficiency measured by the oxidation stability time measured by ASTM D6186). The lubricating oil disclosed herein is particularly advantageous as a passenger vehicle engine oil (PVEO) product.

Compared to conventional lubricating base oils, the lubricating base oils of the present disclosure provide several advantages, including (but not limited to) improved oxidation performance in motor oils, such as the differential pressure scanning calorimetry method (CEC-L -85, which corresponds to the oxidation induction time measured by ASTM D6186).

Lubricant compositions can be used in this disclosure for various end uses related to lubricants, such as lubricating oils or greases, for moving and / or interacting mechanical parts, components, or devices or equipment that require lubrication. Available equipment includes engines and machinery. The disclosed lubricating base oil is suitable for automotive crankcase lubricants, automotive gear oils, transmission oils, and many industrial lubricants (including circulating lubricants, industrial gear lubricants, greases, compressor oils, pump oils) , Refrigeration lubricants, hydraulic lubricants, and metalworking fluid formulations. Furthermore, the lubricating base oils of the present disclosure can be obtained from renewable resources; these base oils can meet the requirements of sustainable products and can meet the requirements of industrial groups or The "sustainability" standard stipulated by government regulations.

The following non-limiting examples are provided to illustrate this disclosure.

Examples

For Examples 1 and 2, feeds A and B were processed according to the method described in this disclosure and described in FIG. In particular, feedstocks with the properties described in Table 3 were processed to make Group III base oils of the present disclosure. After the stage 1 hydrogen treatment, the intermediate feed with the properties described in Table 4 is subjected to the stage 2 hydrogen treatment to manufacture the Group III base oil of the present disclosure. Feed A represents a raffinate feed with ~ 67 VI, and feed B represents a high-quality VGO feed with ~ 92 VI.

Five different catalysts were used for the treatment in Examples 1 and 2, the details are as follows. For these two examples, the catalysts A and B used in stage 1 hydrogen treatment, and the catalysts C, D and E used in stage 2 hydrogen treatment.

Catalyst A: A commercially available hydrogen treatment catalyst composed of NiMo supported by Al ₂ O ₃ .

Catalyst B: A commercially available hydrogen treatment catalyst, which consists of massive NiMoW oxide.

Catalyst C: 0.6 wt% Pt on USY, combined with Versal-300 alumina. USY has a silica to alumina ratio (SiO ₂ : Al ₂ O ₃ ) of about 75: 1. USY is a zeolite with 12-member ring pore channels.

Catalyst D: A commercially available dewaxing catalyst consisting of Pt supported on ZSM-48.

Catalyst E: A commercially available hydrorefining catalyst consisting of Pt / Pd supported on MCM-41.

Example 1:

The properties of feed A are shown in Table 3. The feed was hydrotreated at two conversion levels (ie, 17% and 33%), and then mixed (44.6 / 55.4) to obtain products having the properties shown in Table 3. Regarding the amount of dry wax, based on the correction of the pour point of -0.33 wt% / ° C, the amount of dry wax was corrected to the expected value of pour point of -18 ° C. Regarding the viscosity index, based on the correction of the pour point of 0.33 VI / ° C, the viscosity index was corrected to the expected value of the pour point of -18 ° C.
table 3

Table 4

Feed A (oil feed viscosity index with solvent dewaxing is about 67) is processed through the first stage (which is mainly a hydrogen treatment unit that raises viscosity index (VI) and removes hydrogen and nitrogen). Both catalysts A and B are loaded in the same reactor, and the feed first contacts catalyst A. The hydrotreated feed is followed by a stripped portion where the light end and diesel are removed. During the stage 1 hydrogen treatment process, feed A is separated and converted at two different levels (labeled "low" and "high" conversion). The properties of the intermediate feeds (A1 and A2) are shown in Table 4. The heavier lubricant fractions from A1 and A2 then enter the second stage, where hydrocracking, dewaxing and hydrofinishing are carried out. Various processing conditions using each of these steps (described below) are used to manufacture five Class III base oils A1-A6, the properties of which are shown in Tables 6 (4-5cSt), 7 (5-7cSt) and 8 (8 -11cSt). This combination of feed and process has been found to produce Group III base oils with unique compositional characteristics. These unique compositional characteristics are observed in the lower and higher viscosity base oils produced, as shown in Figures 3 and 4.

Based on the desired conversion rate and VI of the final base oil product, the processing conditions of each of the above steps-hydrogen treatment, hydrocracking, catalytic dewaxing, and hydrofinishing-are adjusted. The conditions used to manufacture Group III base oils of the subject matter of this disclosure can be found in Table 5. The 700 ° F + conversion rate in the first hydrogen treatment stage ranges from 20 to 40%, and the treatment conditions in the first stage include temperatures from 635 ° F to 725 ° F; hydrogen partial pressure from 500 psig to 3000 psig; liquid space The speed is from 0.5 hr ^-1 to 1.5 hr ^-1 ; and the hydrogen circulation rate is from 3500 scf / bbl to 6000 scf / bbl.

The second stage consisting of hydrocracking, catalytic dewaxing and hydrofinishing is performed in a single reactor with a hydrogen partial pressure of 300 psig to 5000 psig and a hydrogen circulation rate from 1000 scf / bbl to 6000 scf / bbl. Catalysts C, D and E are loaded in the same reactor in the second stage, and the order of feed contact is C, D and E. Adjust the process parameters to achieve the desired 700 ° F + conversion rate of 15-70%.

The processing conditions in the hydrocracking step include temperatures from 250 ° F to 700 ° F; the liquid space velocity is 0.5 hr ^-1 to 1.5 hr ^-1 . The processing conditions in the catalytic dewaxing step include temperatures from 250 ° F to 660 ° F; and liquid space velocity from 1.0 hr ^-1 to 3.0 hr ^-1 . The processing conditions in the hydrogen treatment step include a temperature from 250 ° F to 480 ° F; and a liquid space velocity from 0.5 hr ^-1 to 1.5 hr ^-1 .

Example 2:

The properties of feed B are shown in Table 3. Feed B is processed through a first stage hydrogen treatment unit (which raises viscosity index (VI) and removes sulfur and nitrogen). The feed to the hydrogen treatment is followed by a stripping section where the light end and diesel are removed. Both catalysts A and B are loaded in the same reactor, and the feed first contacts catalyst A. During the stage 1 hydrogen treatment, feed B undergoes a conversion level and shows the properties shown in Table 4. The heavier lubricating oil fraction from this middle then enters the second stage, in which hydrocracking, dewaxing and hydrofinishing are carried out. Various processing conditions for each of these steps as shown in Table 4 were used to manufacture six Group III base oils B1-B6, as shown in Table 6-8. This combination of feed and process has been found to produce base oils with unique compositional characteristics.

Based on the desired conversion rate and VI of the final base oil product, the processing conditions of each of the above steps-hydrogen treatment, hydrocracking, catalytic dewaxing, and hydrofinishing-are adjusted. The conditions used to manufacture Group III base oils of the subject matter of this disclosure can be found in Table 5. The 700 ° F + conversion rate in the first hydrogen treatment stage ranges from 20 to 40%, and the treatment conditions in the first stage include temperatures from 635 ° F to 725 ° F; hydrogen partial pressure from 500 psig to 3000 psig; liquid space Speed from 0.5 hr ^-1 to 1.5 hr ^-1 (preferably from 0.5 hr ^-1 to 1.0 hr ^-1 , most preferably from 0.7 hr ^-1 to 0.9 hr ^-1 ); and hydrogen circulation rate from 3500 scf / bbl To 6000 scf / bbl.

The second stage consisting of hydrocracking, catalytic dewaxing and hydrofinishing is performed in a single reactor with a hydrogen partial pressure of 300 psig to 5000 psig and a hydrogen circulation rate from 1000 scf / bbl to 6000 scf / bbl. Catalysts C, D and E are loaded in the same reactor in the second stage, and the order of feed contact is C, D and E. Adjust the process parameters to achieve the desired 700 ° F + conversion rate of 15-70%, preferably 15-55%.

The processing conditions in the hydrocracking step include temperatures from 250 ° F to 700 ° F; and the liquid space velocity is 0.5 hr ^-1 to 1.5 hr ^-1 .

The processing conditions in the catalytic dewaxing step include temperatures from 250 ° F to 660 ° F; and liquid space velocity from 1.0 hr ^-1 to 3.0 hr ^-1 . The processing conditions in the hydrogen treatment step include a temperature from 250 ° F to 480 ° F; and a liquid space velocity from 0.5 hr ^-1 to 1.5 hr ^-1 .
table 5

Table 5: Continue



Table 5: Continue

Example 3 (comparative):

According to the conventional base oil hydrogen treatment scheme shown in Fig. 1, high-quality vacuum gas oil raw materials are processed. This conventional light treatment scheme widely uses commercially available catalysts and refers to the representative of conventional Group III base oils for hydrogen treatment. The base oil produced by this method is represented by K1 and K2 in the tables and drawings. In addition, the properties of some commercially available base oils can be found in the following tables and diagrams and labeled as commercially available comparative examples. Commercially available comparative base oils are widely available and are representative of the range of Group III products offered on the market today. In short, these commercially available base oils and base oils K1 and K2 are used to illustrate the uniqueness of the base oil of the present invention (the subject of the present disclosure).

Measurement procedures

Use advanced analysis techniques (including gas chromatography mass spectrometry (GCMS), supercritical fluid chromatography (SFC) and carbon-13 nuclear magnetic resonance ( ^13C NMR)) to determine Lubricating oil base oil composition.

The viscosity index (VI) is determined according to ASTM method D2270. VI is about kinematic viscosity measured at 40 ° C and 100 ° C using ASTM method D445. Note that these will be referred to simply as KV100 and KV40. The pour point is measured by ASTM D5950.

The correlation between the results of gas chromatograph distillation (GCD) and the previously established key boiling point and Noack measured using ASTM D5800 was used to estimate Noack volatility. This correlation has been found to predict the measurement results within the reproducibility of ASTM D5800. Similarly, a cold cranking simulator (CCS) estimated at -35 ° C using the Walther equation. The equations entered are the kinematic viscosity measured at 40 ° C and 100 ° C (ASTM D445) and the density at 15.6 ° C (ASTM D4052). On average, these estimated CCS results at -35 ° C match the measurement results of other base oils within the reproducibility of ASTM D5293. Use the above method to estimate all the results of Noack and CCS shown in Table 6-8, so they can be compared with each other.

The unique composition characteristics of the lubricating base oil of the present disclosure can be determined by the amount and distribution of naphthenes, branched carbons, linear carbons, and terminal carbons measured by GCMS, as shown in Figures 5-8. Preferably, the GCMS result is corrected by SFC; however, it is found that the 2R + N / 1RN ratio is the same regardless of whether the GCMS result is corrected by SFC.

SFC was performed on a commercially available supercritical fluid chromatography system. The system is equipped with the following components: a high-pressure pump for delivering supercritical carbon dioxide mobile phase; a temperature controlled column oven; an automatic sampler with a high-pressure liquid injection valve for delivering sample material to the mobile phase Medium; flame ionization detector; mobile phase separator (low dead volume tee); back pressure regulator to maintain CO ₂ in the supercritical phase; and computer and data systems, used Used to control components and record data signals.

For analysis, dilute ~ 75 mg of the sample in 2 mL of toluene and fill it into a standard septum cap autosampler vial. The sample is introduced via a high-pressure sampling valve. SFC separation was performed using multiple commercially available silica packed columns (5 μm with 60 or 30Å pores) connected in series (250 mm length and 2 mm or 4 mm inner diameter). The column temperature is usually maintained at 35 or 40 ° C. For analysis, the column head pressure is usually 250 bar. For a 2 mm inner diameter (id) column, the liquid CO ₂ flow rate is usually 0.3 mL / min, or 2.0 mL / min for a 4 mm id column. The samples run were mainly all saturated compounds eluted before the solvent (toluene in this article). The SFC FID signal is integrated into the paraffin and naphthene areas. The lubricating base oil was analyzed for the split of total alkanes and total naphthenes using chromatographic analysis. Using various standard materials, calibrate the alkane / cycloalkane ratio.

SFC was performed on a commercially available supercritical fluid chromatography system. The system is equipped with the following components: a high-pressure pump for delivering supercritical carbon dioxide mobile phase; a temperature controlled column oven; an automatic sampler with a high-pressure liquid injection valve for delivering sample material to the mobile phase Medium; flame ionization detector; mobile phase separator (low dead volume tee); back pressure regulator to maintain CO ₂ in the supercritical phase; and computer and data systems, used Used to control components and record data signals. For analysis, dilute ~ 75 mg of the sample in 2 mL of toluene and fill it into a standard septum cap autosampler vial. The sample is introduced via a high-pressure sampling valve. SFC separation was performed using multiple commercially available silica packed columns (5 μm with 60 or 30Å pores) connected in series (250 mm length and 2 mm or 4 mm inner diameter). The column temperature is usually maintained at 35 or 40 ° C. For analysis, the column head pressure is usually 250 bar. For a 2 mm inner diameter (id) column, the liquid CO ₂ flow rate is usually 0.3 mL / min, or 2.0 mL / min for a 4 mm id column. The samples run were mainly all saturated compounds eluted before the solvent (toluene in this article). The SFC FID signal is integrated into the paraffin and naphthene areas. The lubricating base oil was analyzed for the split of total alkanes and total naphthenes using chromatographic analysis. Using various standard materials, calibrate the alkane / cycloalkane ratio.

Regarding the GCMS used herein, approximately 50 mg of base oil sample was added to a standard 2 microliter autosampler vial and diluted with methylene chloride solvent to fill the vial. Seal the vial with a septum cap. The samples were run using an Agilent 5975C GCMS (Gas Chromatography Mass Spectrometer) equipped with an autosampler. A non-polar GC column was used to simulate the distillation or carbon number elution characteristics of the GC. The GC column used was Restek Rxi -1ms. The column size is 30 meters in length x 0.32 mm in inner diameter and has a 0.25 micron film thickness for stationary phase coating. The GC column was connected to the GC's split / split-less injection port (maintained at 360 ° C and operated in splitless mode). Helium (~ 7PSI) in constant pressure mode was used for the GC carrier phase. The outlet of the GC column enters the mass spectrometer via a transfer line maintained at 350 ° C. The temperature program of the GC column is as follows: at 100 ° C for 2 minutes, at 5 ° C per minute, at 350 ° C for 30 minutes. The mass spectrometer was operated using an electron impact ionization source (maintained at 250 ° C) and standard conditions (70 eV ionization). Use Agilent Chemstation software to obtain instrument control and mass spectrometry data acquisition. Use the standards provided by the supplier based on the automatic tuning function of the instrument to verify the quality calibration and instrument tuning performance.

Based on the analysis of standard samples containing known normal paraffins, the GCMS retention time of the samples relative to normal paraffins was determined. Then, the mass spectrum is averaged.

Samples were prepared for ¹³ C NMR by dissolving 25-30 wt% of the sample in CDCl ₃ and adding 7% Cr (III) -acetylacetonate (Cr (III) -acetylacetonate) as a relaxing agent. NMR experiments were performed on the JEOL ECS NMR spectrometer, and the proton resonance frequency was 400 MHz. A quantitative ¹³ C NMR experiment was performed using an inverse gated decoupling experiment at 27 ° C, with a 45 ° flip angle, 6.6 seconds between pulses, 64k data points, and 2400 scans. Refer to all spectra of trimethylsiloxane (TMS) at 0 ppm. The spectrum was processed with a line broadening of 0.2-1 Hz, and a baseline correction was applied before manual integration. Integrate the entire spectrum to determine the mol% of the different integrated areas as follows: 32.19-31.90 ppm γ carbon, 30.05-29.65 ppm ε carbon; 29.65-29.17 ppm δ carbon; 22.96-22.76 ppm β carbon; 22.76-22.50 ppm pendant and terminal alpha Radical; 19.87-18.89 ppm side chain methyl; 14.73-14.53 ppm side chain propyl; 14.53-14.35 ppm terminal propyl; 14.35-13.80 ppm alpha carbon; 11.67-11.22 ppm terminal ethyl; and 11.19-10.57 ppm side chain Ethyl.

For the analysis in this article, linear carbon is defined as the sum of α, β, γ, δ, and ε peaks. Branched carbon is defined as the sum of side chain methyl, side chain ethyl, and side chain propyl. Terminal carbon is defined as the sum of terminal methyl, terminal ethyl, and terminal propyl.

Examples of the Group III low-viscosity lubricating oil base oil of the present disclosure and having KV100 in the range of 4-5 cSt are shown in Table 6. For example, comparing the low-viscosity lubricating oil base oil disclosed in this disclosure with a typical Group III low-viscosity base oil having the same viscosity range. Group III base oils with unique compositions manufactured by advanced hydrocracking processes exhibit a range of 4 cSt to 12 cSt base oil KV100. The differences in composition include the ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN), the ratio of branched carbon to linear carbon (BC / SC), and the ratio of branched carbon to terminal carbon (BC / TC), as shown in Tables 6 to 8 and Figures 3 to 8.


Table 6
Properties of Light Neutral Base Stocks



Table 6: Continue



Table 6: Continue



Table 7
Properties of Medium Neutral Base Stocks



Table 7: Continue

Table 7: Continue
Table 8
Nature of Heavy Neutral Base Stocks

Table 8: Continue

Table 8: Continue

Figures 5 and 6 and Tables 6 to 8 illustrate the unique areas that make up the space divided by the disclosed light neutral (LN) base oil. Figure 5 depicts the naphthenic ratio (measured by GCMS) and the degree of branching (measured by NMR), and illustrates that the base oil of the present disclosure occupies a unique area of the chart. This area, indicated by the dotted line, occurs when the cycloalkane ratio value ≤ 0.52 and the degree of branching ≤ 0.21.

A similar situation is carried out using Figure 6, which describes the naphthenic ratio (measured by GCMS) and the nature of branching (measured by NMR). The phrase "essence of branching" means the ratio of branched carbon to terminal carbon, with a higher ratio indicating more internal branching. A lower ratio in this context means that there are more branches near the end of the molecule (terminal C). As in the case of FIG. 5, the base oil of the present disclosure in FIG. 6 occupies a unique area of the chart represented by the dotted line.

As in the case of the LN base oil, FIGS. 7 and 8 and Tables 6 to 8 illustrate the unique regions of the composition space divided by the MN base oil. Figure 7 illustrates the naphthenic ratio (measured by GCMS) and the degree of branching (measured by NMR), and illustrates that the base oil of the present invention occupies a unique area of the chart. This area, indicated by the dotted line, occurs when the cycloalkane ratio value is <0.59 and the degree of branching is ≤ 0.216.

Figure 8 illustrates the cycloalkane ratio (measured by GCMS) and the degree of branching (measured by NMR). The phrase "essence of branching" means the ratio of branched carbon to terminal carbon, with a higher ratio indicating more internal branching. A lower ratio indicates that there are more branches near the end of the molecule (terminal C). The area marked by the dotted line occurs when the ratio of naphthenes is <0.59 and the degree of branching is <0.23. Unlike FIG. 7, the base oil of the present disclosure now occupies the area of the figure represented by lines (rather than boxes).

Example 4

For testing the low temperature of Group III MN base oil, 10W-40 heavy-duty engine oil (HDEO) formula was used as the "parent" formula. The selected formula uses additive packaging, which is formulated for ACEA E6, 9 SSI styrene-isoprene VM, and Class III light neutral co-base oil. The formulation strategy requires that all non-base oil components remain constant between the mixtures; only Group III base oils are different. The formulation is provided in Table 9 and the low temperature results are provided in Figure 5. Once mixed, the low temperature performance of HDEO was tested using a mini-rotary viscometer (MRV) at -30 ° C according to ASTM D4684. Table 9 illustrates the formulations used to test the Group III MN base oil in HDEO. The low temperature efficacy data (MRV) is shown in Table 5.
Table 9

Regarding the nature of MRV and branching of the medium-neutral (MN) base oil, that is, the ratio of branched chain C / terminal C measured by NMR, the lubricant prepared with the Group III base oil of the present disclosure is shown and conventional hydrogen treatment The base oil behaves almost orthogonally. A similar trend can be seen in the MRV behavior of light neutral (MN) base oils blended into 0W-20 PCMO.

Example 5

For testing in fully formulated passenger car motor oil (PCMO), choose the "parent" 0W-20 formula, which uses the market's common GF-5 additive packaging, 50 SSI high ethylene olefin copolymer (high ethylene olefin copolymer, HE OCP) VM, polymethacrylate (PMA) PPD. Table 10 below provides recipes. The formulation strategy keeps all non-base oil components fixed between the mixtures; only the Group III base oil changes. Once mixed, PCMO was tested for low temperature performance in MRV at -40 ° C (ASTM D4684).
Table 10

FIG. 9 illustrates that the MRV behavior of a lubricating composition prepared by mixing light neutral (LN) base oil into 0W-20 PCMO is almost independent of pour point. One notable exception is samples with relatively high pour points (-8 ° C), which show MRV results that are substantially solid (> 400,000 mPa.s) at the test temperature. For clarity, this point is omitted in FIG. 9.

Figure 10 shows the MRV behavior of a lubricating composition prepared with light neutral (LN) base oil mixed into 0W-20 PCMO as a function of naphthenic ratio. Unlike the MRV viscosity plotted against the pour point, the ratio of naphthenes to the lubricating composition prepared with the base oil of the present disclosure and the lubricating composition prepared with the base oil treated with conventional hydrogen showed significantly different. The equation of the line in Figure 10 is:
The line of the composition of the present invention: VI = 89582-167956 * (2R + N / 1RN)
Conventional HDP line: VI = -8840 + 49814 * (2R + N / 1RN)

Fig. 11 shows that the MRV behavior of a lubricating composition prepared by mixing a medium-neutral (MN) base oil into 10W-40 HDEO is roughly independent of the pour point. This is similar to the conclusion reached by LN base oil. Similarly, Figure 12 shows the MRV behavior of a lubricating composition prepared with a medium neutral (MN) base oil mixed into 10W-40 HDEO as a function of naphthenic ratio. Unlike the MRV viscosity plotted against the pour point, the ratio of naphthenes to the lubricating composition prepared with the base oil of the present disclosure and the lubricating composition prepared with the base oil treated with conventional hydrogen showed significantly different. It is worth noting that the same trend is observed in the two viscosity grades of base oils-the lubricating composition prepared with the base oil of the present disclosure shows a negative correlation between the MRV viscosity and the naphthene ratio, while using conventional hydrogen The lubricating composition prepared from the treated base oil showed a positive correlation. This can be seen by the similar appearance of Figures 10 and 12. The equation of the line in Figure 12 is:
The line of the composition of the present invention: VI = 39054-44125 * (2R + N / 1RN)
The conventional line: VI = -1480 + 28197 * (2R + N / 1RN)

PCT and EP terms

1. A lubricating composition comprising: a Group III base oil comprising at least 90 wt% saturated hydrocarbons and having a kinematic viscosity (KV100) at 100 ° C of 4.0 cSt to 12.0 cSt and a viscosity index of 120 to 133, and the ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.43; and an effective amount of one or more lubricant additives.

2. The composition as described in Article 1, wherein the base oil has a KV100 of 4.0 cSt to 5.0 cSt.

3. The composition as described in Article 1, wherein the KV100 of the base oil is from 5.0 cSt to 7.0 cSt.

4. The composition as described in Article 2, wherein the viscosity index is 120 to 133 and is less than or equal to 142 * (1-0.0025 exp (8 * (2R + N / 1RN))).

5. The composition as described in Article 3, wherein the viscosity index is 120 to 133 and is less than or equal to 150.07 * (1-0.0106 * exp (4.5 * (2R + N / 1RN))).

6. A passenger car engine oil composition, comprising: a Group III base oil, the Group III base oil comprising: at least 90 wt% saturated hydrocarbon; a kinematic viscosity at 100 ° C from 4.0 cSt to 5.0 cSt; a viscosity index of From 120 to less than 140; the ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.45; and an effective amount of one or more lubricant additives.

7. The composition as described in Article 6, wherein the viscosity index is 120 to 140 and less than or equal to 142 * (1-0.0025 exp (8 * (2R + N / 1RN))).

8. A heavy-duty diesel engine lubricating oil composition, comprising: a Group III base oil, the Group III base oil comprising: at least 90 wt% saturated hydrocarbons; the kinematic viscosity at 100 ° C is from 5.5 cSt to 7.0 cSt; The viscosity index is from 120 to less than 144; the ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.56; and an effective amount of one or more lubricant additives.

9. The composition as described in Article 8, wherein the viscosity index is 120 to 144 and is less than or equal to 142 * (1-0.0025 exp (8 * (2R + N / 1RN))).

10. A lubricating composition comprising: a Group III base oil, the Group III base oil comprising: at least 90 wt% saturated hydrocarbon; a kinematic viscosity at 100 ° C of 4.0 cSt to 5.0 cSt; a viscosity index of 120 to 140 ; The ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.52; the ratio of branched carbon to linear carbon (BC / SC) is less than or equal to 0.21; additive.

11. The lubricating composition of clause 10, wherein the base oil has a branched carbon to terminal carbon ratio (BC / TC) of less than or equal to 2.1.

12. A lubricating composition, comprising: a Group III base oil, the Group III base oil comprising: at least 90 wt% saturated hydrocarbon; a kinematic viscosity at 100 ° C of 5.0 cSt to 12.0 cSt; a viscosity index of 120 to 140 ; The ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.59; the ratio of branched carbon to linear carbon (BC / SC) is less than or equal to 0.26; and the effective amount of one or more lubricants additive.

13. The lubricating composition according to clause 12, wherein the base oil has a ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) less than 0.59 and BC / TC ≤ 2.3.

14. A lubricating composition, comprising: a Group III base oil, the Group III base oil comprising: at least 90 wt% saturated hydrocarbon; a kinematic viscosity KV (100) at 100 ° C of 4.0 cSt to 5.0 cSt; a viscosity index From 120 to 140; and the ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.45; and an effective amount of one or more lubricant additives.

15. The composition as described in Article 14, wherein the base oil has a KV100 of 4.0 to 4.7.

16. A lubricating composition comprising: a Group III base oil, the Group III base oil comprising: at least 90 wt% saturated hydrocarbon; a kinematic viscosity (KV100) at 100 ° C of 5.0 cSt to 12.0 cSt; a viscosity index of From 120 to 144; the ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.56; and an effective amount of one or more lubricant additives.

17. The composition as described in Article 16, wherein the base oil has a KV100 of 5.5 to 7.0.

All patents and patent applications, test procedures (such as ASTM method, UL method, etc.) and other documents cited in this article are fully incorporated by reference in this case, as long as these disclosures are consistent with the contents of this disclosure and are applicable to allow such All jurisdictions merged.

When a numerical lower limit and an upper numerical limit are listed herein, the range from any lower limit to any upper limit is covered. Although the illustrative embodiments of the present disclosure have been specifically described, it should be understood that those skilled in the art will understand and easily make various other modifications without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended to limit the scope of the patent application to the examples and descriptions set forth herein, but to interpret the patent application scope to include all features of the patentable novelty in this disclosure, including those skilled Will be considered as all features of its equivalent.

This disclosure has been described in many of the above embodiments and specific examples. In view of the above detailed description, those skilled in the art will think of many changes. All these obvious changes are within the full expected scope of the attached patent application.

105‧‧‧Raw materials

110‧‧‧ First reactor

120‧‧‧ Second reactor

125‧‧‧ Hydrogenated effluent

130‧‧‧ Fractionator

132‧‧‧ light end fraction

135‧‧‧ lubricant boiling range fraction

137‧‧‧ Fuel boiling range fraction

140‧‧‧second stage hydrocracking reactor

145‧‧‧ effluent

150‧‧‧hydrorefining reactor

152‧‧‧ light end

157‧‧‧ Fuel boiling range fraction

155‧‧‧ effluent

160‧‧‧Fractionated

FIG. 1 is a multi-stage reaction system according to an embodiment of the present disclosure.

FIG. 2 shows an example of a processing structure suitable for manufacturing the Group III base oil of the present disclosure.

FIG. 3 is a diagram illustrating molecules of polycyclic naphthenes versus molecules of monocyclic naphthenes in light neutral Group III base stock (light neutral Group III base stock) of this disclosure compared to other Group III base oil Diagram of the relationship between the ratio (2R + N / 1RN) and the viscosity index.

FIG. 4 is a diagram illustrating molecules of polycyclic naphthenic hydrocarbons versus molecules of monocyclic naphthenic hydrocarbons of medium neutral Group III base stock (medium neutral Group III base stock) compared to other Group III base oils. Diagram of the relationship between the ratio (2R + N / 1RN) and the viscosity index.

Figure 5 illustrates the ratio of molecules with polycyclic naphthenes to molecules with monocyclic naphthenes (2R + N / 1RN) compared to other Group III base oils in the disclosed light neutral Group III base oil And the degree of branching (branched carbon / linear carbon).

Figure 6 illustrates the ratio of molecules with polycyclic naphthenes to molecules with monocyclic naphthenes (2R + N / 1RN) compared to other Group III base oils according to the disclosed light neutral Group III base oil And the nature of the branch (branched carbon / terminal carbon).

FIG. 7 illustrates that compared with other Group III base oils, the molecular pairs with polycyclic naphthenic hydrocarbons of the medium and high neutral Group III base stock (medium and high neutral Group III base stock) have a single ring Diagram of the relationship between the ratio of naphthenic molecules (2R + N / 1RN) and the degree of branching (branched carbon / linear carbon).

FIG. 8 illustrates that compared to other Group III base oils, the disclosed medium and heavy neutral Group III base stocks (medium and heavy neutral Group III base stock) have polycyclic naphthenic molecule pairs with monocyclic rings Diagram of the relationship between the ratio of alkane molecules (2R + N / 1RN) and the nature of branching (branched carbon / terminal carbon)

FIG. 9 illustrates the pour point and mini-rotary viscosity (MRV) of the light-weight neutral Group III base oil prepared according to the present disclosure compared to other Group III base oils. Diagram of the relationship between behaviors.

10 is a graph illustrating the ratio of molecules with polycyclic naphthenic hydrocarbons to molecules with monocyclic naphthenic hydrocarbons of the formulated light neutral Group III base oil prepared according to the present disclosure compared to other Group III base oils ( 2R + N / 1RN) and the relationship between micro-rotational viscosity (MRV) behavior.

FIG. 11 is a graph illustrating the relationship between the pour point and micro-rotational viscosity (MRV) behavior of the formulated medium-neutral Group III base oil prepared according to the present disclosure compared to other Group III base oils.

FIG. 12 is a graph illustrating the ratio of molecules with polycyclic naphthenes to molecules with monocyclic naphthenes prepared according to the formulated medium-neutral Group III base oil prepared according to the present disclosure compared to other Group III base oils ( 2R + N / 1RN) and the relationship between micro-rotational viscosity (MRV) behavior.

Claims (17)

A lubricating composition, including: Group III base oil, which includes at least 90 wt% saturated hydrocarbons and has a kinematic viscosity (KV100) at 100 ° C of 4.0 cSt to 12.0 cSt, and a viscosity index of 120 to 133; The ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.43; and An effective amount of one or more lubricant additives. The composition as described in item 1 of the scope of patent application, wherein the KV100 of the base oil is from 4.0 cSt to 5.0 cSt. The composition as described in item 1 of the patent application scope, wherein the KV100 of the base oil is from 5.0 cSt to 7.0 cSt. The composition as described in item 2 of the patent application range, wherein the viscosity index is 120 to 133 and is less than or equal to 142 * (1-0.0025 exp (8 * (2R + N / 1RN))). The composition as described in item 3 of the patent application range, wherein the viscosity index is 120 to 133 and is less than or equal to 150.07 * (1-0.0106 * exp (4.5 * (2R + N / 1RN))). A passenger car engine oil composition, including: Group III base oil. The Group III base oil includes: At least 90 wt% saturated hydrocarbon; The kinematic viscosity at 100 ℃ is from 4.0cSt to 5.0cSt; Viscosity index is from 120 to less than 140; The ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.45; and An effective amount of one or more lubricant additives. The composition as described in item 6 of the patent application range, wherein the viscosity index is 120 to 140 and is less than or equal to 142 * (1-0.0025 exp (8 * (2R + N / 1RN))). A heavy-duty diesel engine lubricating oil composition, which includes: Group III base oil, which includes: at least 90 wt% saturated hydrocarbons; The kinematic viscosity at 100 ℃ is from 5.5cSt to 7.0cSt; the viscosity index is from 120 to less than 144; The ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.56; and An effective amount of one or more lubricant additives. The composition as described in item 8 of the patent application range, wherein the viscosity index is 120 to 144 and is less than or equal to 142 * (1-0.0025 exp (8 * (2R + N / 1RN))). A lubricating composition, including: Group III base oil, which includes: at least 90 wt% saturated hydrocarbons; Kinematic viscosity at 100 ℃ is 4.0cSt to 5.0cSt; Viscosity index is 120 to 140; The ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.52; The ratio of branched carbon to linear carbon (BC / SC) is less than or equal to 0.21; and An effective amount of one or more lubricant additives. The lubricating composition as described in item 10 of the patent application range, wherein the base oil has a branched carbon to terminal carbon ratio (BC / TC) less than or equal to 2.1. A lubricating composition, including: Group III base oil. The Group III base oil includes: At least 90 wt% saturated hydrocarbon; The kinematic viscosity at 100 ℃ is 5.0cSt to 12.0cSt; Viscosity index is 120 to 140; The ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.59; The ratio of branched carbon to linear carbon (BC / SC) is less than or equal to 0.26; and An effective amount of one or more lubricant additives. The lubricating composition as described in item 12 of the patent application range, wherein the base oil has a ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) less than 0.59 and BC / TC≤2.3. A lubricating composition, including: Group III base oil. The Group III base oil includes: At least 90 wt% saturated hydrocarbon; The kinematic viscosity (KV100) at 100 ° C is 4.0 cSt to 5.0 cSt; the viscosity index is from 120 to 140; and The ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.45; and An effective amount of one or more lubricant additives. The composition as described in item 14 of the patent application scope, wherein the base oil has a KV100 of 4.0 to 4.7. A lubricating composition, including: Group III base oil. The Group III base oil includes: At least 90 wt% saturated hydrocarbon; The kinematic viscosity (KV100) at 100 ° C is 5.0 cSt to 12.0 cSt; the viscosity index is from 120 to 144; The ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.56; and An effective amount of one or more lubricant additives. The composition as described in item 16 of the patent application scope, wherein the base oil has a KV100 of 5.5 to 7.0.