阅读说明：本技术 具有改善的氧化性能的润滑油组合物 (Lubricating oil compositions having improved oxidative properties ) 是由 丹尼尔·J·艾歇尔德费尔 理查德·C·多尔蒂 小查尔斯·L·贝克 于 2018-12-17 设计创作，主要内容包括：本发明公开了用III类基础油料制备的具有改善的氧化稳定性的润滑油组合物,所述III类基础油料包含大于或等于90重量％的饱和烃；粘度指数是从120至145；独特的多环环烷与单环环烷分子比率(2R+N/1RN)；独特的支链碳与直链碳比率(BC/SC)；以及独特的支链碳与末端碳比率(BC/TC)。(Lubricating oil compositions having improved oxidation stability prepared with a group III basestock comprising greater than or equal to 90 wt.% saturated hydrocarbons; viscosity index is from 120 to 145; a unique polycyclic to monocyclic cycloalkane molecular ratio (2R + N/1 RN); a unique branched carbon to linear carbon ratio (BC/SC); and a unique branched carbon to terminal carbon ratio (BC/TC).)

1. A lubricating composition comprising:

a group III base stock having at least 90 wt% saturates, a kinematic viscosity at 100 ℃ (KV100) of 4.0cSt to 12.0cSt, and a viscosity index of from 120 to 133; and is

A ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.43; and

an effective amount of one or more lubricating oil additives;

wherein the lubricating composition has an oxidation induction time of greater than 120 minutes.

2. The composition of claim 1 wherein the KV100 of the base stock is from 4.0cSt to 5.0 cSt.

3. The composition of claim 1 wherein the KV100 of the base stock is from 5.0cSt to 7.0 cSt.

4. The composition according to claim 1 or 2, wherein the viscosity index is from 120 to 133 and less than or equal to 142 × (1-0.0025 exp (8 × (2R + N/1 RN))).

5. The composition according to claim or 3, wherein the viscosity index is from 120 to 133 and less than or equal to 150.07 × (1-0.0106 × (4.5 × (2R + N/1 RN))).

6. A passenger car oil composition, the passenger car oil composition comprising:

a group III base stock having at least 90 wt% saturates, a kinematic viscosity at 100 ℃ of from 4.0cSt up to 5.0cSt, a viscosity index of from 120 to less than 140;

a ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.45; and

an effective amount of one or more lubricating oil additives;

wherein the oil composition has an oxidation induction time of greater than 120 minutes.

7. The composition according to claim 6, wherein the viscosity index is from 120 to 140 and less than or equal to 142 × (1-0.0025 exp (8 × (2R + N/1 RN))).

8. A heavy duty diesel engine lubricating oil composition comprising:

a group III base stock having at least 90 wt% saturates, a kinematic viscosity at 100 ℃ of from 5.5cSt up to 7.0cSt, a viscosity index of from 120 to less than 144; and is

A ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.56; and

an effective amount of one or more lubricating oil additives;

wherein the lubricating oil composition has an oxidation induction time of greater than 120 minutes.

9. The composition according to claim 8, wherein the viscosity index is from 120 to 144 and less than or equal to 142 x (1-0.0025 exp (8 x (2R + N/1 RN))).

10. A lubricating composition comprising:

a group III base stock having at least 90 wt% saturates, a kinematic viscosity at 100 ℃ of 4.0cSt to 5.0cSt, a viscosity index of 120 to 140, a ratio of polycyclic to monocyclic cycloalkanes (2R + N/1RN) of less than 0.52, and a ratio of branched to linear carbons (BC/SC) of less than or equal to 0.21; and

an effective amount of one or more lubricating oil additives;

wherein the lubricating composition has an oxidation induction time of greater than 120 minutes.

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

12. A lubricating composition comprising:

a group III base stock having at least 90 wt% saturates, a kinematic viscosity at 100 ℃ of from 5.0cSt to 12.0cSt, a viscosity index of from 120 to 140, a ratio of polycyclic naphthenes to monocyclic naphthenes (2R + N/1RN) of less than 0.59; and is

A ratio of branched carbons to linear carbons (BC/SC) less than or equal to 0.26; and

an effective amount of one or more lubricating oil additives;

wherein the lubricating composition has an oxidation induction time of greater than 120 minutes.

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

14. A lubricating composition comprising:

a group III basestock, said group III basestock having:

at least 90% by weight of saturated hydrocarbons;

a kinematic viscosity (KV100) at 100 ℃ of 4.0cSt to 5.0 cSt; viscosity index is from 120 to 140;

a ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.45; and

an effective amount of one or more lubricating oil additives;

wherein the lubricating composition has an oxidation induction time of greater than 120 minutes.

15. The composition of claim 14 wherein the base stock has a KV100 of from 4.0 to 4.7.

16. A lubricating composition comprising a group III base stock having:

at least 90% by weight of saturated hydrocarbons;

a kinematic viscosity (KV100) at 100 ℃ of 5.0cSt to 12.0 cSt;

viscosity index is from 120 to 144;

a ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.56; and

an effective amount of one or more lubricating oil additives;

wherein the lubricating composition has an oxidation induction time of greater than 120 minutes.

17. The composition of claim 16 wherein the base stock has a KV100 of from 5.5 to 7.0.

Technical Field

The present disclosure relates to lubricating oil compositions formulated with unique group III basestocks and blends of such basestocks.

Background

Base oils are the major component in finished lubricants and contribute greatly to the properties of the lubricant. For example, engine oils are finished crankcase lubricating oils intended for use in automotive and diesel engines and contain two common components, namely a base stock or base oil (a base stock or base stock blend) and additives. Generally, several lubricating base oils are used, and various engine oils are produced by changing the mixture of each lubricating base oil and each additive.

Base stocks are classified into five groups according to the American Petroleum Institute (API) classification based on their saturates content, sulfur levels, and viscosity index (table 1) lubricant base stocks are typically produced on a large scale from non-renewable Petroleum sources both I, II and group III base stocks are derived from crude oil by extensive processing such as solvent extraction, solvent or catalytic dewaxing, and hydroisomerization, group III base stocks may also be produced from liquid synthetic hydrocarbons derived from natural gas, coal, or other fossil resources, group IV base stocks are poly α -olefins (PAO) and are produced by oligomerization of α -olefins such as 1-decene, group V base stocks include all base stocks not belonging to groups I-IV such as naphthenes, polyalkyl glycols (PAGs), and esters.

The base oil is typically produced from a higher boiling fraction recovered from a vacuum distillation operation. They may be prepared from petroleum-derived or synthetic crude oil (syncrude) -derived feedstocks, 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 to the minimum performance standard of the finished lubricant grade. For example, additives added to engine oils can be used to improve the oxidation stability, increase the viscosity index, and control deposits of lubricating oils. Additives are expensive and can cause miscibility problems in the finished lubricant. For these reasons, it is often desirable to optimize the additive content of an engine oil to the minimum amount necessary to meet the appropriate requirements.

Driven by the need to improve quality, formulations are undergoing changes. For example, regulatory organizations (e.g., the american petroleum institute) help define engine oil specifications. Increasingly, the specifications of engine oils require products with excellent low temperature properties and high oxidation stability. Currently, only a small fraction of the base oils incorporated into engine oils are able to meet the most stringent engine oil specifications. Currently, formulators are formulating their products using a range of base stocks, including group I, II, III, IV and V base stocks.

Improved qualities in terms of oxidation stability, cleanliness, interfacial properties and deposit control are also urgently needed for industrial oils.

Despite advances in lubricating base oil and lubricating oil formulation technology, there remains a need to improve the oxidation performance (e.g., for longer-life engine and industrial oils) and low temperature performance of formulated oils. In particular, there is a need to improve the oxidation and low temperature properties of formulated oils without adding more additives to the lubricating oil formulation.

Disclosure of Invention

The present disclosure relates to formulated lubricating oil compositions containing unique group III base oils and blends. The present disclosure relates in part to lubricating compositions prepared with group III basestocks having a kinematic viscosity at 100 ℃ greater than 2cSt, e.g., from 2cSt to greater than 14cSt, e.g., from 2cSt to 12cSt, and from 4cSt to 7 cSt. These base stocks are also referred to in this disclosure as lubricant base stocks or products. In one embodiment, the present disclosure provides a lubricating composition comprising a group III base stock having: at least 90% by weight of saturated hydrocarbons; a kinematic viscosity (KV100) at 100 ℃ of 4.0cSt to 12.0 cSt; the viscosity index is from 120 to 133; a ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.43; and an effective amount of one or more lubricating oil additives; wherein the lubricating composition has an oxidation induction time of greater than 120 minutes.

In another embodiment, the present disclosure provides a passenger car motor oil composition comprising a group III base stock having: at least 90% by weight of saturated hydrocarbons; kinematic viscosity at 100 ℃ from 4.0cSt up to 5.0 cSt; a viscosity index of from 120 to less than 140; a ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.45; and an effective amount of one or more lubricating oil additives; wherein the oil composition has an oxidation induction time of greater than 120 minutes.

In another embodiment, the present disclosure provides a heavy duty diesel engine lubricating oil composition comprising a group III basestock, the group III basestock having: at least 90% by weight of saturated hydrocarbons; kinematic viscosity at 100 ℃ is from 5.5cSt up to 7.0 cSt; a viscosity index from 120 to less than 144; a ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.56; and an effective amount of one or more lubricating oil additives; wherein the lubricating oil composition has an oxidation induction time of greater than 120 minutes.

In another embodiment, the present disclosure provides a lubricating composition comprising a group III base stock having: at least 90% by weight of saturated hydrocarbons; a kinematic viscosity at 100 ℃ of 4.0 to 5.0 cSt; a viscosity index of 120 to 140; a ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.52; and the ratio of branched carbons to linear carbons (BC/SC) is less than or equal to 0.21; and an effective amount of one or more lubricating oil additives; wherein the lubricating composition has an oxidation induction time of greater than 120 minutes.

In another embodiment, the present disclosure provides a lubricating composition comprising a group III base stock having: at least 90% by weight of saturated hydrocarbons; a kinematic viscosity at 100 ℃ of 5.0 to 12.0 cSt; viscosity index is from 120 to 140; a ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.59; and the ratio of branched carbons to linear carbons (BC/SC) is less than or equal to 0.26; and an effective amount of one or more lubricating oil additives; wherein the lubricating oil composition has an oxidation induction time of greater than 120 minutes.

In another embodiment, the present disclosure provides a lubricating composition comprising a group III base stock having: at least 90% by weight of saturated hydrocarbons; a kinematic viscosity (KV100) at 100 ℃ of 5.0cSt to 12.0 cSt; viscosity index is from 120 to 144; a ratio of polycyclic cycloalkanes to monocyclic cycloalkanes (2R + N/1RN) of less than 0.56; and an effective amount of one or more lubricating oil additives; wherein the lubricating oil composition has an oxidation induction time of greater than 120 minutes.

Group III basestocks useful in preparing the lubricating oil compositions of the present disclosure may be obtained using processes for producing diesel fuel and group III basestocks. Typically, a feedstock (e.g., a heavy vacuum gas oil feedstock having a solvent dewaxed oil feed viscosity index from about 45 to about 150) or a mixed feedstock having a solvent dewaxed oil feed viscosity index from about 45 to about 150 is processed through a first stage, which is primarily a hydroprocessing unit that increases the Viscosity Index (VI) and removes sulfur and nitrogen. This is followed by a stripping section to remove light ends and diesel. The heavier lubricant fraction then passes to a second stage where it is hydrocracked, dewaxed and hydrofinished. This combination of feedstock and process pathways produces a base stock with unique compositional characteristics. These unique compositional features are observed in the resulting low, medium and high viscosity base stocks.

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

Drawings

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

Fig. 2 shows one example of a processing configuration suitable for producing the group III basestocks of the present disclosure.

Fig. 3 is a graph showing the relationship between the ratio of molecules with multi-cyclic naphthenes to molecules with single-cyclic naphthenes (2R + N/1RN) and viscosity index for light neutral group III base stocks of the present disclosure compared to other group III base stocks.

Fig. 4 is a graph showing the relationship between the ratio of molecules with multi-cyclic naphthenes to molecules with single-cyclic naphthenes (2R + N/1RN) and viscosity index for a medium neutral group III base stock of the present disclosure compared to other group III base stocks.

Fig. 5 is a graph showing the relationship between the ratio of molecules with multi-cyclic naphthenes to molecules with single-cyclic naphthenes (2R + N/1RN) and the degree of branching (branched carbon/straight carbon) compared to other group III base stocks for light neutral group III base stocks of the present disclosure.

Fig. 6 is a graph showing the relationship between the ratio of molecules with multi-cyclic naphthenes to molecules with single-cyclic naphthenes (2R + N/1RN) and the branching properties (branched carbon/terminal carbon) for light neutral group III basestocks of the present disclosure compared to other group III basestocks.

Fig. 7 is a graph showing the relationship between the ratio of molecules with multi-cyclic naphthenes to molecules with single-cyclic naphthenes (2R + N/1RN) and the degree of branching (branched carbon/straight carbon) compared to other group III base stocks for medium and high quality neutral group III base stocks of the present disclosure.

Fig. 8 is a graph showing the relationship between the ratio of molecules with multi-cyclic naphthenes to molecules with single-cyclic naphthenes (2R + N/1RN) and the branching properties (branched carbon/terminal carbon) for medium and heavy neutral group III base stocks of the present disclosure compared to other group III base stocks.

Fig. 9 is a graph showing the relationship between pour point and micro-rotational viscosity (MRV) characteristics of formulated light neutral group III base stocks prepared according to the present disclosure compared to other group III base stocks.

FIG. 10 is a graph showing the relationship between the ratio of molecules with multi-cyclic naphthenes to molecules with single-cyclic naphthenes (2R + N/1RN) and the micro-rotational viscosity (MRV) characteristics for formulated light neutral group III basestocks prepared according to the present disclosure compared to other group III basestocks.

Fig. 11 is a graph showing the relationship between pour point and micro-rotational viscosity (MRV) characteristics of formulated neutral group III basestocks prepared according to the present disclosure compared to other group III basestocks.

FIG. 12 is a graph showing the relationship between the ratio of molecules with multi-cyclic naphthenes to molecules with single-cyclic naphthenes (2R + N/1RN) and the microrotational viscosity (MRV) characteristics for a formulated neutral group III basestock prepared according to the present disclosure compared to other group III basestocks.

Fig. 13 is a graph of oxidation induction time versus viscosity index for base stocks according to one embodiment.

Fig. 14 is a graph of oxidation induction time versus viscosity index for a base stock according to one embodiment.

FIG. 15 is a graph of oxidation induction time versus 2R + N/1RN (measured by SFC-calibrated GCMS) for base stocks according to one embodiment.

FIG. 16 is a graph of oxidation induction time versus 2R + N/1RN (measured by SFC-calibrated GCMS) for base stocks according to one embodiment.

Detailed Description

All numbers within the detailed description and claims herein are to be modified by the term "about" or "approximately" in order to modify the indicated value, taking into account experimental error and variations that would be apparent to one of ordinary skill in the art.

The term "major component" as used herein refers to a component (e.g., a basestock) present in the lubricating oil of the present disclosure in an amount greater than about 50 weight percent (wt%).

The term "minor component" as used herein refers to a component (e.g., one or more lubricating oil additives) present in the lubricating oils of the present disclosure in an amount of less than 50 wt.%.

As used hereinThe term "monocyclic cycloalkane" refers to a monocyclic cycloalkane arranged in a single closed ring having the general formula C_nH_2nWherein n is the number of carbon atoms. Also denoted herein as 1 RN.

The term "polycyclic cycloalkane" as used herein refers to a compound having the formula C arranged in multiple closed rings_nH_2(n+1-r)Wherein n is the number of carbon atoms and r is the number of rings (here, r is>1). Also denoted herein as 2+ RN.

As used herein, "kinematic viscosity at 100 ℃" will be used interchangeably with "KV 100" and "kinematic viscosity at 40 ℃" will be used interchangeably with "KV 40". These two terms should be considered equivalent.

The term "straight chain carbon" as used herein refers to a carbon molecule obtained by passing through¹³The sum of α, β, γ, and peaks as measured by C Nuclear Magnetic Resonance (NMR) spectroscopy.

The term "branched carbon" as used herein is meant to pass through¹³C NMR measured the sum of pendant methyl, pendant ethyl and pendant propyl groups.

The term "terminal carbon" as used herein refers to a carbon atom through which¹³C NMR measured the sum of terminal methyl, terminal ethyl and terminal propyl groups.

Lubricating oil base stocks

In accordance with the present disclosure, lubricating oil compositions, such as engine lubricating oil compositions, having a particular class of paraffinic hydrocarbon molecules are provided the present inventors have unexpectedly discovered that lubricating oil compositions prepared with base stocks having low 2R + N/1RN ratios and/or less branched carbons, such as those produced by methods such as described herein, exhibit improved oxidation performance as compared to existing commercial base stocks.

The oxidation performance may be determined by the Oxidation Induction Time (OIT) as measured by pressurized differential scanning calorimetry (CEC-L-85). The oxidation induction time is measured by maintaining the sample temperature at 175 ℃ for a period of time, such as 2 hours in at least one embodiment, the lubricating oil compositions of the present disclosure have an oxidation induction time of 90 minutes or greater, such as 100 minutes or greater, such as 110 minutes or greater, such as 120 minutes or greater in at least one embodiment, the lubricating oil compositions have an oxidation induction time of 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 disclosure, the base stock used in the lubricating composition of the present disclosure is an apiii base stock. Group III base stocks of the present disclosure can be produced by advanced hydrocracking processes using feedstocks such as vacuum gas oil feedstocks having a solvent dewaxed oil feed viscosity index of at least 45, such as at least 55, such as at least 60 up to 150, or 60 to 90, or mixed feedstocks of heavy vacuum gas oil and heavy atmospheric gas oil having a solvent dewaxed oil feed viscosity index of at least 45, such as at least 55, such as at least 60 to about 150, or 60 to 90. Class III is at least 45, such as at least 55, such as at least 60 to 150, or 60 to 90. Group III basestocks of the present disclosure can have a kinematic viscosity at 100 ℃ greater than 2cSt, e.g., from 2cSt to 14cSt, e.g., from 2cSt to 12cSt and from 4cSt to 12 cSt. The group III basestocks of the present disclosure may have a ratio of polycyclic to monocyclic naphthenes (2R + N/1RN) of less than about 0.59 and a ratio of branched to linear carbons of less than or equal to 0.21. The group III basestocks of the present disclosure may also have a ratio of branched carbon to terminal carbon of less than 2.1.

The API group III base stock used in the lubricating oil composition of the present disclosure may have a ratio of polycyclic to monocyclic naphthenes of less than 0.59, such as less than 0.52, such as less than 0.46, for example less than 0.45 or less than 0.43 for base stocks having a kinematic viscosity at 100 ℃ of 4 to 12 cSt. The base stock may have a (branched carbon to terminal carbon) ratio (BC/TC), where BC/TC ≦ 2.3. The viscosity index of the light neutral base stock may be from 102 to 133 and less than or equal to 142 x (1-0.0025 exp (8 x (2R + N/1 RN))). The viscosity index of the medium and heavy neutral base stocks may be 102 to 133, less than or equal to 150.07 (1-0.0106 exp (4.5 (2R + N/1 RN))). Additionally, the naphthene levels in the base stocks of the present disclosure may be lower compared to commercially known base stocks in this viscosity range. The cycloalkane content may be 30 to 70 wt%.

Group III basestocks of the present disclosure may have less than 0.03 wt% sulfur, a pour point of-10 ℃ to-30 ℃, a Noack volatility of 0.5 wt% to 20 wt%, a CCS (cold start simulator) value at-35 ℃ of 100cP up to 70,000cP, and a naphthene content of 30 wt% to 70 wt%. The light neutral group III basestocks, i.e., those having KV100 from 2cSt to 5cSt, can have a Noack volatility from 8 wt% to 20 wt%, a CCS value at-35 ℃ can be from 100cP to 6,000cP, a pour point can be from-10 ℃ to-30 ℃, and a naphthenic content can be from 30 wt% to 60 wt%. The neutral group III basestocks of the present disclosure, i.e., those having KV100 from 5cSt to 7cSt, can have a Noack volatility from 2 wt% to 10 wt%, a CCS value at-35 ℃ from 3,500cP to 20,000cP, a pour point from-10 ℃ to-30 ℃, and a naphthenic content from 30 wt% to 60 wt%. Heavy neutral group III basestocks of the present disclosure, i.e., those having KV100 from 7cSt to 12cSt, can have a Noack volatility from 0.5 wt% to 4 wt%, CCS values at-35 ℃ can be from 10,000cP to 70,000cP, pour points can be from-10 ℃ to-30 ℃, and naphthene content can be from 30 wt% to 70 wt%. According to various embodiments of the invention, the group III basestock comprises 30 wt% to 70 wt% paraffins, or 31 wt% to 69 wt% paraffins, or 32 wt% to 68 wt% paraffins. According to various embodiments of the present invention, the light neutral group III base stock may contain from 40 wt% to 70 wt%, or from 45 wt% to 65 wt% paraffins. According to various embodiments of the present invention, the medium neutral group III basestock may contain from 35 wt% to 65 wt%, or from 40 wt% to 60 wt% paraffins. According to various embodiments of the present invention, the heavy neutral group III base stock may contain from 30 wt% to 60 wt%, or from 30 wt% to 55 wt%, or from 30 wt% to 50 wt%, or from 30 wt% to 45 wt%, or from 30 wt% to 40 wt% paraffins.

Process for the preparation of a coating

The following process may be used to produce the compositionally advantageous group III base stocks of the present disclosure. Typically, a feedstock, for example, a heavy vacuum gas oil feedstock having a solvent dewaxed oil feed viscosity index of from at least 45, preferably at least 55, and more preferably at least 60 up to about 150, or a mixed feedstock having a solvent dewaxed oil feed viscosity index of from at least about 45, preferably at least 55, and more preferably at least 60 up to about 150, is processed through a first stage which is primarily a hydroprocessing unit that increases the Viscosity Index (VI) and removes sulfur and nitrogen. This is followed by a stripping section to remove light ends and diesel. The heavier lubricant fraction then enters a second stage where it is hydrocracked, dewaxed and hydrofinished. This combination of feedstock and process pathways produces a base stock with unique compositional characteristics. These unique compositional features are observed in the resulting low, medium and high viscosity base stocks.

The process configuration of the present disclosure produces a high quality group III base stock having unique compositional characteristics relative to conventional group III base stocks. The compositional advantage may result from the ratio of polycyclic to monocyclic cycloalkanes in the composition.

The process of the present disclosure can produce a base stock having a kinematic viscosity (KV100) at 100 ℃ of greater than or equal to 2cSt, or greater than or equal to 4cSt, such as from 4cSt to 7cSt, or greater than or equal to 6cSt, or greater than or equal to 8cSt, or greater than or equal to 10cSt, or greater than or equal to 12cSt, or greater than or equal to 14 cSt. Base stocks produced using the process of the present disclosure may produce base stocks having a VI of at least 120 up to about 145, for example 120 to 140 or 120 to 133.

A stage as used herein may correspond to a single reactor or a plurality of reactors. Optionally, multiple parallel reactors may be used to perform one or more of the processes, or multiple parallel reactors may be used for all processes in a stage. Each stage and/or reactor may include one or more catalyst beds containing a hydroprocessing catalyst or a dewaxing catalyst. It is noted that a "bed" of catalyst may refer to a partially solid catalyst bed. For example, the catalyst bed within the reactor may be partially filled with hydrocracking catalyst and partially filled with dewaxing catalyst. For ease of description, the hydrocracking catalyst and the dewaxing catalyst may each be conceptually referred to as separate catalyst beds, even though the two catalysts may be stacked together in a single catalyst bed.

Configuration example

Fig. 1 shows one example of a processing configuration suitable for making base stocks in the present disclosure. Figure 2 shows an example of a general processing configuration suitable for processing feedstock to produce base stocks. Note 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 regarding the processing configuration can be found in U.S. application 2015/715,555. In fig. 2, a feedstock 105 may be introduced into a first reactor 110. A reactor, such as the first reactor 110, may include a feed inlet and an effluent outlet. The first reactor 110 may correspond to a hydrotreating reactor, a hydrocracking reactor, or a combination thereof. Optionally, multiple reactors may be used to enable different conditions to be selected. 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 hydrotreating reactor and the second reactor 120 may correspond to a hydrocracking reactor. Other options may also be used to arrange the reactor and/or the catalyst within the reactor to perform the initial hydrotreating and/or hydrocracking of the feedstock. Optionally, if a configuration includes multiple reactors in the initial stage, gas-liquid separation may be performed between the reactors to enable removal of light ends and contaminant gases. In aspects in which the starting stage includes a hydrocracking reactor, the hydrocracking reactor in the starting stage may be referred to as an additional hydrocracking reactor.

The hydroprocessed effluent 125 from the last reactor of the initial stage (e.g., reactor 120) may then be sent to a fractionation column 130, or other type of separation stage. The fractionation column 130 (or other separation stage) can separate the hydroprocessed effluent to form one or more fuel boiling range fractions 137, light fractions 132, and lube oil boiling range fractions 135. The lube oil boiling-range fraction 135 can often correspond to a bottoms fraction from the fractionation column 130. The lube oil boiling-range fraction 135 can undergo further hydrocracking in a second stage hydrocracking reactor 140. The effluent 145 from the second stage hydrocracking reactor 140 may then be passed to a dewaxing/hydrofinishing reactor 150 to further improve the properties of the finally produced lube oil boiling-range products. In the configuration shown in fig. 2, the effluent 155 from the second stage dewaxing/hydrofinishing reactor 150 can be subjected to fractionation 160 to separate a light fraction 152 and/or a fuel boiling range fraction 157 from one or more desired lube oil boiling range fractions 155.

The configuration in fig. 2 may be such that the second stage hydrocracking reactor 140 and the dewaxing/hydrofinishing reactor 150 are operated at low sulfur (sweet) processing conditions corresponding to equivalent conditions where the sulfur content of the feed (to the second stage) is 100wppm or less. Under such "low sulfur" processing conditions, the configuration of fig. 2, in combination with the use of a high surface area, low acidity catalyst, enables the production of a hydrocracked effluent with reduced or minimized aromatics content.

In the configuration shown in fig. 2, the last reactor in the initial stage (e.g., reactor 120) may be said to be in direct fluid communication with an inlet of a fractionation column 130 (or an inlet of another type of separation stage). Based on the indirect fluid communication provided by the last reactor in the initial stage, the other reactors in the initial stage may be said to be in indirect fluid communication with the inlet of the separation stage. The reactor in the initial stage may be generally referred to as being in fluid communication with the separation stage, based on either direct fluid communication or indirect fluid communication. In some optional aspects, one or more recycle loops may be included as part of the reaction system configuration. The recycle loop enables quenching of effluent between reactors/stages as well as quenching within reactors/stages.

In one embodiment, the feedstock is introduced into the reactor under hydrotreating conditions. The hydrotreated effluent is then sent to a fractionation column where the effluent is separated into a fuel boiling range fraction and a lube oil boiling range fraction. The lube oil boiling-range fraction is then sent to a second stage where hydrocracking, dewaxing and hydrofinishing steps are performed. The effluent from the second stage is then sent to a fractionation column where the group III base stocks of the present disclosure are recovered.

Raw materials

Suitable feedstocks include whole and post-distillation (reduced) petroleum crudes such as, for example, Arab L light, extra L light, Midland Sweet, Delaware base, West Texas intermedite, Eagle Ford, Murban and Mars crudes, atmospheric, cycle, gas, including vacuum and coker gas oils, light to heavy distillates, including raw distillates (rawvirginin distils), hydrocracked oils, hydrotreated oils, petroleum derived waxes (including slack waxes), Fischer-Tropsch (Fischer-Tropsch) waxes, raffinates, deasphalted oils, and mixtures of these materials.

One way to define the feedstock is based on the boiling range of the feed. One option for defining the boiling range is to use the initial boiling point of the feed and/or the final boiling point of the feed. Another option is to characterize the feed based on the amount of feed that boils at one or more temperatures. For example, the "T5" boiling point/distillation point of a feed is defined as the temperature at which boiling will remove 5 wt% of the feed. Similarly, the "T95" boiling point/distillation point is the temperature at which 95 wt% of the feed will boil. Boiling points, including fractional weight Boiling points, may be determined using suitable ASTM test methods such as the procedures described in ASTM D2887, D2892, D6352, D7129 and/or D86.

Typical feeds include, for example, feeds with an initial boiling point of at least 600 ° f (-316 ℃); similarly, the T5 and/or T10 boiling point of the feed can be at least 600 ° F (. about.316 ℃). Additionally or alternatively, the final boiling point of the feed may be 1100 ° f (-593 ℃) or less; similarly, the T95 boiling point and/or the T90 boiling point of the feed may also be 1100 ° F (. about.593 ℃) or less. As a non-limiting example, a typical feed may have a T5 boiling point of at least 600F. (-316℃.) and a T95 boiling point of 1100F. (-593℃.) or less. Optionally, if hydroprocessing is also used to form the fuel, the feed may include a lower boiling range portion. For example, such feeds may have an initial boiling point of at least 350 ° F (-177 ℃) and a final boiling point of 1100 ° F (-593 ℃) or less.

In some aspects, the aromatics content in the feed may 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 from 15 wt.% to 75 wt.% or up to 90 wt.%, as determined by uv-vis absorption or equivalent methods, such as ASTM D7419 or ASTM D2007 or equivalent methods. In particular, the aromatic content may be from 25 wt% to 75 wt%, or from 25 wt% to 90 wt%, or from 35 wt% to 75 wt%, or from 35 wt% to 90 wt%. In other aspects, the feed can have a relatively low aromatics content, such as an aromatics content of 35 wt.% or less, or 25 wt.% or less, such as low as 0 wt.%. In particular, the aromatic content may be from 0 wt% to 35 wt%, or from 0 wt% to 25 wt%, or from 5.0 wt% to 35 wt%, or from 5.0 wt% to 25 wt%.

Specific feedstock components that may be used in the processes of the present disclosure include vacuum gas oil feedstocks (e.g., medium vacuum gas oil feedstocks (MVGO)) having 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 specific feedstock components that may be used in the processes of the present disclosure include feedstocks having a mixed vacuum gas oil feed (e.g., medium vacuum gas oil feed (MVGO)) and a heavy atmospheric gas oil feed, wherein the mixed feedstock has a solvent dewaxed oil feed viscosity index 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.

In aspects where the hydroprocessing includes a hydrotreating process and/or a sulfur-containing (sour) hydrocracking process, the sulfur content of the feed can be from 500wppm to 20000wppm or more, or from 500wppm to 10000wppm, or from 500wppm to 5000 wppm. Additionally or alternatively, the nitrogen content of such feeds can be from 20wppm to 4000wppm, or from 50wppm to 2000 wppm. In some aspects, the feed may correspond to a "low sulfur" feed, such that the feed has a sulfur content of from 25wppm to 500wppm and/or a nitrogen content of from 1wppm to 100 wppm.

First hydroprocessing stage-hydrotreating and/or hydrocracking

In various aspects, the first hydroprocessing stage can be used to improve one or more qualities of a feedstock for lubricant base oil production. Examples of feedstock improvements may include, but are not limited to, reducing the heteroatom content of the feed, converting the feed to provide a viscosity index increase, and/or aromatic saturation of the feed.

With respect to heteroatom removal, the conditions in the initial hydroprocessing stage (hydrotreating and/or hydrocracking) can be sufficient to reduce the sulfur content of the hydroprocessed effluent to 250wppm or less, alternatively 200wppm or less, alternatively 150wppm or less, alternatively 100wppm or less, alternatively 50wppm or less, alternatively 25wppm or less, alternatively 10wppm or less. In particular, the effluent from the hydroprocessing may have a sulfur content of from 1wppm to 250wppm, or from 1wppm to 50wppm, or from 1wppm to 10 wppm. Additionally or alternatively, the conditions in the initial hydroprocessing stage can be sufficient to reduce the nitrogen content to 100wppm or less, or 50wppm or less, or 25wppm or less, or 10wppm or less. In particular, the nitrogen content can be from 1wppm to 100wppm, or from 1wppm to 25wppm, or from 1wppm to 10 wppm.

In aspects that include hydrotreating as part of the initial hydroprocessing stage, the hydrotreating catalyst can include any suitable hydrotreating catalyst, for example, a catalyst comprising at least one group 8-10 non-noble metal (e.g., selected from Ni, Co, and combinations thereof) and at least one group 6 metal (e.g., selected from Mo, W, and combinations thereof), optionally including a suitable support and/or filler material (e.g., comprising alumina, silica, titania, zirconia, or combinations thereof). The hydroprocessing catalyst according to aspects of the invention may be a bulk catalyst or a supported catalyst. Techniques for producing supported catalysts are well known in the art. Techniques for producing bulk metal catalyst particles are known and have been previously described, for example, in U.S. Pat. No.6,162,350, which is incorporated herein by reference. The preparation of the bulk metal catalyst particles may be carried out by a process wherein all metal catalyst precursors are in solution or by a process wherein at least one precursor is at least partially in solid form, optionally but preferably while at least another precursor is provided in solution. For example, providing the metal precursor in at least partially solid form may be achieved by providing a solution of the metal precursor in which the solid and/or precipitated metal is also contained, for example in the form of suspended particles. By way of illustration, some examples of suitable hydrotreating catalysts are described in one or more of the following: U.S. Pat. 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, 7,544,632 and 8,294,255, U.S. patent application publication Nos. 2005/0277545, 2006/0060502, 2007/0084754 and 2008/0132407, and International publication Nos. WO 04/007646, WO 2007/084437, WO 2007/084438, WO 2007/084439 and WO 2007/084471, among others. Preferred metal catalysts include cobalt/molybdenum (1-10% Co as oxide, 10-40% molybdenum as oxide), nickel/molybdenum (1-10% Ni as oxide, 10-40% Co as oxide) or nickel/tungsten (1-10% Ni as oxide, 10-40% W as oxide) on alumina.

In aspects, the hydrotreating conditions can include a temperature of 200 ℃ to 450 ℃, or 315 ℃ to 425 ℃, a pressure of 250psig (1.8 MPag) to 5000psig (34.6 MPag) or 500psig (3.4 MPag) to 3000psig (20.8 MPag), or 800psig (5.5 MPag) to 2500psig (17.2 MPag), and a liquid hourly space velocity (L HSV) of 0.2 to 10hr^-1(ii) a And a hydrogen treatment rate of 200scf/B (35.6m3/m3) to 10,000scf/B (1781m3/m3), or 500(89m3/m3) to 10,000scf/B (1781m3/m 3).

The hydrotreating catalyst is typically a catalyst containing a group 6 metal and a group 8 metalSuitable metal oxide supports include low acid oxides, such as silica, alumina or titania, preferably alumina, in some aspects, the preferred alumina may correspond to porous alumina, such as gamma or η alumina, having an average pore size from 50 toOr 75 toSurface area from 100 to 300m²Per g, or from 150 to 250m²(ii)/g; and/or pore volume from 0.25 to 1.0cm³In terms of/g, or 0.35 to 0.8cm³(ii) in terms of/g. The support is preferably not promoted by halogens such as fluorine as this generally increases the acidity of the support.

External surface area and micropore surface area are one way to characterize the total surface area of a catalyst, these surface areas are calculated based on analysis of nitrogen porosimetry data using the BET method for surface area measurement, see, e.g., Johnson, M.F, L, jour.catal, 52, 425 (1978).

Alternatively, the hydrotreating catalyst may be a bulk metal catalyst, or a combination of stacked beds of supported and bulk metal catalysts. By bulk metal is meant that the catalyst is unsupported, wherein the bulk catalyst particles comprise 30-100 wt.%, calculated as metal oxide, of at least one non-noble group 8-10 metal and at least one group 6 metal, based on the total weight of the bulk catalyst particles, and wherein the bulk catalyst particles have a surface area of at least 10m²(ii) in terms of/g. It is also preferred that the bulk metal hydroprocessing catalyst used herein comprises from 50 to 50, calculated as metal oxide based on the total weight of the particles100 wt.%, and even more preferably 70 to 100 wt.% of at least one group 8-10 non-noble metal and at least one group 6 metal. The amount of the group 6 and group 8-10 non-noble metals can be determined by TEM-EDX.

Bulk catalyst compositions comprising one non-noble group 8-10 metal and two group 6 metals are preferred. It has been found that in this case the bulk catalyst particles are resistant to sintering. Thus, the active surface area of the bulk catalyst particles is maintained during use. The molar ratio of group 6 to non-noble group 8-10 metals generally ranges from 10:1 to 1:10 and preferably from 3:1 to 1:3, these ratios naturally applying to the metal contained in the shell in the case of core-shell structured particles. If more than one group 6 metal is contained in the bulk catalyst particles, the ratio of different group 6 metals is generally not critical. This is also true when more than one non-noble group 8-10 metal is employed. In the case where molybdenum and tungsten are present as the group 6 metal, the ratio of molybdenum to tungsten is preferably in the range of 9:1 to 1: 9. Preferably, the group 8-10 non-noble metal comprises nickel and/or cobalt. It is also preferred that the group 6 metal comprises a combination of molybdenum and tungsten. Preferably, nickel/molybdenum/tungsten and cobalt/molybdenum/tungsten and nickel/cobalt/molybdenum/tungsten compositions are used. These types of precipitates appear to be resistant to sintering. Thus, the active surface area of the precipitate is maintained during use. The metal is preferably present as an oxidic compound of the corresponding metal or, if the catalyst composition has been sulphided, as a sulphided compound of the corresponding metal.

In some optional aspects, the bulk metal hydroprocessing catalyst used herein has a surface area of at least 50m²A/g, and more preferably at least 100m²(ii) in terms of/g. In such aspects, it is also desirable that the pore size distribution of the bulk metal hydroprocessing catalyst be about the same as that of conventional hydroprocessing catalysts. The bulk metal hydroprocessing catalyst can have a pore volume, as determined by nitrogen adsorption, of from 0.05 to 5ml/g, or from 0.1 to 4ml/g, or from 0.1 to 3ml/g, or from 0.1 to 2 ml/g. Preferably, no pores smaller than 1nm are present. The median diameter of the bulk metal hydroprocessing catalyst can be at least 50nm or at least 100 nm. The bodyThe median diameter of the metal hydrotreating catalyst may be no more than 5000 μm or no more than 3000 μm. In one embodiment, the median particle diameter is in the range of 0.1 to 50 μm, most preferably in the range of 0.5 to 50 μm.

Examples of suitable hydrotreating catalysts include, but are not limited to, Albemarle KF 848, KF 860, KF868, KF 870, KF 880, KF 861, KF 905, KF 907, and Nebuli;TK-560BRIM, TK-562HyBRIM, TK-565HyBRIM, TK-569HyBRIM, TK-907, TK-911, and TK-951; axens HR 504, HR 508, HR 526, and HR 544. Hydrotreating may be carried out by one or a combination of the catalysts listed above.

Second stage processing-hydrocracking or conversion conditions

In various aspects, instead of using a conventional hydrocracking catalyst to convert the feedstock in the second (low sulfur) reaction stage, the reaction system may include a high surface area, low acidity conversion catalyst as described herein. In aspects where the lube oil boiling-range feed has a sufficiently low heteroatom content, e.g., the feed corresponds to a "low sulfur" feed, the feed can be contacted with a high surface area, low acidity conversion catalyst as described herein without prior hydroprocessing to heteroatom removal.

In various aspects, the conditions selected for conversion in lube oil base stock production may be determined depending on the desired conversion level, the level of contaminants in the input feed to the conversion stage, and potentially other factors. For example, hydrocracking and/or conversion conditions in a single stage system, or in the first and/or second stages of a multi-stage system, may be selected to achieve a desired level of conversion in the reaction system. Hydrocracking and/or conversion conditions may be referred to as sour or sweet conditions depending on the level of sulfur and/or nitrogen present within the feed and/or present in the gas phase of the reaction environment. For example, a feed having 100wppm or less sulfur and 50wppm or less nitrogen, preferably less than 25wppm sulfur and/or less than 10wppm nitrogen, represents a feed that is hydrocracked and/or converted under low sulfur conditions. Feeds with sulfur contents of 250wppm or more can be processed under sulfur-containing conditions. Feeds with intermediate levels of sulfur can be processed under low sulfur or sulfur containing conditions.

In aspects that include hydrocracking under sulfur-containing conditions as part of the initial hydrocracking stage, the initial hydrocracking catalyst may comprise any suitable or standard hydrocracking catalyst, e.g., a Zeolite matrix selected from the group consisting of β -type Zeolite, X-type Zeolite, Y-type Zeolite, faujasite, ultrastable Y (USY), dealuminized Y (Deal Y), mordenlite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, ZSM-48, and combinations thereof, which may be advantageously loaded with 20 or more active metals (e.g., (i) group 8-10 noble metals, such as platinum and/or palladium, or (ii) group 8-10 non-noble metals, such as nickel, cobalt, iron, and combinations thereof, and group 6 metals, such as molybdenum and/or tungsten.) in this discussion, the zeolitic material is defined to include materials having a recognized Zeolite framework structure, such as the material of the International Zeolite Association (International Association Zeolite Association) framework structure, such as material 715555, or other suitable crystalline materials for forming alumina, silica or other suitable combinations of alumina, silica, alumina, or other suitable Zeolite materials, or other suitable crystalline materials, e.g., silica or silica, in combination with other suitable Zeolite materials.

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

The hydrocracking process in the first stage (or under sulfur-containing conditions) can be carried out at a temperature of 200 ℃ to 450 ℃, a hydrogen partial pressure of from 250psig to 5000psig (-1.8 MPag to-34.6 MPag), and a liquid hourly space velocity of from 0.2hr^-1To 10hr^-1And hydrogen treat gas rates from 35.6m3/m3 to 1781m3/m3 (-200 SCF/B to-10,000 SCF/B). In general, in most cases, conditions may include temperatureA hydrogen partial pressure from 500psig to 2000psig (-3.5 MPag to-13.9 MPag) and a liquid hourly space velocity from 0.3hr over a range of 300 ℃ to 450 DEG C^-1To 5hr^-1And hydrogen treat gas rates from 213m3/m3 to 1068m3/m3 (-1200 SCF/B to-6000 SCF/B).

In a multi-stage reaction system, the first reaction stage of the hydroprocessing reaction system may include one or more hydrotreating and/or hydrocracking catalysts. A separator may then be used between the first and second stages of the reaction system to remove sulfur and nitrogen contaminants in the vapor phase. One option for the separator is to simply perform a gas-liquid separation to remove the contaminants. Another option is to use a separator, such as a flash separator, which can perform the separation at higher temperatures. Such high temperature separators may be used, for example, to separate a feed into a portion having a boiling point below a temperature fractionation point, such as about 350 ° f (177 ℃) or about 400 ° f (204 ℃), and a portion having a boiling point above the temperature fractionation point. In this type of separation, the naphtha boiling range portion of the effluent of the first effect may also be removed, thereby reducing the volume of effluent processed in the second or other subsequent stages. Of course, any low boiling contaminants in the effluent of the first stage will also be separated into portions boiling below the temperature fractionation point. If sufficient contaminant removal is performed in the first stage, the second stage can be operated as a "low sulfur" or low contaminant stage.

Yet another option may be to use a separator between the first and second stages of the hydroprocessing reaction system, which separator may also at least partially fractionate the effluent of the first stage. In this type of aspect, the effluent of the first hydroprocessing stage can be separated into at least a portion boiling below the distillate fuel range (e.g., diesel), a portion boiling in the distillate fuel range, and a portion boiling above the distillate fuel range. The distillate fuel range can be defined based on conventional diesel boiling ranges, such as a lower cut point temperature of at least about 350 ° f (177 ℃) or at least about 400 ° f (204 ℃) to an upper cut point temperature of about 700 ° f (371 ℃) or less or 650 ° f (343 ℃) or less. Optionally, the distillate fuel range can be extended to include additional kerosene, for example, by selecting a lower end fractionation point temperature of at least about 300 ° f (149 ℃).

In aspects where an interstage separator is also used to produce the distillate fuel fraction, the portion boiling below the distillate fuel fraction includes naphtha boiling range molecules, light fractions, and contaminants such as H₂And S. These different products may be separated from each other in any convenient manner. Similarly, one or more distillate fuel fractions may be formed from distillate boiling range fractions, if desired. The portion boiling above the distillate fuel range represents a potential lubricant base stock. In such aspects, the portion boiling above the distillate fuel boiling range is subjected to further hydroprocessing in a second hydroprocessing stage. The portion boiling above the distillate fuel boiling range may correspond to a lube oil boiling range fraction, for example a fraction boiling at least about 343 ℃ in T5 or T10. Optionally, the lighter lubricant fractions may be distilled and operated in a catalyst dewaxing stage in a blocked operation in which conditions are adjusted to maximize the yield and properties of each lubricant cut fraction.

The conversion process under low sulfur conditions may be carried out under conditions similar to those used in the sulfur containing hydrocracking process, or the conditions may be different. In one embodiment, the conditions in the low sulfur conversion stage may be less severe than the conditions of the hydrocracking process in the sulfur-containing stage. Suitable conversion conditions for the non-sulfur containing stage may include, but are not limited to, conditions similar to those of the first or sulfur containing stage. Suitable conversion conditions may include a temperature of about 550F (288℃.) to about 840F (449℃.), a hydrogen partial pressure of from about 1000psia to about 5000psia (-6.9 MPa-a to 34.6MPa-a), and a liquid hourly space velocity of from 0.05hr^-1To 10hr^-1And a hydrotreating gas rate of from 35.6m3/m3 to 1781m3/m3(200SCF/B to 10,000 SCF/B). in other embodiments, conditions may include a temperature in the range of about 600 ° f (343 ℃) to about 815 ° f (435 ℃), a hydrogen partial pressure of from about 1000psia to about 3000psia (6.9 MPa-a to 20.9MPa-a), and a hydrotreating gas rate of from about 213m3/m3 to about 1068m3/m3(1200SCF/B to 6000 SCF/B). L HSV may be from about 0.25hr^-1To about 50hr^-1Or from about 0.5hr^-1To about 20hr^-1And preferably from about 1.0hr^-1To about 4.0hr^-1。

In yet another aspect, the beds or stages of hydrotreating, hydrocracking, and/or converting may use the same conditions, e.g., all beds or stages use hydrotreating conditions, all beds or stages use hydrocracking conditions, and/or conversion conditions for all beds or stages. In yet another embodiment, the pressure of the beds or stages of hydrotreating, hydrocracking, and/or reforming may be the same.

In yet another aspect, the hydroprocessing reaction system can include more than one hydrocracking and/or conversion stage. If multiple hydrocracking and/or conversion stages are present, at least one of the hydrocracking stages may have effective hydrocracking conditions as described above, including a hydrogen partial pressure of at least about 1000psia (-6.9 MPa-a). In such aspects, other (subsequent) conversion processes may be conducted under conditions that may include lower hydrogen partial pressures. Suitable conversion conditions for the additional conversion stage may include, but are not limited to, a temperature of about 550 ° F (288 ℃) to about 840 ° F (449 ℃), a hydrogen partial pressure of from about 250psia to about 5000psia (1.8MPa-a to 34.6MPa-a), and a liquid hourly space velocity of from 0.05hr^-1To 10hr^-1And a hydrotreating gas rate of from 35.6m3/m3 to 1781m3/m3(200SCF/5B to 10,000SCF/B) in other embodiments, conditions for additional conversion stages may include a temperature in the range of about 600 ° f (343 ℃) to about 815 ° f (435 ℃), a hydrogen partial pressure of from about 500psia to about 3000psia (3.5MPa-a to 20.9MPa-a), and a hydrotreating gas rate of from about 213m3/m3 to about 1068m3/m3(1200SCF/B to 6000SCF/B), L HSV may be from about 0.25hr^-1To about 50hr^-1Or from about 0.5hr^-1To about 20hr^-1And preferably from about 1.0hr^-1To about 4.0hr^-1。

Additional second stage processing-dewaxing and hydrofinishing/aromatics saturation

In various aspects, catalytic dewaxing may be included as part of a second and/or low sulfur and/or subsequent processing stage, for example 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 crystals) which is dewaxed primarily by isomerizing a hydrocarbon feedstock. More preferably, the catalyst is a zeolite having a one-dimensional pore structure. Suitable catalysts include 10-membered ring pore zeolites, such as EU-1, ZSM-35 (or ferrierite), ZSM-11, ZSM-57, NU-87, SAPO-11, and ZSM-22. Preferred materials are EU-2, EU-11, ZBM-30, ZSM-48 or ZSM-23. ZSM-48 is most preferred. Note that zeolites having the ZSM-23 structure with a silica to alumina ratio of from 20:1 to 40:1 may sometimes be referred to as SSZ-32. Other zeolite crystals isomorphic with the above materials include Theta-1, NU-10, EU-13, KZ-1 and NU-23. U.S. patent nos. 7,625,478, 7,482,300, 5,075,269 and 4,585,747, which are all incorporated herein by reference in their entirety, further disclose dewaxing catalysts that can be used in the processes of the present disclosure.

In various embodiments, the dewaxing catalyst may further include a metal hydrogenation component. The metal hydrogenation component is typically a group 6 and/or group 8-10 metal. Preferably, the metal hydrogenation component is a group 8-10 noble metal. Preferably, the metal hydrogenation component is Pt, Pd or mixtures thereof. In an alternative preferred embodiment, the metal hydrogenation component may be a combination of a non-noble group 8-10 metal and a group 6 metal. Suitable combinations may include Ni, Co or Fe with Mo or W, preferably Ni with Mo or W.

The metal hydrogenation component may be added to the dewaxing catalyst in any convenient manner. One technique for adding the metal hydrogenation component is by incipient wetness impregnation. For example, after the zeolite and binder are combined, the combined zeolite and binder can be extruded into catalyst particles. These catalyst particles may then be contacted with a solution containing a suitable metal precursor. Alternatively, the metal may be added to the catalyst by ion exchange, wherein the metal precursor is added to the mixture of zeolite (or zeolite and binder) prior to extrusion.

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

Preferably, the dewaxing catalyst may be a catalyst having a low silica to alumina ratio. For example, for ZSM-48, the silica to alumina ratio 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 silica to alumina ratio 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 binder. In some embodiments, the dewaxing catalysts used in the processes of the present invention are formulated using a low surface area binder, meaning a binder having a surface area of 100m²(ii)/g or less, or 80m²(ii)/g or less, or 70m²A/g or less, e.g. as low as 40m²A binder per gram or even lower.

Alternatively, the binder and zeolite particle size may be selected to provide a catalyst having a desired ratio of micropore surface area to total surface area. In the dewaxing catalysts used in the present invention, the micropore surface area corresponds to the surface area of the unidimensional pores from the zeolite in the dewaxing catalyst. The total surface corresponds to the micropore surface area plus the external surface area. Any binder used in the catalyst does not contribute to the micropore surface area and does not significantly increase the total surface area of the catalyst. The external surface area represents the total catalyst surface area minus the balance of the micropore surface area. Both the binder and the zeolite may contribute to the value of the external surface area. Preferably, the ratio of the micropore surface area to the total surface area of the dewaxing catalyst will be equal to or greater than 25%.

The zeolite (or other zeolitic material) may be combined with the binder in any convenient manner. For example, the bound catalyst can be produced by starting with powders of both the zeolite and the binder, combining and milling the powders with added water to form a mixture, and then extruding the mixture to produce the bound catalyst of the desired size. Extrusion aids may also be used to modify the extrusion flow properties of the zeolite and binder mixture. Optionally, a binder, which may be composed of two or more metal oxides, may also be used.

Process conditions in the catalytic dewaxing zone can include: a temperature of from 200 to 450 ℃, preferably 270 to 400 ℃, a hydrogen partial pressure of from 1.8 to 34.6MPag (-250 to 5000psi), preferably 4.8 to 20.8MPag, and a liquid hourly space velocity of from 0.2 to 10hr^-1Preferably 0.5 to 3.0hr^-1And a hydrogen circulation rate of from 35.6 to 1781m3/m3 (-200 to-10,000 SCF/B), preferably 178 to 890.6m3/m3 (-1000 to 5000 SCF/B). Additionally or alternatively, the conditions may include a temperature in the range of 600 degrees Fahrenheit (343 ℃) to 815 degrees Fahrenheit (435 ℃), a hydrogen partial pressure from 500psig to 3000psig (3.5 MPag to 20.9MPag), and a hydrogen treat gas rate from 213m3/m3 to 1068m3/m3(1200SCF/B to 6000 SCF/B).

In various aspects, hydrofinishing and/or aromatics saturation processes may also be provided. Hydrofinishing and/or aromatics saturation may occur before and/or after dewaxing. Hydrofinishing and/or aromatics saturation can occur before or after fractionation. If hydrofinishing and/or aromatic saturation occurs after fractionation, one or more portions of the fractionated products may be hydrofinished, for example, one or more lubricant base stock portions. Alternatively, the entire effluent of the last conversion or dewaxing process may be hydrofinished and/or subjected to aromatics saturation.

In some cases, the hydrofinishing process and the aromatics saturation process may refer to a single process performed using the same catalyst. Alternatively, one type of catalyst or catalyst system may be provided for aromatics saturation, while a second catalyst or catalyst system may be used for hydrofinishing. Typically, for practical reasons, for example, to facilitate the use of lower temperatures for hydrofinishing or aromatics saturation processes, the hydrofinishing and/or aromatics saturation processes will be carried out in a reactor separate from the dewaxing or hydrocracking process. However, additional hydrofinishing reactors after the hydrocracking or dewaxing process but prior to fractionation may still conceptually be considered as part of the second stage of the reaction system.

Hydrofinishing and/or aromatics saturation catalysts may include catalysts comprising a group 6 metal, a group 8-10 metal, and mixtures thereof. In one embodiment, the preferred metal comprises at least one metal sulfide having a strong hydrogenation function. In another embodiment, the hydrofinishing catalyst may comprise a group 8-10 noble metal, such as Pt, Pd, or combinations thereof. The metal mixture may also be present as a bulk metal catalyst, wherein the amount of metal is 30 wt% or more based on the catalyst. Suitable metal oxide supports include low acid oxides such as silica, alumina, silica-alumina or titania, preferably alumina. A preferred hydrofinishing catalyst for aromatics saturation will comprise 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 may also be modified, for example by halogenation, or in particular fluorination. For non-noble metals, the metal content of the catalyst is often up to 20 wt.%. In one embodiment, a preferred hydrofinishing catalyst may include a crystalline material belonging to the M41S class or family of catalysts. The M41S family of catalysts are mesoporous materials with high silica content. Examples include MCM-41, MCM-48, and MCM-50. A preferred member of this class is MCM-41. If separate catalysts are used for aromatics saturation and hydrofinishing, the aromatics saturation catalyst may be selected based on activity and/or selectivity to aromatics saturation, while the hydrofinishing catalyst may be selected based on activity to improve product specifications such as product color and polynuclear aromatics reduction. U.S. patent nos. 7,686,949, 7,682,502, and 8,425,762, which are incorporated herein by reference in their entirety, further disclose catalysts useful in the processes of the present disclosure.

Hydrofinishing conditions can include a temperature from 125 deg.C to 425 deg.C, preferably 180 deg.C to 280 deg.C, a total pressure from 500psig (-3.4 MPag) to 3000psig (-20.7 MPag), preferably 1500psig (-10.3 MPag) to 2500psig (-17.2 MPag), and a liquid hourly space velocity (L HSV) from 0.1hr^-1To 5hr^-1Preferably 0.5hr^-1To 1.5hr^-1。

The second fractionation or separation may be performed at one or more locations after the second or subsequent stage. In some aspects, fractionation may be performed in the second stage after hydrocracking under low sulfur conditions in the presence of a USY catalyst. At least the lube oil boiling range portion of the second stage hydrocracked effluent may then be passed to a dewaxing and/or hydrofinishing reactor for further processing. In some aspects, hydrocracking and dewaxing may be performed prior to the second fractionation. In some aspects, hydrocracking, dewaxing, and aromatics saturation may be performed prior to the second fractionation. Optionally, aromatics saturation and/or hydrofinishing can be performed before the second fractionation, after the second fractionation, or both.

If a lubricant base stock product is desired, the lubricant base stock product may be further fractionated to form a plurality of products. For example, lubricant base stock products corresponding to 2cSt cut fractions, 4cSt cut fractions, 6cSt cut fractions, and/or cut fractions having a viscosity greater than 6cSt may be produced. For example, the lubricant base oil product fraction having a viscosity of at least 2cSt may be a fraction suitable for low pour point applications such as transformer oil, low temperature hydraulic oil or automatic transmission oil. The lubricant base oil product fraction having a viscosity of at least 4cSt may be a fraction having a controlled volatility and a low pour point, such that the fraction is suitable for engine oils made according to the 0W or 5W or 10W grades of SAE J300. This fractionation may be performed while the diesel (or other fuel) product from the second stage is separated from the lubricant base stock product, or the fractionation may occur at a later time. Any hydrofinishing and/or aromatics saturation may occur before or after fractionation. After fractionation, the lubricant base oil product fraction may be combined with suitable additives for use as an engine oil or for other lubricating services. Illustrative process flow schemes useful in the present disclosure are disclosed in 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, the disclosures of which are incorporated herein by reference in their entirety.

Lubricating oil additive

The base oil constitutes the major component of the lubricating oil composition for engine or other machine component oils of the present disclosure, and is generally present in an amount of from about 50 to about 99 weight percent, preferably from about 70 to about 95 weight percent, and more preferably from about 85 to about 95 weight percent, based on the total weight of the composition. As described herein, the additives constitute a minor component of the disclosed engine or other machine component oil lubricating oil compositions and are generally present in an amount of less than about 50 weight percent, preferably less than about 30 weight percent, more preferably less than about 15 weight percent, based on the total weight of the composition.

Mixtures of base oils, e.g., base stock components and co-base stock components, may be used if desired. The co-basestock component is present in the lubricating oil of the present disclosure in an amount of from about 1 to about 99 weight percent, preferably from about 5 to about 95 weight percent, more preferably from about 10 to about 90 weight percent, based on the total weight of the composition. In a preferred aspect of the present disclosure, the low and high viscosity base stocks are used in the form of a base stock blend comprising from 5 to 95 wt% of the low viscosity base stock and from 5 to 95 wt% of the high viscosity base stock. Preferred ranges include from 10 to 90 wt% of the low viscosity base stock and from 10 to 90 wt% of the high viscosity base stock. The base stock blend may be present in an engine or other machine component oil lubricating oil composition in from 15 to 85 wt% of a low viscosity base stock and from 15 to 85 wt% of a high viscosity base stock, preferably from 20 to 80 wt% of a low viscosity base stock and from 20 to 80 wt% of a high viscosity base stock, and more preferably from 25 to 75 wt% of a low viscosity base stock and from 25 to 75 wt% of a high viscosity base stock, based on the total weight of the oil lubricating oil composition.

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

Formulated lubricating oils useful in the present disclosure may contain one or more other conventional lubricating oil performance Additives including, but not limited to, antiwear Additives, detergents, dispersants, viscosity modifiers, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure Additives, anti-seizure agents, wax modifiers, other viscosity modifiers, fluid loss Additives, seal compatibilisers, lubricity agents, anti-fouling agents, colour developers, anti-foaming agents, demulsifiers, emulsifiers, thickeners, wetting agents, gelling agents, masticants, colorants, and others for a review of many conventional Additives, see "lubricating oil Additives, Chemistry and Applications" (L ubricant Additives, Chemistry and Applications), "L. r. rudnick master edition, Marcel dekkkerrm, inc.270 new york madison great street, n.10016, 2003, and Klamann lubricating oils and related products (L and reidducts), Verlag Chemistry, delield, bediend bereaf, Corporation, published under the teachings of the same patent publication No. wo, published under the content of published by No. 99.7,85, published under the content of these Additives, published under No. 99.7,177, published under the content of published by published under No. 250.

Additives useful in the present disclosure need not be soluble in the lubricating oil. Insoluble additives in the oil, such as zinc stearate, may be dispersed in the lubricating oil of the present disclosure.

When a lubricating oil composition contains one or more additives, the additive is incorporated into the composition in an amount sufficient for it to perform its intended function. As noted above, the additives are typically present in the lubricating oil composition as a minor component, typically in an amount of less than 50 wt.%, preferably less than about 30 wt.%, more preferably less than about 15 wt.%, based on the total weight of the composition. Additives are most often added to lubricating oil compositions in amounts of at least 0.1 wt.%, preferably at least 1 wt.%, more preferably at least 5 wt.%. Typical amounts of such additives useful in the present disclosure are shown in table 1 below.

It is noted that many additives are shipped from additive manufacturers as concentrates containing one or more additives, along with a certain amount of base oil diluent. Thus, the weight measurements in Table 1 below, as well as other amounts referred to herein, refer to the amount of active ingredient (i.e., the undiluted portion of the ingredient). The weight percentages (wt%) indicated below are based on the total weight of the lubricating oil composition.

TABLE 2

Typical amounts of other lubricating oil components

The foregoing additives are all commercially available materials. These additives may be added separately, but are typically pre-combined in packages available from suppliers of lubricating oil additives. Additive packages having a variety of ingredients, proportions and characteristics are readily available, and the selection of the appropriate package takes into account the final composition that must be used.

The low temperature and oxidation properties of the lubricating oil base stock in formulated lubricating oils are determined from the low temperature properties measured by ASTM D4684, or the oxidation properties measured by pressurized differential scanning calorimetry (CEC-L-85, which is equivalent to ASTM D6186) for oxidation stability times in MRV (micro rotary viscometer), the lubricating oil composition comprising the base stock of the present disclosure is particularly advantageous as a passenger car engine oil (PVEO) product.

The lubricating oil base stocks of the present disclosure provide a number of advantages over typical conventional lubricating oil base stocks, including, but not limited to, improved oxidation performance, such as oxidation induction time as measured by pressurized differential scanning calorimetry (CEC-L-85, which is equivalent to ASTM D6186) in engine oils.

The lubricating oil compositions may be used in the present disclosure for a variety of end uses in relation to lubricating oils, such as lubricating oils or greases for devices or equipment requiring lubrication of moving and/or interacting mechanical parts, components or surfaces. Useful devices include engines and machines. The lubricating oil basestocks of the present disclosure are suitable for use in formulating automotive crankcase lubricating oils, automotive gear oils, transmission oils, many industrial lubricating oils including circulating lubricating oils, industrial gear lubricating oils, greases, compressor oils, pump oils, refrigeration lubricating oils, hydraulic lubricating oils, and metal working fluids. Further, the lubricating oil basestocks of the present disclosure may be derived from renewable sources; such base stocks may qualify as sustainable products and may meet "sustainability" standards set by industry groups or government regulations.

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