TW201934734A - Lubricant compositions having improved oxidation performance - Google Patents

Abstract

Disclosed are lubricant compositions with improved oxidation stability which are 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); a unique ratio of branched carbons to straight chain (BC/SC) carbons; and a unique ratio of branched carbons to terminal chain (BC/TC) carbons.

Description

Lubricant composition with improved oxidation performance

The present invention relates to a lubricant composition formulated with a unique Group III base oil and a mixture of these base oils.

Base oil is the main component of the finished lubricant and contributes significantly to the properties of the lubricant. For example, motor oil is a finished crankcase lubricant for automotive and diesel engines, and contains two common ingredients, base stock or base oil (a base oil or a mixture of base oils) And additives. Generally, by changing the mixture of individual lubricating base oils and individual additives, some lubricating base oils are used to make various motor oils.

According to the American Petroleum Institute (API) classification, base oils are classified into five categories based on their saturated hydrocarbon content, sulfur content, and viscosity index (Table 1). Lubricant base oils are typically manufactured on a large scale from non-renewable petroleum sources. Groups I, II, and III base oils are all derived from crude oil and undergo a number of processes such as solvent extraction, solvent or catalytic dewaxing, and hydroisomerization. Group III base oils can also be made from synthetic hydrocarbon liquids obtained from natural gas, coal or other fossil resources. Group IV base oils are polyalphaolefins (PAO) and Decene). 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 a vacuum distillation operation. They can be prepared from petroleum-derived or from syncrude-derived raw materials or from the synthesis of lower molecular weight molecules. Additives are chemicals added to the base oil to improve certain properties of the finished lubricant so that it meets the minimum performance standards for the grade of the finished lubricant. For example, additives added to engine oil can be used to improve the oxidative stability of the lubricant, increase its viscosity, increase its viscosity index, and control deposits. Additives are expensive and can cause miscibility issues with the finished lubricant. For these reasons, it is often desirable to optimize the additive content of motor oils to the minimum required to meet the appropriate requirements.

The need to improve quality is driving formulation changes. For example, regulatory organizations (such as the American Petroleum Institute) help define the specifications of motor oils. More and more engine oil specifications require products with excellent low temperature properties and high oxidation stability. Currently, only a small percentage of base oils blended into engine oils meet the most demanding required oil specifications. Formulators are currently using a range 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 quality of oxidation stability, cleanliness, interfacial properties, and sediment control.

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

The present invention relates to a formulated lubricant composition containing a unique Group III base oil and mixture. This invention relates in part to a lubricating composition prepared from a Group III base oil having a kinematic viscosity at 100 ° C of greater than 2 cSt, such as from 2.0 cSt to 14 cSt or higher, such as from 2 cSt to 12 cSt and from 4 cSt to 7 cSt. These base oils are also referred to as lubricant base oils or products in the present invention. In one embodiment, the present invention provides a lubricating composition comprising a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbons; a kinematic viscosity (KV100) at 100 ° C of 4.0 cSt to 12.0 cSt; viscosity index of 120 to 133; ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) less than 0.43; and an effective amount of one or more lubricant additives; wherein the lubrication composition is oxidatively induced The time is more than 120 minutes.

In another embodiment, the present invention provides a passenger car engine oil composition including a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbons; a kinematic viscosity at 100 ° C of 4.0 cSt 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; The oxidation induction time was greater than 120 minutes.

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

In another embodiment, the present invention provides a lubricating composition comprising a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbons; a kinematic viscosity at 100 ° C of 4.0 cSt to 5.0 cSt; viscosity index of 120 to 140; ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.52; and 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; wherein the oxidation induction time of the lubricating composition is greater than 120 minutes.

In another embodiment, the present invention provides a lubricating composition comprising a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbons; a kinematic viscosity at 100 ° C of 5.0 cSt to 12.0 cSt; viscosity index of 120 to 140; ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.59; and 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; wherein the oxidation induction time of the lubricating oil composition is greater than 120 minutes.

In another embodiment, the present invention provides a lubricating composition comprising a Group III base oil, the Group III base oil having: at least 90 wt% saturated hydrocarbons; a kinematic viscosity (KV100) at 100 ° C of 5.0 cSt to 12.0 cSt; viscosity index of 120 to 144; 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 oxidation induction time was greater than 120 minutes.

The method for manufacturing a diesel fuel and a Group III base oil can obtain a Group III base oil for use in preparing the lubricant composition of the present invention. Generally, the feedstock is processed (eg, having a solvent dewaxed oil feed viscosity index (through a first stage) which is mainly a hydroprocessing unit that raises the viscosity index (VI) and removes sulfur and nitrogen) (solve dewaxed oil feed viscosity index) is a heavy vacuum gas oil feed stock from about 45 to about 150 or a mixed raw material with a solvent dewaxed oil feed viscosity index from about 45 to about 150) . Next is the stripping section, where the light end and diesel are removed. The heavier lubricating oil fraction then enters a second stage where hydrocracking, dewaxing, and hydrofinishing are performed. This combination of raw materials and processing methods produces base oils with unique composition characteristics. These unique composition characteristics were observed in the low, medium and high viscosity base oils manufactured.

Other objects and advantages of the present invention will become apparent from the following detailed description.

All the values in the detailed description and patent application range in this article are modified to "about" or "approximately" the indicated value, and the experimental errors and variations known to those skilled in the art are considered in this technology.

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

As used herein, the term "minor ingredient" means that the amount of ingredient (eg, one or more lubricant additives) present in the lubricating oil of the present invention is less than 50 weight percent.

As used herein, the term "monocyclic cycloalkane" refers to a saturated hydrocarbon group having the general formula C _n H _{2 n} , which is arranged in a single closed ring form, where n is the number of carbon atoms. It is also referred to herein as 1RN.

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

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

As used herein, the term "straight-chain carbon" refers to the sum of the 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 as measured by ¹³ C NMR.

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

Lubricant base oil

According to the present invention, a lubricating composition (for example, an engine lubricating oil composition) having certain kinds of paraffin molecules is provided. The inventors of the present case were surprised to find that a lubricant composition prepared from a base oil having a lower 2R + N / 1RN ratio and / or less branched carbon than existing commercially available base oils, such as described herein The manufacturer of this method shows improved oxidation performance. 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 oxidation efficiency of the formulated oil. The inventors of the present case have also found that a lubricant composition prepared with a base oil having a lower ratio of branched carbon to terminal carbon than existing commercially available base oils also shows improved oxidation efficiency. For example, the oxidation efficiency of the formulated base oil of the present invention (using CEC-L-85 or ASTM D6186) shows a 10-100 times improvement over the lubricants prepared with currently commercially available base oils, such as 20-50 times, such as 30-40 times.

Oxidation efficiency can be determined by oxidation induction time (OIT) measured by pressure differential scanning calorimetry (CEC-L-85). The oxidation induction time was measured by maintaining the sample temperature constant at 175 ° C for a period of time (for example, 2 hours). In at least one embodiment, the lubricant composition of the present invention has an oxidation induction time of 90 minutes or longer, such as 100 minutes or longer, such as 110 minutes or longer, such as 120 minutes or longer. In at least one embodiment, the lubricant composition has an oxidation induction time from 60 minutes to 120 minutes, such as from 70 minutes to 120 minutes, such as from 80 minutes to 120 minutes.

According to various embodiments of the present invention, the base oil used in the lubricating composition of the present invention is an API Group III base oil. A feedstock (e.g., a vacuum gas oil feedstock with a solvent dewaxed oil feed viscosity index of at least 45 (eg, at least 55, such as at least 60 to 150, or 60 to 90) or a solvent dewaxed oil feedstock viscosity index of At least 45 (e.g., at least 55, such as at least 60 to about 150, or 60 to 90) a heavy vacuum gas oil mixed with a major gas gas oil), the advanced class III of the present invention is manufactured by an advanced hydrocracking process Base oil. Class 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 invention may have a kinematic viscosity at 100 ° C. of more than 2 cSt, such as from 2 cSt to 14 cSt, such as from 2 cSt to 12 cSt and from 4 cSt to 12 cSt. The III base oil of the present invention may have a ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) less than about 0.59, and a ratio of branched carbon to linear carbon less than or equal to 0.21. The Group III base oil of the present invention may have a ratio of branched carbon to terminal carbon of less than 2.1.

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 invention 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. Light neutral base oils may have a viscosity index from 102 to 133 and 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 less than or equal to 150.07 * (1-0.0106 * exp (4.5 * (2R + N / 1RN))). In addition, the amount of naphthenes in the base oil of the present invention may be lower than the viscosity range of a commercially known base oil. The naphthene content may be from 30 wt% to 70 wt%.

The Group III base oil of the present invention may have less than 0.03 wt% sulfur, pour point of -10 ° C to -30 ° C, Noack volatility of 0.5 wt% to 20 wt%, and CCS at -35 ° C. (Cold crank simulator (CCS) values are 100 cP to 70,000 cP, and naphthenes are 30 wt% to 70 wt%. Lightweight neutral Group III base oils, that is, with KV100 of 2 cSt to 5 cSt base oil, which can have a Noack volatility of 8 wt% to 20 wt%, a CCS value at -35 ° C of 100 cP to 6,000cP, a pour point of -10 ° C to -30 ° C and a naphthenic content 30 wt% to 60 wt%. The neutral neutral group III base oil of the present invention, that is, a base oil having a KV100 of 5 cSt to 7 cSt, may have a Noack volatility of 2 wt% to 10 wt%, at − The CCS value at 35 ° C is 3,500 cP to 20,000 cP, the pour point is -10 ° C to -30 ° C, and the content of naphthenes is 30 wt% to 60 wt%. The heavy neutral Group III base oil of the present invention, that is, Base oil with KV100 of 7 cSt to 12 cSt, can have Noack volatility of 0.5 wt% to 4 wt%, CCS value at -35 ° C of 10,000 cP to 70,000 cP, pour point of -10 ° C to -30 ° C and naphthenic content from 30 wt% to 70 wt% According to various embodiments of the present invention, the Group III base oil includes 30 wt% to 70% paraffin, or 31 wt% to 69 wt% paraffin, or 32 wt% to 68 wt% paraffin. According to the present invention, In various embodiments of the 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% paraffin. According to various implementations of the present invention For example, a medium-sized neutral Group III base oil may contain 35 wt% to 65 wt%, or 40 wt% to 65 wt%, or 40 wt% to 60 wt% paraffin. According to various embodiments of the present invention, heavy medium Base Group III base oils 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 % Paraffin.

Process

The process described below can be used to make a compositionally advantageous Group III base oil of the present invention. Generally, raw materials (e.g., with solvent dewaxing oil feed viscosity) are processed through a first stage (which is primarily a hydroprocessing unit that increases the viscosity index (VI) and removes sulfur and nitrogen). Heavy vacuum gas oil feedstock with an index from at least 45 (preferably at least 55, and more preferably at least 60 to about 150) or having a solvent dewaxed oil feed viscosity index from at least 45 (preferably at least 55) And more preferably at least 60 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, where hydrocracking, dewaxing, and hydrofinishing are performed. This combination of raw materials and processing methods produces base oils with unique composition characteristics. These unique composition characteristics were observed in the low, medium and high viscosity base oils manufactured.

Compared with the conventional Group III base oil, the process architecture of the present invention manufactures high-quality Group III base oils, which have unique composition characteristics. The compositional advantage can be obtained from the ratio of polycyclic cycloalkanes to monocyclic cycloalkanes of the composition.

The process of the present invention can produce a base oil having a kinematic viscosity (KV100) at 100 ° C of 2 cSt or more, or 4 cSt (e.g., from 4 cSt to 7 cSt), or 6 or more cSt, or greater than or equal to 8 cSt, or greater than or equal to 10 cSt, or greater than or equal to 12 cSt, or greater than or equal to 14 cSt. The base oil produced using the process of the present invention can produce a base oil having a VI of at least 120 to about 145 (for example, 120 to 140 or 120 to 133).

As used herein, a stage may correspond to a single reactor or a plurality of 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 include one or more catalyst beds that contain a hydrotreating catalyst or a dewaxing catalyst. It should be noted that the "bed" of a catalyst may refer to a portion of a physical catalyst bed. For example, the catalyst bed in the reactor may be partially filled with a hydrocracking catalyst and may be partially filled with a dewaxing catalyst. For convenience of explanation, even if two catalysts can be stacked together in a single catalyst bed, the hydrocracking catalyst and the dewaxing catalyst may be conceptually referred to as separate catalyst beds, respectively.

Architecture example

FIG. 1 shows an example of a processing architecture suitable for manufacturing a base oil in the present invention. Figure 2 shows an example of a general processing architecture suitable for processing feedstocks to make base oils. It should be noted that R1 corresponds to 110 in FIG. 2; further, 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 U.S. Patent Application Publication No. 2015 / 715,555. In FIG. 2, the raw material 105 may be introduced into the first reactor 110. A reactor (eg, the first reactor 110) may include a feed inlet and an effluent outlet. The first reactor 110 may correspond to a hydroprocessing reactor, a hydrocracking reactor, or a combination thereof. Optionally, a plurality of reactors can be used for the 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 hydroprocessing reactor, and the second reactor 120 may correspond to a hydrogenation Cracking reactor. Other options for arranging the reactor and / or catalyst in the reactor may also be used for initial hydrotreating 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 removal of light oil and pollutant gases. In the case where the initial stage includes a hydrocracking reactor, the hydrocracking reactor in the initial stage may refer to an additional hydrocracking reactor.

Thereafter, the hydrotreated effluent 125 from the final reactor (eg, reactor 120) in the initial stage may enter the fractionator 130 or enter another separation stage. The fractionator 130 (or other separation stage) may separate the hydrotreated effluent to form one or more fuel boiling range fractions 137, light oil fractions 132, and lubricant boiling range fractions 135. The lubricant boiling point range fraction 135 may generally correspond to the bottom fraction from the fractionator 130. The lubricant boiling point range fraction 135 may be further hydrocracked in the second-stage hydrocracking reactor 140. Thereafter, the effluent 145 from the second-stage hydrocracking reactor 140 may enter the dewaxing / hydrorefining reactor 150 to further improve the properties of the lubricant boiling range product of the final manufactured lubricant. In the architecture shown in FIG. 2, the effluent 155 from the second stage dewaxing / hydrorefining reactor 150 may be fractionated 160 to separate light oil 152 from one or more desired lubricant boiling point range fractions 155. And / or fuel boiling point range fraction 157.

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

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

In one embodiment, the feedstock is introduced into the reactor under hydroprocessing conditions. Then, the hydrotreated effluent enters a fractionator, where the effluent is separated into a fuel boiling point range fraction and a lubricant boiling point range fraction. Then, the boiling point range of the lubricant enters the second stage, where the steps of hydrocracking, dewaxing and hydrorefining are performed. Then, the effluent from the second stage enters the fractionator, where the Group III base oil of the present invention is recovered.

raw material

According to the present invention, a wide range of petroleum and chemical feedstocks can be hydrotreated. Suitable raw materials include whole petroleum crude and reduced petroleum crudes, such as Arab Light, extra Light, Midland Sweet, Delaware Basin, West Texas Intermediate, Eagle Ford, Murban and Mars crude, atmospheric oil , Circulating oil, gas oil (including vacuum gas oil and coking gas oil), light to heavy distillate (including original initial distillate), hydrocracking products, hydrotreating oil, petroleum-derived wax (including pine Waxes), Fischer-Tropsch waxes, raffinate, deasphalted oils, and mixtures of these substances.

One way to define a feedstock is based on the boiling range of the feed. One option to define the boiling point 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 that boils at one or more temperatures. For example, the "T5" boiling / distillation point of a feed is defined as the temperature at which 5 wt% of the feed will boil. Likewise, a "T95" temperature at which the boiling point / distillation point of 95% by weight of the feed will boil. The boiling point (including fractional weight boiling point) can be determined using appropriate ASTM test methods (such as those described in ASTM D2887, D2892, D6352, D7129, and / or D86).

A typical feed comprises, for example, a feed having an initial boiling point of at least 600 ° F (~ 316 ° C); as such, 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; likewise, the T95 and / or T90 boiling point of the feed may 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 hydroprocessing is also used to form the fuel, the feed may include a lower boiling point 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 (determined by UV-Vis absorption or equalization methods (such as ASTM D7419 or ASTM D2007 or equalization methods)) can be at least 20 wt%, or at least 25 wt%, or at least 30 wt %, Or at least 40 wt%, or at least 50 wt%, or at least 60 wt%, such as 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%.

Special raw material ingredients that can be used in the process of the present invention include vacuum gas oil feedstocks (e.g., medium vacuum gas oil feeds (MVGO)), which have a solvent dewaxed oil feed viscosity index from at least 45, at least 50, at least 55, or at least 60 to 150, such as from 65 to 125, at least 65 to 110, from 65 to 100 or 65 to 90.

Other special raw material ingredients that can be used in the process of the present invention include raw materials having a mixed vacuum gas oil feed (e.g., medium vacuum gas oil feed (MVGO)) and heavy atmospheric gas oil feed, where the mixed raw material has a solvent The dewaxed oil feed viscosity index is from at least 45, at least 55, at least 60 to 150, such as from 65 to 145, from 65 to 125, from 65 to 100 or 65 to 90.

Where the hydroprocessing includes a hydroprocessing 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 from 20 wppm to 4000 wppm, or from 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.

First hydrotreating stage-hydrotreating and / or hydrocracking

In various aspects, the first hydrotreating stage can be used to improve one or more qualities of the raw materials for the manufacture of lubricant base oils. Examples of improvements to the feedstock may include, but are not limited to, reducing the heteroatom content of the feedstock, converting on the feedstock to provide a viscosity index increase, and / or performing an aromatic saturation reaction on the feedstock.

With regard to heteroatom removal, conditions in the initial hydroprocessing stage (hydroprocessing and / or hydrocracking) may be sufficient to reduce the sulfur content of the hydrotreated 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 hydrotreated effluent may be from 1 wppm to 250 wppm, or from 1 wppm to 50 wppm, or from 1 wppm to 10 wppm. Additionally or alternatively, conditions in the initial hydroprocessing 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 or less.

In terms of including hydrotreating as part of the initial hydrotreating stage, the hydrotreating catalyst may include any suitable hydrotreating catalyst, such as including Group 8-10 non-noble metals (e.g., selected from Ni, Co, and combinations thereof) A catalyst for at least one of, and at least one Group 6 metal (e.g., selected from Mo, W, and combinations thereof), optionally comprising a suitable support and / or filler material (e.g., including alumina, silicon dioxide, Titanium dioxide, zirconia, or a combination thereof). The hydrotreating catalyst according to aspects of the present invention may be a bulk catalyst or a supported catalyst. Techniques for making supported catalysts are well known in the art. Techniques for making loose 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. This may be via a method in which all metal catalyst precursors are in solution, or via at least one of the precursors being at least partially in solid form and optionally but preferably at least one of the precursors This method is provided only as a solution to make loose metal catalyst particles. For example, providing the metal precursor is 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). For 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, 7,410,924, Nos. 7,544,632 and 8,294,255, U.S. Patent Application Publication Nos. 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 hydroprocessing catalysts. Preferred metal catalysts include cobalt / molybdenum (1-10% Co oxide, 10-40% Mo oxide), nickel / molybdenum (1-10% Ni oxide, 10-40% Co oxide), or nickel / Tungsten (1-10% Ni oxide, 10-40% W oxide) on alumina.

In various aspects, the hydrotreating conditions may include a temperature of 200 ° C to 450 ° C, or 315 ° C to 425 ° C; a pressure of 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 Velocity (LHSV) per hour is 0.2-10 hr ^-1 ; and Hydrogen treatment rates from 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 ).

Hydrotreating 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 typically present in the form of oxides or sulfides on refractory metal oxide supports. 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, having an average pore size of 50 to 200 Å, or 75 to 150 Å; a surface area of 100 to 300 m ² / g, or 150 To 250 m ² / g; and / or pore volume from 0.25 to 1.0 cm ³ / g, or 0.35 to 0.8 cm ³ / g. It is preferred not to use halogens (e.g. fluorine) to promote the support, as this generally increases the acidity of the support.

External surface area and microporous surface area are one way of specifying the total surface area of the catalyst. These surface areas were calculated based on 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). Micropore surface area refers to the surface area obtained based on the one-dimensional pores of the zeolite in the catalyst. Only the zeolite in the catalyst will contribute to this surface area. The external surface area can be attributed to zeolites or binders within the catalyst.

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

A loose catalyst composition comprising one Group 8-10 non-noble metal and two Group 6 metals is preferred. It has been found that in this case, the loose catalyst particles are sintering-resistant. Therefore, the active surface area of the loose catalyst particles is maintained during use. The Mohr ratios of the Group 6 and Group 8-10 non-noble metals usually range from 10: 1 to 1:10, and preferably from 3: 1 to 1: 3. In the case of particles with a core-shell structure, these ratios certainly apply to the metals contained in the shell. If the loose catalyst particles contain more than one Group 6 metal, the ratio of different Group 6 metals is usually not critical. The same applies when more than one Group 8-10 non-precious metal is used. When molybdenum and tungsten are present as a Group 6 metal, the range of the molybdenum: tungsten ratio 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. These metals are preferably present in the form of a compound corresponding to the oxidation of the metal, or, if the catalyst composition has been sulfided, a compound corresponding to the sulfidation of the metal.

In some optional aspects, the loose metal hydrotreating 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 distribution of the loose metal hydrotreating catalyst is approximately the same as the pore size distribution of the conventional hydrotreating catalyst. A loose metal hydrotreating catalyst determined by nitrogen adsorption may have 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 ml / g. Preferably, there are no pores smaller than 1 nm. The loose metal hydrotreating catalyst may have a median diameter of at least 50 nm, or at least 100 nm. The loose metal hydrotreating catalyst may have a median diameter of not more than 5000 μm, or not more than 3000 μm. In one embodiment, the median particle diameter ranges from 0.1 to 50 μm, and the optimal range is from 0.5 to 50 μm.

Examples of suitable hydroprocessing 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 With 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 hydrotreating 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 the conventional hydrocracking catalyst in the second (sweet) reaction stage of the conversion feed, the reaction system may include a high surface area, low acidity conversion catalyst as described herein. Where the lubricant boiling point range feed (e.g., a feed equivalent to a "sweet" feed) has a sufficiently low level of heteroatoms, the feed can be exposed to a high surface area, low acid conversion catalyst, as described herein, without having to first Hydroprocessing is performed to remove heteroatoms.

In various aspects, the conversion conditions selected for the manufacture of lubricant base oils may depend on the amount of conversion desired, the amount of contaminants input to the conversion stage, and potentially other factors. For example, hydrocracking and / or conversion conditions can be selected in a single stage or in the first and / or second stages of a multi-stage system to achieve the desired conversion in the reaction system. 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 of the reaction environment. For example, a feed with 100 wppm or less of sulfur and 50 wppm or less of nitrogen (preferably less than 25 wppm of sulfur and / or less than 10 wppm of nitrogen) represents a sweetener for adding Hydrocracking and / or conversion feed. Feeds with a sulfur content of 250 wppm or more can be processed under acidic conditions. Feeds with intermediate amounts of sulfur can be processed under sweet or sour conditions.

In terms of including hydrocracking as part of the initial hydrotreating stage under acidic conditions, the initial stage hydrocracking catalyst may include any suitable or standard hydrocracking catalyst, such as selected from zeolite beta, zeolite X, zeolite Y, faujasite, ultrastable Y (USY), dealuminated Y zeolite (Deal Y), mordenite (Mordenite), ZSM-3, ZSM-4, ZSM-18, ZSM- 20. ZSM-48, and a zeolitic base thereof, which can advantageously support one or more active metals (e.g. (i) Group 8-10 precious 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, a zeolite material is defined as comprising a material having a recognized zeolite framework structure, such as a framework recognized by the International Zeolite Association. These zeolite materials can correspond to silicoaluminate, silicoaluminophosphate, aluminophosphate, and / or other combinations of atoms that can be used to form a zeolite framework structure. 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 can be found in US2015 / 715555.

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

Available at temperatures from 200 ° C to 450 ° C, hydrogen partial pressures from 250 psig to 5000 psig (~ 1.8 MPag to ~ 34.6 MPag), liquid space velocities per hour from 0.2 hr ^-1 to 10 hr ^-1, and hydrotreating The gas velocity is from 35.6 m ³ / m ³ to 1781 m ³ / m ³ (~ 200 SCF / B to ~ 10,000 SCF / B) in the first stage (or under acidic conditions) of a hydrocracking process. Generally, In most cases, conditions can include a temperature range of 300 ° C to 450 ° C, a hydrogen partial pressure of 500 psig to 2000 psig (~ 3.5 MPag to ~ 13.9 MPag), and a liquid space velocity per hour from 0.3 hr ^-1 To 5 hr ^-1 and hydroprocessing gas rates from 213 m ³ / m ³ to 1068 m ³ / m ³ (~ 1200 SCF / B to ~ 6,000 SCF / B).

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

Another option may be to use a separator between the first and second stages of the hydroprocessing reaction system, which may also perform at least a partial fractionation of the effluent from the first stage. In this regard, the effluent from the first hydroprocessing stage may be separated into at least a portion having a boiling point below the distillate (e.g. diesel) fuel range, a portion having a boiling point in the distillate fuel range, and a boiling point above Part of the distillate fuel range. A distillate fuel range may be defined based on the conventional boiling point range of diesel, 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 a 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 a lower cut point temperature of at least about 300 ° F (149 ° C).

Where interstage separators are also used to make distillate fuel fractions, the boiling point lower than the distillate fuel fraction contains molecules of naphtha boiling point, light oils, and pollutants 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 point range fractions. Boiling points above the distillate fuel range represent potential lubricant base oils. In these respects, the portion having a boiling point higher than the boiling point range of the distillate fuel is used for further hydroprocessing in the second hydroprocessing stage. The portion having a boiling point higher than the boiling point range of the distillate fuel may correspond to a lubricant boiling point range fraction, such as a fraction having a T5 or T10 boiling point of at least about 343 ° C. Optionally, lighter lube oil fractions can be distilled and manipulated in a catalyst dewaxing section in a closed operation, where conditions are adjusted to maximize the yield and properties of each lube oil cut.

The conversion method under sweet conditions may be performed under conditions similar to those used in an acid hydrocracking process, or the conditions may be different. In one embodiment, the conditions of the sweet transition stage may have less stringent conditions than those of the hydrocracking process in the acid stage. Suitable transition 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 temperatures from about 550 ° F (288 ° C) to about 840 ° F (449 ° C), hydrogen partial pressures from about 1000 psia to about 5000 psia (~ 6.9 MPa-a to 34.6 MPa-a), per The hourly liquid space velocity is from 0.05 hr ^-1 to 10 hr ^-1 and the hydroprocessing gas velocity 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 range of 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 rate of the hydrotreating gas 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 hydrotreating, hydrocracking and / or switching beds or stages, such as using hydrotreating conditions on all beds or stages, using hydrocracking conditions on all beds or stages, And / or use transition conditions for all beds or stages. In another embodiment, the pressures for the hydrotreating, hydrocracking, and / or switching beds or stages may be the same.

In another aspect, a hydroprocessing 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 lower hydrogen partial pressures. Suitable conversion conditions for other conversion stages may include, but are not limited to, temperatures from about 550 ° F (288 ° C) to about 840 ° F (449 ° C), and hydrogen partial pressures from about 250 psia to about 5000 psia (1.8 MPa -a to 34.6 MPa-a), liquid space velocity per hour from 0.05 hr ^-1 to 10 hr ^-1 , and hydroprocessing gas rate 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 for other conversion stages may include a temperature range of about 600 ° F (343 ° C) to about 815 ° F (435 ° C), a hydrogen partial pressure of from about 500 psia to about 3000 psia (3.5 MPa -a to 20.9 MPa-a), and the hydroprocessing 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

In various aspects, catalytic dewaxing can be included as part of a second and / or sweet and / or subsequent processing stage (eg, a processing stage that also includes conversion in the presence of a high surface area, low acidity catalyst). Preferably, the dewaxing catalyst is a zeolite (and / or zeolite crystal), which is mainly dewaxed by isomerizing a hydrocarbon feedstock. More preferably, the catalyst is a zeolite having a one-dimensional pore structure. Suitable catalysts include 10-membered cycloporous 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 a zeolite having a ZSM-23 structure having a ratio of silica to alumina from 20: 1 to 40: 1 may sometimes be referred to as SSZ-32. Other zeolite crystals with the same structure as the above materials include Theta-1, NU-10, EU-13, KZ-1, and NU-23. US Patent Nos. 7,625,478, 7,482,300, 5,075,269, and 4,585,747 further disclose dewaxing catalysts that can be used in the process of the present invention, and the above-mentioned US patents are 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 precious 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-noble Group 8-10 metals and Group 6 metals. A suitable combination 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 a metal hydrogenation component is by the incipient wetness method. For example, after combining the zeolite and binder, the combined zeolite and binder can be extruded into catalyst particles. These catalyst particles can then be exposed to a solution containing a suitable metal precursor. Alternatively, the metal can be added to the catalyst by ion exchange, wherein the metal precursor is added to the zeolite (or zeolite and binder) mixture before extrusion.

The amount of metal in the dewaxing catalyst may be at least 0.1 wt%, or at least 0.15 wt%, or at least 0.2 wt%, or at least 0.25%, 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 aspect that the metal is Pt, Pd, another metal Group 8-10 precious metal, or a combination thereof, the metal amount may be from 0.1 to 5 wt%, more preferably from 0.1 to 2 wt%, or from 0.25 to 1.8 wt% , Or 0.4 to 1.5 wt%. For the aspect that the metal is a combination of a non-noble Group 8-10 metal and a Group 6 metal, the combined amount of the metal may be from 0.5 wt% to 20 wt%, or from 1 wt% to 15 wt%, or from 2.5 wt% 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 may 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 silicon dioxide to aluminum oxide 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 include a binding agent. In some embodiments, a low surface area binder is used to formulate a dewaxing catalyst for use in a process according to the present invention. A low surface area binder is said to have 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, such as as low as 40 m ² / g or less.

Alternatively, the binder and zeolite particle size can be selected to provide a catalyst having a desired ratio of micropore surface area to total surface area. In the dewaxing catalyst used according to the present invention, the microporous surface area corresponds to the surface area of one-dimensional pores of the zeolite in the dewaxing catalyst. The total surface area is equivalent to the microporous surface area plus the external surface area. Any binder used in the catalyst will not contribute to the microporous 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 microporous surface area to the total surface area of the dewaxing catalyst may be equal to or greater than 25%.

The zeolite (or other zeolite material) can be combined with a binder in any convenient manner. For example, a bound catalyst can be made by starting with a powder of both zeolite and a binder, combining the powder with added water and grinding to form a mixture, and then extruding the mixture to make a desired size bound catalyst. . Extrusion aids can also be used to modify the extrusion fluid properties of zeolite and binder mixtures. 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 per hour 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 (~ 343 ° C) to 815 ° F (~ 435 ° C), a hydrogen partial pressure of 500 psig to 3000 psig (~ 3.5 MPag to ~ 20.9 MPag), and hydrogenation The process gas rate is from 213 m ³ / m ³ to 1068 m ³ / m ³ (~ 1200 SCF / B to ~ 6000 SCF / B).

In various aspects, hydrorefining and / or aromatic saturation processes can also be provided. Hydrorefining and / or aromatic saturation processes can occur before and / or after dewaxing. Hydrorefining and / or aromatic saturation processes can occur before or after fractionation. If the hydrorefining and / or aromatic saturation process occurs after fractionation, the hydrorefining may be performed on one or more portions of the fractionated product, such as on one or more lubricant base oil portions. Alternatively, the entire effluent from the last conversion or dewaxing process can be hydrorefined and / or aromatic saturated.

In some cases, the hydrorefining 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 hydrorefining. Generally, for practical reasons, such as facilitating the use of lower temperatures in hydrorefining or aromatic saturation processes, the hydrorefining and / or aromatic saturation processes will be dewaxed or hydrocracked in separate reactors. However, after the hydrocracking or dewaxing process but before the fractionation, another hydrorefining reaction can conceptually be considered as part of the second stage of the reaction system.

The hydrorefining and / or aromatic saturation catalyst may include a catalyst having a Group 6 metal, a Group 8-10 metal, and a mixture thereof. In one embodiment, the preferred metal comprises at least one metal sulfide having a strong hydrogenation function. In another embodiment, the hydrorefining catalyst may include Group 8-10 precious metals, such as Pt, Pd, or a combination thereof. A mixture of metals may also be present as a loose metal catalyst, where the amount of metal is 30 wt% or more based on the catalyst. Suitable metal oxide supports include low acid oxides, such as silicon dioxide, aluminum oxide, silicon dioxide-alumina, or titanium dioxide, preferably alumina. A preferred hydrorefining catalyst for aromatic saturation will include at least one metal having a relatively strong hydrogenation function on a porous support. Typical support materials include amorphous or crystalline oxide materials such as alumina, silica, and silica-alumina. The support material can also be modified, for example by halogenation, or in particular fluorination. The metal content of the catalyst is usually up to 20 weight percent for non-noble metals. In one embodiment, a preferred hydrorefining catalyst may include a crystalline material of a catalyst belonging to the M41S class or family. The M41S family of catalysts are mesoporous materials with high silica content. Examples include MCM-41, MCM-48, and MCM-50. A preferred member of this class is MCM-41. If individual catalysts are used for aromatic saturation and hydrorefining, aromatic saturation catalysts can be selected based on the activity and / or selectivity of aromatic saturation, and can be used to improve product specifications (such as product color and polycyclic aromatics). Hydrorefining catalyst was selected for its polynuclear aromatic reduction) activity. US Pat. Nos. 7,686,949, 7,682,502, and 8,425,762 further disclose catalysts that can be used in the process of the present invention, all of which are incorporated herein by reference.

Hydrorefining 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 the liquid space velocity (LHSV) per hour is 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 the hydrocracking in the second stage, fractionation can be performed. Thereafter, at least one of the boiling point range of the lubricant in the second stage hydrocracking effluent may be partially transferred to a dewaxing and / or hydrofining reactor for further processing. In some aspects, hydrocracking and dewaxing can be performed before the second fractionation. In some aspects, hydrorefining, 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 a lubricant base oil product is desired, the lubricant base oil product may be further fractionated to form a plurality of products. For example, the lubricant base oil product can be made into a cut having a viscosity equivalent to 2 cSt, a 4 cSt fraction, a 6 cSt fraction, and / or a fraction greater than 6 cSt. For example, a lubricant base oil fraction having a viscosity of at least 2 cSt may be suitable for use in low pour point applications (such as transformer oil, low temperature hydraulic oil, or automatic transmission fluid )). Lubricant base oil fractions with a viscosity of at least 4 cSt may be fractions with controlled volatility and low pour point, so this fraction is suitable for use in 0W- or 5W- or 10W grade motor oils manufactured according to SAE J300. This fractionation can be performed when the diesel (or other fuel) product is separated from the lubricant base oil product from the second stage, or the fractionation can occur later. Any hydrorefining and / or aromatic saturation can occur before or after fractionation. After fractionation, the lubricant base oil product fraction can be combined with suitable additives for engine oil or other lubricant applications. 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 disclose illustrative process flow schemes that can be used in the present invention, such disclosures The entire contents are incorporated herein by reference.

Lubricant additives

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

If desired, a mixture of base oils can be used, for example, a base oil component and a co-base stock component. In the lubricating oil of the present invention, based on the total weight of the composition, the amount of the co-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 10 to About 90 weight percent. In a preferred aspect of the present invention, low-viscosity and high-viscosity base oils are used in the form of a base oil mixture, which includes low-viscosity base oils from 5 to 95 wt% and high-viscosity base oils from 5 to 95 wt%. A preferred range includes low viscosity base oils from 10 to 90 wt% and high viscosity base oils from 10 to 90 wt%. Based on the total weight of the oil lubricant composition, in an oil lubricant composition of an engine or other mechanical component, the base oil mixture may include a low viscosity base oil from 15 to 85% by weight and a high viscosity from 15 to 85% by weight 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 invention, low viscosity, medium viscosity, and / or high viscosity base oils are present in the oil lubricant composition of an engine or other mechanical component from about 50 to about 99 weight based on the total weight of the composition. The percentage is preferably from about 70 to about 95 weight percent, and more preferably from about 85 to about 95 weight percent.

The formulated lubricating oils that can be used in the present invention may contain one or more other commonly used lubricating oil performance additives, including (but not limited to) anti-wear additives, detergents, dispersants, viscosity modifiers, corrosion inhibitors, anti- Rust inhibitor, metal deactivator, extreme pressure additive, anti-seizure, wax modifier, other viscosity modifier, fluid-loss additive, seal compatibility agent, lubricant, anti-seize Stain, chromophoric agent, defoamer, demulsifier, emulsifier, thickener, wetting agent, gelling agent, tackiness agent, colorant Wait. 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. See also "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 disclosure of which is incorporated herein by reference in its entirety. These additives are typically 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 useful in the present invention need not necessarily be soluble in the lubricating oil. Insoluble additives, such as zinc stearate in oil, may be dispersed in the lubricating oil of the present invention.

When the lubricating oil composition contains one or more additives, the additives are mixed into the composition in an amount sufficient to enable it to perform its intended function. As mentioned above, additives are usually present in the lubricating oil composition as a minor component, and their content is usually less than 50 weight percent, preferably less than about 30 weight percent, and more preferably less than about 15 based on the total weight of the composition. Weight percent. The amount of the additive most commonly 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. Typical amounts of these additives that can be used in the present invention are shown in Table 1 below.

It should be noted that many of the additives are shipped as concentrates by the additive manufacturer, containing one or more additives with certain amounts of base oil diluent. Accordingly, the weight content in Table 1 below and other amounts mentioned herein refer to the amount of the 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.

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

The lubricant composition containing the base oil of the present invention has improved oxidation stability relative to the conventional lubricant composition containing the Group III base oil. The low temperature and oxidation performance of lubricating base oils in formulated lubricants are measured by MRV (Miniature Rotary Viscometer), low temperature performance is measured according to ASTM D4684, or by differential pressure scanning calorimetry (CEC-L-85, It is equivalent to the oxidation efficiency measured by ASTM D6186) measuring the oxidation stability time. The lubricating oil of the present invention is particularly advantageous as a passenger vehicle engine oil (PVEO) product.

Compared with the conventionally known lubricating base oils, the lubricating base oils of the present invention provide some advantages, including (but not limited to) improved oxidation performance in engine oils, such as the differential scanning calorimetry method (CEC-L) -85, which is equivalent to the oxidation induction time measured by ASTM D6186).

The lubricant composition of the present invention can be used for various lubricant-related end uses, such as lubricating oil or grease, for moving and / or interacting mechanical parts, components, or devices or equipment that require lubrication. Available equipment includes engines and machinery. The lubricating base oil of the present invention is suitable for blending automobile crankcase lubricating oil, automobile gear oil, transmission oil, and many industrial lubricants (including circulating lubricants, industrial gear lubricants, greases, compressor oils, pumps, etc. Oils, refrigeration lubricants, hydraulic lubricants, and metalworking fluids. Furthermore, the lubricating base oils of the present invention can be obtained from renewable resources; these base oils can meet the requirements of sustainable products and can meet industry groups or government regulations Prescribed "sustainability" standards.

The following non-limiting examples are provided to illustrate the invention.

Examples

For Examples 1 and 2, feeds A and B were processed according to the method described herein and in FIG. In particular, feeds having the properties described in Table 3 were processed to make a Group III base oil of the present invention. After the stage 1 hydrotreating, the intermediate feed having the properties described in Table 4 was subjected to the stage 2 hydrotreating to produce the Group III base oil of the present invention. Feed A represents a raffinate feed with ~ 67 VI, and Feed B represents a high quality VGO feed with ~ 92 VI.

The treatments in Examples 1 and 2 were performed using 5 different catalysts, the details of which are described below. For these two examples, catalysts A and B were used in the stage 1 hydrotreating, and catalysts C, D, and E were used in the stage 2 hydrotreating.

Catalyst A: A commercially available hydrotreating catalyst consisting of NiMo supported by Al ₂ O ₃ , such as Criterion KF-868.

Catalyst B: A commercially available hydrotreating catalyst consisting of loose NiMoW oxides, such as ExxonMobil Nebula-20.

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

Catalyst D: A commercially available dewaxing catalyst consisting of Pt supported by ZSM-48, such as ExxonMobil MSDW.

Catalyst E: A commercially available hydrorefining catalyst consisting of Pt / Pd supported by MCM-41, such as ExxonMobil MaxSat.

Example 1:

Feed A properties are shown in Table 3. The feed was hydrotreated with two degrees of conversion (i.e., 17% and 33%), and then mixed (44.6 / 55.4) to give a product with 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 the 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.

Feed A (having a solvent dewaxed oil feed viscosity index of about 67) is processed through a first stage (which is mainly a hydrotreating unit that raises the viscosity index (VI) and removes nitrogen and nitrogen). Catalysts A and B are both loaded in the same reactor, and the feed contacts catalyst A first. The hydrotreated feed enters the stripping section where the light oil and diesel are removed. During the stage 1 hydrotreating process, feed A was separated and converted at two different levels (labeled "low" and "high" conversions). 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 performed. The various processing conditions of each of these steps (described below) were used to make five Group III base stocks A1 to A6 with properties as shown in Tables 6 (4-5 cSt), 7 (5-7 cSt), and 8 ( 8-11 cSt). This combination of feed and process has been found to produce Group III base oils with unique compositional properties. These unique composition characteristics were observed in both the lower and higher viscosity base oils manufactured, 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 (hydrotreating, hydrocracking, catalytic dewaxing, and hydrorefining) are adjusted. The conditions used to make the target Group III base oil of the present invention can be found in Table 5. The degree of 700 ° F + conversion in the first hydroprocessing stage ranges from 20 to 40%, and the processing conditions in the first stage include temperatures from 635 ° F to 725 ° F; hydrogen partial pressures from 500 psig to 3000 psig; each The hourly liquid space velocity 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 hydrorefining was performed in a single reactor with a hydrogen partial pressure of 300 psig to 5000 psig and a hydrogen cycle rate from 1000 scf / bbl to 6000 scf / bbl. Catalysts C, D, and E were loaded in the same reactor in the second stage, and the order of contact with the feed was 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 per hour 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 per hour from 1.0 hr ^-1 to 3.0 hr ^-1 . The processing conditions in the hydrotreating step include temperatures from 250 ° F to 480 ° F; and liquid space velocity per hour 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 via a first stage hydroprocessing unit, which raises the viscosity index (VI) and removes sulfur and nitrogen. The hydrotreated feed then enters the stripping section where the light oil and diesel are removed. Catalysts A and B are both loaded in the same reactor, and the feed contacts catalyst A first. During the Phase 1 hydrotreating process, Feed B undergoes a transition and shows properties as shown in Table 4. The heavier lubricating oil fraction from this intermediate then enters the second stage, where hydrocracking, dewaxing and hydrofinishing are performed. Various processing conditions (as shown in Table 4) of each of these steps were used to make six Group III base stocks B1 to B6, as shown in Tables 6 to 8. This combination of feed and process has been found to produce base oils with unique compositional properties.

Based on the desired conversion rate and VI of the final base oil product, the processing conditions of each of the above steps (hydrotreating, hydrocracking, catalytic dewaxing, and hydrorefining) are adjusted. The conditions used to make the target Group III base oil of the present invention can be found in Table 5. The degree of 700 ° F + conversion in the first hydroprocessing stage ranges from 20 to 40%, and the processing conditions in the first stage include temperatures from 635 ° F to 725 ° F; hydrogen partial pressures from 500 psig to 3000 psig; each h liquid hourly space velocity from 0.5 hr ^-1 to 1.5 hr ^-1 (preferably from 0.5 hr ^-1 to 1.0 hr ^-1, and most preferably from 0.7 hr ^-1 to 0.9 hr ^-); and a hydrogen circulation rate from 3500 scf / bbl to 6000 scf / bbl.

The second stage consisting of hydrocracking, catalytic dewaxing and hydrorefining was performed in a single reactor with a hydrogen partial pressure of 300 psig to 5000 psig and a hydrogen cycle rate from 1000 scf / bbl to 6000 scf / bbl. Catalysts C, D, and E were loaded in the same reactor in the second stage, and the order of contact with the feed was 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 per hour 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 per hour from 1.0 hr ^-1 to 3.0 hr ^-1 . The processing conditions in the hydrotreating step include temperatures from 250 ° F to 480 ° F; and liquid space velocity per hour from 0.5 hr ^-1 to 1.5 hr ^-1 .



Example 3 (comparative example):

According to the conventional base oil hydrotreating scheme shown in Fig. 1, high-quality vacuum gas oil feedstock is processed. This conventional hydroprocessing scheme makes extensive use of commercially available catalysts and is representative of the conventional hydrotreated Group III base oils. 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 tables and figures below and labeled as commercially available comparative examples. Commercially available comparative base oils are widely available commercially and are representative of the range of Class III products available on the market today. In summary, 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 matter of the present invention).

Measuring procedure

Determination using advanced analytical techniques (including gas chromatography mass spectrometry (GCMS), supercritical fluid chromatography (SFC), and carbon-13 nuclear magnetic resonance ( ^13C NMR)) Lubricant base oil composition.

The viscosity index (VI) was measured 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 as KV100 and KV40 for short. Pour point was measured by ASTM D5950.

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

The unique composition characteristics of the lubricating base oil of the present invention can be determined by the amount and distribution of naphthenes, branched carbons, linear carbons, and terminal carbons measured by GCMS, as shown in FIGS. 5 to 8. Preferably, the GCMS results are corrected by SFC; however, it is found that the 2R + N / 1RN ratio is the same whether or not the GCMS results are 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 autosampler with a high-pressure liquid injection valve (for delivering sample material to the mobile phase Middle); 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 (For controlling components and recording data signals).

For analysis, a ~ 75 mg sample was diluted in 2 mL toluene and loaded into a standard septum cap autosampler bottle. The sample is introduced via a high-pressure sampling valve. SFC separation was performed using a number of commercially available silicone-filled columns (5 μm with 60 or 30 Å holes) connected in series (250 mm in length and 2 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 for a 4 mm id column, 2.0 mL / min. The samples run were mainly all the saturated compounds eluted before the solvent (toluene herein). The SFC FID signal is integrated into paraffin and naphthene regions. The separation of total paraffin and total naphthenes of the lubricating base oil was analyzed using chromatographic analysis. Calibration of paraffin / cycloparaffin ratios using a variety of standard materials.

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 autosampler with a high-pressure liquid injection valve (for delivering sample material to the mobile phase Middle); 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 (For controlling components and recording data signals). For analysis, a ~ 75 mg sample was diluted in 2 mL of toluene and loaded into a standard gasket-cap autosampler bottle. The sample is introduced via a high-pressure sampling valve. SFC separation was performed using a number of commercially available silicone-filled columns (5 μm with 60 or 30 Å holes) connected in series (250 mm in length and 2 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 for a 4 mm id column, 2.0 mL / min. The samples run were mainly all the saturated compounds eluted before the solvent (toluene herein). The SFC FID signal is integrated into paraffin and naphthene regions. The separation of total paraffin and total naphthenes of the lubricating base oil was analyzed using chromatographic analysis. Calibration of paraffin / cycloparaffin ratios using a variety of standard materials.

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

Based on the analysis of a standard sample containing a known normal paraffin, the GCMS lag time of the sample relative to the lag time of the linear paraffin was determined. The mass spectra were then averaged.

A sample for ¹³ C NMR was prepared by dissolving a 25-30 wt% sample in CDCl ₃ and adding 7% Cr (III) -acetylacetonate (Cr (III) -acetylacetonate) as a relaxant. NMR experiments were performed on a JEOL ECS NMR spectrometer. The proton resonance frequency was 400 MHz. A quantitative ¹³ C NMR experiment was performed at 27 ° C using an inverse gated decoupling experiment, which has a 45 ° flip angle, 6.6 seconds between pulses, 64k data points, and 2400 scans. All spectra refer to trimethylsiloxane (TMS) at 0 ppm. The spectrum was processed with 0.2-1 Hz line broadening and baseline correction was applied before manual integration. The entire spectrum was integrated to determine the mole% of different integration regions 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 methyl groups; 19.87-18.89 ppm pendant methyl groups; 14.73-14.53 ppm pendant propyl groups; 14.53-14.35 ppm terminal propyl groups; 14.35-13.80 ppm alpha carbon; 11.67-11.22 ppm Terminal ethyl; and pendant ethyl at 11.19-10.57 ppm.

For the analysis herein, linear carbon is defined as the sum of the α, β, γ, δ, and ε peaks. Branched carbon is defined as the sum of pendant methyl, pendant ethyl, and pendant propyl. The terminal carbon is defined as the sum of the terminal methyl group, the terminal ethyl group, and the terminal propyl group.

Examples of the Group III low-viscosity lubricating base oils of the present invention and having KV100 in the range of 4-5 cSt are shown in Table 6. For example, the low-viscosity lubricating base oil of the present invention is compared with a typical Group III low-viscosity base oil having the same viscosity range. Group III base stocks with unique compositions made by advanced hydrocracking processes exhibit a base oil KV100 range of 4 cSt to 12 cSt. The composition difference includes the ratio of polycyclic naphthenes to monocyclic naphthenes (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 FIGS. 3 to 8.

5 and 6 and Tables 6 to 8 illustrate unique areas of the composition space divided by the light neutral (LN) base oil of the present invention. 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 invention occupies a unique area of the graph. This region indicated by the dashed line occurs when the value of the naphthenic ratio is ≤ 0.52 and the degree of branching is ≤ 0.21.

A similar situation was performed using Figure 6, which describes the naphthenic ratio (measured by GCMS) and the nature of the branching (measured by NMR). The phrase "branch nature" indicates the ratio of branched carbon to terminal carbon, with higher ratios indicating more internal branches. A lower ratio in this context indicates 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 invention in FIG. 6 occupies a unique area of a graph represented by a dotted line.

As in the case of the LN base oil, FIGS. 7 and 8 and Tables 6 to 8 illustrate unique areas 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 graph. This region, indicated by the dashed line, occurs when the value of the cycloalkane ratio 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 "branch nature" indicates the ratio of branched carbon to terminal carbon, with higher ratios indicating more internal branches. A lower ratio indicates that there are more branches near the end of the molecule (terminal C). The area indicated by the dashed line occurs when the value of the cycloalkane ratio is <0.59 and the degree of branching is <0.23. Unlike FIG. 7, the base oil of the present invention now occupies the area of the graph represented by lines (rather than boxes).

Example 4

Regarding the testing of Group III MN base oil, a 10W-40 heavy-duty engine oil (HDEO) formula was used as the "main body" formula. The selected formulations are packaged in additives that are formulated for ACEA E6, 9 SSI styrene-isoprene VM, and light neutral co-base oils. Also choose Yubase 4 for this purpose. The formulations are provided in Table 9 and the low temperature results are provided in Figure 5. Once mixed, the low temperature efficacy of HDEO was tested at -30 ° C using a mini-rotary viscometer (MRV) in accordance with ASTM D4684. Table 9 illustrates the formula used to test Group III MN base oils in HDEO. Low temperature efficacy data (MRV) are shown in Table 5.

The pour point of medium-sized neutral (MN) base oils is compared to the nature of branching, that is, the branched C / terminal C ratio measured by NMR. Lubricants prepared with the Group III base oils of the present invention exhibit almost orthogonal (irrelevant) behavior to conventional hydrotreated base oils. A similar trend can be seen in the MRV behavior of medium-neutral (MN) base oils mixed into 10W-40 HDEO.

Example 5

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

Example 6

Regarding the testing of lubricant compositions with a Group III MN base oil, a similar strategy was used, but using a 10W-40 heavy engine oil (HDEO) formulation instead of the PCMO formulation. The selected formulations were packaged with additives, formulated for ACEA E6 and 9 SSI styrene-isoprene VM. Unlike the 0W-20 PCMO used to test LN base oils, the 10W-40 HDEO used to test MN base oils requires the use of LN co-base oils. Also choose Yubase 4 for this purpose. The formulations are provided in Table 9 above. Once mixed, HDEO was tested for its low temperature performance in MRV at -30 ° C (ASTM D4684). The results are shown in Table 6 above.

FIG. 9 illustrates that the MRV behavior of a lubricating composition prepared by mixing a light neutral (LN) base oil into 0W-20 PCMO is substantially independent of the 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 the sake of clarity, this point is omitted in FIG. 9.

FIG. 10 shows the MRV behavior related to the naphthenic ratio of a lubricating composition prepared by mixing a light neutral (LN) base oil into 0W-20 PCMO. Unlike the plot of MRV viscosity versus pour point, the naphthenic ratios of the lubricating composition prepared with the base oil of the present invention and the lubricating composition prepared with the conventionally hydrotreated base oil show marked differences. The equation of the line in Figure 10 is:
The line of the composition of the present invention: VI = 89582-167956 * (2R + N / 1RN)
Known HDP line: VI = -8840 + 49814 * (2R + N / 1RN)

FIG. 11 shows that the MRV behavior of the lubricating composition prepared by mixing a medium-neutral (MN) base oil into 10W-40 HDEO is substantially independent of the pour point. This is similar to the conclusion reached by the LN base oil. Similarly, FIG. 12 shows the MRV behavior related to the naphthenic ratio of a lubricating composition prepared by mixing a medium-sized neutral (MN) base oil into 10W-40 HDEO. Unlike the plot of MRV viscosity versus pour point, the naphthenic ratios of the lubricating composition prepared with the base oil of the present invention and the lubricating composition prepared with the conventionally hydrotreated base oil show marked differences. It is worth noting that the same trend was observed in the two base oil grades of viscosity: the lubricating composition prepared with the base oil of the present invention showed a negative correlation between the MRV viscosity and the naphthenic ratio, and Lubricating compositions prepared from hydrotreated base oils showed a positive correlation. This can be seen by the similar appearance of Figs. The equation of the line in Figure 12 is:
Line of the composition of the present invention: VI = 39054-44125 * (2R + N / 1RN)
Conventional composition line: VI = -1480 + 28197 * (2R + N / 1RN)

Example 7

Oxidation induction time (OIT) measured by differential pressure calorimetry (CEC-L-85) was used to test the oxidation performance of the HDEO lubricant composition prepared in Example 4 above. The ASTM equivalent of CEC-L-85 is D6186. The OIT was measured by maintaining the sample temperature at 175 ° C for 2 hours, at which point the test was terminated. Samples that did not oxidize during the two-hour test period are indicated by ">120" in the "OIT" column of Table 11.

13 and 14 are diagrams illustrating oxidation induction time (OIT) and viscosity index (VI). Figure 14 uses the same data as Figure 13, but with a smaller y-axis range. A larger number (corresponding to a longer OIT) indicates better oxidation efficiency. The test ends in 120 minutes (so 120 minutes is the maximum possible value). Figure 14 shows that OIT generally improves with increasing VI, but Figure 13 shows that VI alone cannot explain the significant performance difference of the lubricating composition of the present invention.

15 and 16 are diagrams illustrating OIT versus 2R + N / 1RN (GCMS measurement corrected by SFC). Figure 16 uses the same data as Figure 15 but with a smaller y-axis range. Compared to lubricating compositions prepared with other base oils, both figures indicate that the lubricating composition of the present invention performs better at OIT.

PCT and EP clauses

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

2. The composition as in clause 1, wherein the base oil has a KV100 from 4.0 cSt to 5.0 cSt.

3. The composition as in clause 1, wherein the base oil has a KV100 of from 5.0 cSt to 7.0 cSt.

4. The composition according to item 1 or 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 according to item 1 or 3, wherein the viscosity index is 120 to 133 and 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 having at least 90 wt% saturated hydrocarbons, a kinematic viscosity at 100 ° C of 4.0 cSt to 5.0 cSt, and a viscosity index 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; wherein the oxidation induction time of the oil composition is greater than 120 minutes.

7. The composition as described in clause 6, wherein the viscosity index is 120 to 140 and is 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 having at least 90 wt% saturated hydrocarbons, a kinematic viscosity at 100 ° C of 5.5 cSt to 7.0 cSt, and a viscosity index Is from 120 to less than 144, and 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; wherein the oxidation induction time of the lubricating oil composition For more than 120 minutes.

9. The composition as in clause 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 having at least 90 wt% saturated hydrocarbons, a kinematic viscosity at 100 ° C of 4.0 cSt to 5.0 cSt, and a viscosity index of 120 to 140 , The ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.52, and 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 kinds of lubrication Additives; wherein the oxidation induction time of the lubricating composition is greater than 120 minutes.

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

12. A lubricating composition comprising: a Group III base oil having at least 90 wt% saturated hydrocarbons, a kinematic viscosity at 100 ° C of 5.0 cSt to 12.0 cSt, and a viscosity index of 120 to 140 , The ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) is less than 0.59, and 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 lubricants Additives; wherein the oxidation induction time of the lubricating composition is greater than 120 minutes.

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

14. A lubricating composition comprising: a Group III base oil having: at least 90 wt% saturated hydrocarbons; a kinematic viscosity (KV100) at 100 ° C of 4.0 cSt to 5.0 cSt; and a viscosity index from 120 to 140 A 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; wherein the oxidation induction time of the lubricating composition is greater than 120 minutes.

15. The composition according to clause 14, wherein the KV100 of the base oil is 4.0 to 4.7.

16. A lubricating composition comprising a Group III base oil having: at least 90 wt% saturated hydrocarbons; a kinematic viscosity (KV100) at 100 ° C of 5.0 cSt to 12.0 cSt; and a viscosity index 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; wherein the oxidation induction time of the lubricating composition is greater than 120 minutes.

17. The composition according to clause 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 herein are fully incorporated into this case by reference, as long as these disclosures are consistent with the content of this invention and are applicable to allow such All jurisdictions merged.

When this article lists lower and upper numerical limits, it covers the range from any lower limit to any upper limit. Although the illustrative embodiments of the present invention have been particularly described, it should be understood that those skilled in the art will understand and can easily make various other modifications without departing from the spirit and scope of the invention. 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 scope of the patent application as including all features of the patentable novelty in the present invention, including those skilled in the art. All features considered equivalents.

The invention has been described above with reference to a number of embodiments and specific examples. In view of the above detailed description, many changes will occur to those skilled in the art. All of these obvious variations are within the full intended range of the scope of the attached patent application.

105‧‧‧ raw materials

110‧‧‧first reactor

120‧‧‧second reactor

125‧‧‧Hydrotreated effluent

130‧‧‧ Fractionator

132‧‧‧ light oil fraction

135‧‧‧ Lubricant boiling range fraction

137‧‧‧ Fuel boiling point range fraction

140‧‧‧Second stage hydrocracking reactor

145‧‧‧effluent

150‧‧‧hydrorefining reactor

152‧‧‧ light oil

157‧‧‧ Fuel boiling point range fraction

155‧‧‧ effluent

160‧‧‧ fractionated

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

Figure 2 shows an example of a processing architecture suitable for use in the manufacture of a Group III base oil of the present invention.

FIG. 3 illustrates the molecular weight of polycyclic naphthenes versus molecules with monocyclic naphthenes of the light neutral Group III base stock of the present invention compared to other type III base oils. A graph of the relationship between the ratio (2R + N / 1RN) and the viscosity index.

FIG. 4 illustrates the comparison of molecules with polycyclic naphthenes to molecules with monocyclic naphthenes in the medium neutral Group III base stock of the present invention compared to other group III base oils. A graph of the relationship between the ratio (2R + N / 1RN) and the viscosity index.

FIG. 5 illustrates the ratio of molecules with polycyclic naphthenes to molecules with monocyclic naphthenes (2R + N / 1RN) of the light neutral group III base oil of the present invention compared to other group III base oils. A graph showing the relationship with 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) of the light neutral group III base oil of the present invention compared to other group III base oils. And the nature of the branch (branched carbon / terminal carbon).

FIG. 7 is a diagram illustrating a molecular pair of a polycyclic naphthene having a monocyclic naphthene in a medium and high neutral Group III base stock of the present invention compared to other group III base oils. A graph showing the relationship between the molecular ratio (2R + N / 1RN) and the degree of branching (branched carbon / linear carbon).

FIG. 8 illustrates the ratio of molecules with polycyclic naphthenes to molecules with monocyclic naphthenes (2R + N / 1RN) in the heavy neutral group III base oil of the present invention compared to other group III base oils. ) And the nature of the branch (branched carbon / terminal carbon).

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

Figure 10 illustrates the ratio of molecules with polycyclic naphthenes to molecules with monocyclic naphthenes prepared from the light neutral neutral group III base oil prepared according to the present invention compared to other group III base oils 2R + N / 1RN) and micro-rotational viscosity (MRV) behavior.

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

FIG. 12 illustrates the ratio of molecules with polycyclic naphthenes to molecules with monocyclic naphthenes prepared from the formulated neutral neutral group III base oil prepared according to the present invention compared to other group III base oils ( 2R + N / 1RN) and micro-rotational viscosity (MRV) behavior.

FIG. 13 is a graph of oxidation induction time and viscosity index of a base oil according to an embodiment.

FIG. 14 is a graph of oxidation induction time and viscosity index of a base oil according to an embodiment.

FIG. 15 is a graph of the oxidation induction time of a base oil and 2R + N / 1RN (measured by GCMS corrected by SFC) according to an embodiment.

FIG. 16 is a graph of the oxidation induction time of a base oil and 2R + N / 1RN (measured by SCMS-corrected GCMS) according to an embodiment.

Claims (17)

A lubricating composition comprising: Group III base oil having at least 90 wt% saturated hydrocarbons, a kinematic viscosity (KV100) at 100 ° C of 4.0 cSt to 12.0 cSt, a viscosity index of 120 to 133, and a polycyclic naphthene pair The ratio of monocyclic naphthenes (2R + N / 1RN) is less than 0.43; and An effective amount of one or more lubricant additives; The oxidation induction time of the lubricating composition is more than 120 minutes. For example, the composition of claim 1 in the patent application range, wherein the base oil has a KV100 of from 4.0 cSt to 5.0 cSt. For example, the composition of claim 1 in the patent application range, wherein the base oil has a KV100 of from 5.0 cSt to 7.0 cSt. For example, the composition of the first or second 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))). For example, the composition of the scope of claims 1 or 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))). A passenger car oil composition comprising: Group III base oil having at least 90 wt% saturated hydrocarbons, a kinematic viscosity at 100 ° C of 4.0 cSt to 5.0 cSt, a viscosity index from 120 to less than 140, polycyclic naphthenes versus monocyclic The ratio of naphthenes (2R + N / 1RN) is less than 0.45; and An effective amount of one or more lubricant additives; The oxidation time of the oil composition is greater than 120 minutes. For example, the composition of the sixth item of the patent application, 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 includes: Group III base oil having at least 90 wt% saturated hydrocarbons, a kinematic viscosity at 100 ° C of 5.5 cSt to 7.0 cSt, a viscosity index from 120 to less than 144, and a polycyclic naphthenic hydrocarbon The ratio of naphthenes (2R + N / 1RN) is less than 0.56; and An effective amount of one or more lubricant additives; The oxidation induction time of the lubricating oil composition is greater than 120 minutes. For example, the composition of the eighth 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 comprising: Group III base oil having at least 90 wt% saturated hydrocarbons, a kinematic viscosity at 100 ° C of 4.0 cSt to 5.0 cSt, a viscosity index of 120 to 140, polycyclic naphthenes versus monocyclic naphthenes The ratio (2R + N / 1RN) is less than 0.52, and 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 oxidation induction time of the lubricating composition is more than 120 minutes. For example, the lubricating composition according to item 10 of the application, wherein the ratio of branched carbon to terminal carbon (BC / TC) of the base oil is less than or equal to 2.1. A lubricating composition comprising: Group III base oil having at least 90 wt% saturated hydrocarbons, a kinematic viscosity at 100 ° C of 5.0 cSt to 12.0 cSt, a viscosity index of 120 to 140, polycyclic naphthenes versus monocyclic naphthenes The ratio (2R + N / 1RN) is less than 0.59, and 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 oxidation induction time of the lubricating composition is more than 120 minutes. For example, the lubricating composition of the scope of application for patent No. 12, wherein the ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N / 1RN) of the base oil is less than 0.59, and BC / TC≤2.3. A lubricating composition comprising: Group III base oils having: At least 90 wt% saturated hydrocarbons; Kinematic viscosity (KV100) at 100 ° C is 4.0 cSt to 5.0 cSt; viscosity index is from 120 to 140; The ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.45; and An effective amount of one or more lubricant additives; The oxidation induction time of the lubricating composition is more than 120 minutes. For example, the composition of claim 14 in the patent application range, wherein the KV100 of the base oil is 4.0 to 4.7. A lubricating composition comprising a Group III base oil, the base oil having: At least 90 wt% saturated hydrocarbons; Kinematic viscosity (KV100) at 100 ° C is 5.0 cSt to 12.0 cSt; Viscosity index from 120 to 144; The ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N / 1RN) is less than 0.56; and An effective amount of one or more lubricant additives; The oxidation induction time of the lubricating composition is more than 120 minutes. For example, the composition of claim 16 in the patent application range, wherein the KV100 of the base oil is 5.5 to 7.0.