TW201934734A - Lubricant compositions having improved oxidation performance - Google Patents

Lubricant compositions having improved oxidation performance Download PDF

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Publication number
TW201934734A
TW201934734A TW107142695A TW107142695A TW201934734A TW 201934734 A TW201934734 A TW 201934734A TW 107142695 A TW107142695 A TW 107142695A TW 107142695 A TW107142695 A TW 107142695A TW 201934734 A TW201934734 A TW 201934734A
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cst
base oil
composition
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oil
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TW107142695A
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Chinese (zh)
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丹尼爾 伊伽多夫
理查 道爾提
查爾斯 貝克二世
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美商艾克頌美孚研究工程公司
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Publication of TW201934734A publication Critical patent/TW201934734A/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
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    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
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    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/04—Well-defined hydrocarbons aliphatic
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    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/02—Specified values of viscosity or viscosity index
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
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    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
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    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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    • C10N2040/252—Diesel engines

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

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

具有改良的氧化效能之潤滑劑組成物Lubricant composition with improved oxidation performance

本發明是關於以獨特的第III類基礎油與此等基礎油混合物所調配之潤滑劑組成物。The present invention relates to a lubricant composition formulated with a unique Group III base oil and a mixture of these base oils.

基礎油是成品潤滑劑的主要成分，並且對潤滑劑的性質有很大貢獻。例如，機油是用於汽車引擎和柴油引擎的成品曲軸箱潤滑劑(finished crankcase lubricant)，並且包含兩種通用成分，即基礎油(base stock或base oil)(一種基礎油或基礎油的混合物)和添加劑。通常，藉由改變個別潤滑基礎油和個別添加劑的混合物，一些潤滑基礎油用於製造各種機油。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.

根據美國石油協會(American Petroleum Institute，API)分類，基礎油基於其飽和烴含量、硫含量和黏度指數分為五類(表1)。潤滑油基礎油通常從不可再生的石油來源大規模製造。第I、II和III類基礎油皆得自於原油，經由大量加工，例如溶劑萃取、溶劑或催化脫蠟、以及加氫異構化(hydroisomerization)。亦可從由天然氣、煤炭或其他化石資源所得到的合成烴液體製造第III類基礎油，第IV類基礎油為聚α-烯烴(polyalphaolefins，PAO)且是藉由α-烯烴(例如1-癸烯)的寡聚合作用而製得。第V類基礎油包含不屬於第I-IV類的所有基礎油，例如環烷(naphthenic)、聚伸烷二醇(polyalkylene glycols，PAG)以及酯類。
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.

通常由從真空蒸餾操作中回收的較高沸點餾分製備基礎油。它們可由石油衍生的或來自合成原油(syncrude)衍生的原料或由較低分子量分子的合成而製備。添加劑是添加到基礎油中的化學品，以改善成品潤滑劑的某些性能，使得其符合成品潤滑劑之等級的最低效能標準。例如，添加至機油的添加物可用以改良潤滑劑的氧化穩定性、增加其黏度、提高黏度指數、並且控制沉積物。添加物是昂貴的，並且可能造成成品潤滑劑的混溶性(miscibility)問題。由於這些原因，通常希望將機油的添加劑含量優化至符合適當要求所需的最小量。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.

由於需要提高品質，驅使配方正在進行改變。例如，管理組織(例如美國石油協會)幫助定義機油的規格。越來越多的機油規格要求產品具有優異的低溫性質和高氧化穩定性。目前，只有一小部分混合到機油中的基礎油能夠符合最苛刻的所需機油規格。目前，配方設計師正在使用一系列基礎油，包含第I、II、III、IV和V類基礎油，以調配其產品。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.

工業油亦被要求改善氧化穩定性、清潔度、界面性質和沈積物控制的品質。Industrial oils are also required to improve the quality of oxidation stability, cleanliness, interfacial properties, and sediment control.

儘管潤滑基礎油和潤滑油配方技術進步了，仍存在改良調配油之氧化效能(例如，對機油與工業油而言，具有較長的壽命)與低溫效能的需求。特別地，存在有改良調配油之氧化效能與低溫效能而不需要添加更多添加劑至潤滑油配方的需求。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.

本發明是關於含有獨特之第III類基礎油與混合物之經調配的潤滑劑組成物。本發明部分是關於以第III類基礎油製備的潤滑組成物，該第III類基礎油具有100℃時的運動黏度為大於2 cSt，例如從2.0 cSt至14 cSt以上，例如從2 cSt至12 cSt 以及從4 cSt至7 cSt。這些基礎油在本發明中亦稱為潤滑油基礎油或產物。在一實施例中，本發明提供潤滑組成物，其包括第III類基礎油，該第III類基礎油具有：至少90 wt%的飽和烴；100℃時的運動黏度(KV100)為4.0 cSt至12.0 cSt；黏度指數為120至133；多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.43；以及有效量的一或多種潤滑劑添加劑；其中該潤滑組成物的氧化誘導時間為大於120分鐘。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.

在另一實施例中，本發明提供一種客車機油組成物，其包括第III類基礎油，該第III類基礎油具有：至少90 wt%的飽和烴；100℃時的運動黏度為4.0 cSt至5.0 cSt、黏度指數為從120至小於140；多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.45；以及有效量的一或多種潤滑劑添加劑；其中該油組成物的氧化誘導時間為大於120分鐘。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.

在另一實施例中，本發明提供一種重型柴油引擎潤滑油組成物，其包括第III類基礎油，該第III類基礎油具有：至少90 wt%的飽和烴；100℃時的運動黏度為5.5 cSt至7.0 cSt；黏度指數為從120至小於144；多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.56；以及有效量的一或多種潤滑劑添加劑；其中該潤滑油組成物的氧化誘導時間為大於120分鐘。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.

在另一實施例中，本發明提供一種潤滑組成物，其包括第III類基礎油，該第III類基礎油具有：至少90 wt%的飽和烴；100℃時的運動黏度為4.0 cSt至5.0 cSt；黏度指數為120至140；多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.52；以及支鏈碳對直鏈碳的比率(BC/SC)小於或等於0.21；以及有效量的一或多種潤滑劑添加劑；其中該潤滑組成物的氧化誘導時間為大於120分鐘。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.

在另一實施例中，本發明提供一種潤滑組成物，其包括第III類基礎油，該第III類基礎油具有：至少90 wt%的飽和烴；100℃時的運動黏度為5.0 cSt至12.0 cSt；黏度指數為120至140；多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.59；以及支鏈碳對直鏈碳的比率(BC/SC)小於或等於0.26；以及有效量的一或多種潤滑劑添加劑；其中該潤滑油組成物的氧化誘導時間為大於120分鐘。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.

在另一實施例中，本發明提供一種潤滑組成物，其包括第III類基礎油，該第III類基礎油具有：至少90 wt%的飽和烴；100℃時的運動黏度(KV100)為5.0 cSt至12.0 cSt；黏度指數為120至144；多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.56；以及有效量的一或多種潤滑劑添加劑；其中該潤滑組成物的氧化誘導時間為大於120分鐘。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.

使用製造柴油燃料和第III類基礎油的方法可獲得用於製備本發明之潤滑劑組成物的第III類基礎油。通常，經由第一階段(stage)(其主要是提升黏度指數(viscosity index, VI)並且移除硫與氮的加氫處理單元)，處理原料(例如，具有溶劑脫蠟油進料黏度指數(solvent dewaxed oil feed viscosity index)為從約45至約150的重真空氣體油原料(heavy vacuum gas oil feed stock)或是具有溶劑脫蠟油進料黏度指數為從約45至約150的混合原料)。接下來是汽提部分，在此移除輕質油(light end)與柴油。而後較重的潤滑油餾分進入第二階段(stage)，在此進行加氫裂化、脫蠟和加氫精製(hydrofinishing)。原料與處理方式的這種組合製造具有獨特之組成特性的基礎油。在所製造的低、中與高黏度基礎油中，皆觀察到這些獨特的組成特性。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.

從以下詳細的說明，本發明的其他目的與優點將變得顯而易見。Other objects and advantages of the present invention will become apparent from the following detailed description.

在本文中的詳細說明與申請專利範圍內的所有數值皆修飾為「約」或「近似」指示值，並且考量該技藝中具有通常技術之人士已知的實驗誤差與變異。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.

如本文所用，術語「主要成分」是指存在本發明的潤滑油中的成分(例如基礎油)的量大於約50重量百分比(wt%)。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%).

如本文所用，術語「次要成分」是指存在本發明的潤滑油中的成分(例如一或多種潤滑油添加劑)的量小於50重量百分比。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.

如本文所用，術語「單環環烷烴」是指具有通式C n H2n 的飽和烴基，其以單個閉環的形式排列，其中n 是碳原子的數目。它在本文中亦表示為1RN。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.

如本文所用，術語「多環環烷烴」是指具有通式C n H2(n +1-r ) 的飽和烴基，其以多個閉環的形式排列，其中n 是碳原子的數目，並且r 是環的數目(在本文，r ＞1)。它在本文中亦表示為2+RN。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.

如本文所用，術語「100℃時的運動黏度」將與「KV100」交換使用，以及「40℃時的運動黏度」將與「KV40」交換使用。該兩個術語應被認為是均等的。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.

如本文所用，術語「直鏈碳」是指藉由13 C核磁共振(nuclear magnetic resonance，NMR)光譜測量的α、β、γ、δ和ε峰的總和。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.

如本文所用，術語「支鏈碳」是指藉由13 C NMR測量的懸垂甲基(pendant methyl)、懸垂乙基(pendant ethyl)、以及懸垂丙基(pendant propyl)的總和。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.

如本文所用，術語「末端碳」是指13 C NMR測量的末端甲基、末端乙基、以及末端丙基的總和。

潤滑油基礎油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

根據本發明，提供具有某些種類的石蠟分子(paraffin molecule)之潤滑組成物(例如引擎潤滑油組成物)。本案發明人驚訝地發現相較於現存的市售基礎油，具有低2R+N/1RN比率與/或較少的支鏈碳的基礎油所製備的潤滑劑組成物，諸如藉由本文所述之方法所製造者，顯示改良的氧化效能。較低含量的2R+N分子和支鏈碳物質在潤滑劑組成物中是理想的，因為高含量的2R+N分子和支鏈碳物質會阻礙所調配的油之氧化效能。本案發明人亦已經發現用具有比現存市售基礎油低的支鏈碳對末端碳的比率之基礎油所製備的潤滑劑組成物亦顯示改良的氧化效能。例如，相較於用目前市售習知的基礎油所製備的潤滑劑，本發明(使用CEC-L-85或ASTM D6186)之經調配的基礎油的氧化效能顯示改良10-100倍，例如20-50倍，例如30-40倍。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.

藉由壓差掃描熱量分析法(pressure differential scanning calorimetry)(CEC-L-85)所測量之氧化誘導時間(oxidation induction time，OIT)可決定氧化效能。藉由將樣品溫度維持恆定在175℃一段時間(例如2小時)以測量氧化誘導時間。在至少一實施例中，本發明之潤滑劑組成物具有氧化誘導時間為90分鐘或更長，例如100分鐘或更長，例如110分鐘或更長，例如120分鐘或更長。在至少一實施例中，潤滑劑組成物具有氧化誘導時間為從60分鐘至120分鐘，例如從70分鐘至120分鐘，例如從80分鐘至120分鐘。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.

根據本發明之各種實施例，本發明之潤滑組成物中所使用的基礎油為API第III類基礎油。可使用原料(例如，具有溶劑脫蠟油進料黏度指數為至少45(例如至少55，例如至少60至150，或60至90)的真空氣體油原料或具有溶劑脫蠟油進料黏度指數為至少45(例如至少55，例如至少60至約150，或60至90)之重真空氣體油與重大氣氣體油的混合原料)，藉由先進的加氫裂化程序而製造本發明的第III類基礎油。第III類是至少45，例如至少55，例如至少60至150，或60至90。本發明的第III類基礎油可具有100℃時的運動黏度為大於2 cSt，例如從2 cSt至14 cSt，例如從2 cSt至12 cSt以及從4 cSt至12 cSt。本發明的第III基礎油可具有多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於約0.59，以及支鏈碳對直鏈碳的比率小於或等於0.21。本發明的第III類基礎油可具有支鏈碳對末端碳的比率小於2.1。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.

對於具有100℃時的運動黏度為4-12 cSt的基礎油，本發明之潤滑劑組成物中所使用的API第III類基礎油可具有多環環烷烴對單環環烷烴的比率小於0.59，例如小於0.52，例如小於0.46，例如小於0.45或是小於0.43。基礎油可具有支鏈碳對末端碳的比率(BC/TC)，其中BC/TC≤2.3。輕型中性基礎油可具有黏度指數從102至133，並且小於或等於142*(1-0.0025 exp(8*(2R+N/1RN)))。中重型中性基礎油可具有黏度指數為120至133，並且小於或等於150.07*(1-0.0106*exp(4.5*(2R+N/1RN)))。此外，相較於市售已知的基礎油之黏度範圍，在本發明的基礎油中之環烷烴的量可為較低。環烷烴含量可為30 wt%至70 wt%。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%.

本發明之第III類基礎油可具有小於0.03 wt%的硫，傾點為-10℃至-30℃，Noack揮發性(volatility)為0.5 wt%至20 wt%，於-35℃時的CCS (冷曲軸模擬器(cold crank simulator，CCS)值為100 cP至70,000cP，以及環烷烴含量為30 wt%至70 wt%。輕型中性第III類基礎油，亦即具有KV100為2 cSt至5 cSt的基礎油，可具有Noack揮發性為8 wt%至20 wt%，於-35℃時的CCS值為100 cP至6,000cP，傾點為-10℃至-30℃以及環烷烴含量為30 wt%至60 wt%。本發明之中型中性第III類基礎油，亦即具有KV100為5 cSt至7 cSt的基礎油，可具有Noack揮發性為2 wt%至10 wt%，於-35℃時的CCS值為3,500 cP至20,000cP，傾點為-10℃至-30℃以及環烷烴含量為30 wt%至60 wt%。本發明之重型中性第III類基礎油，亦即具有KV100為7 cSt至12 cSt的基礎油，可具有Noack揮發性為0.5 wt%至4 wt%，於-35℃時的CCS值為10,000 cP至70,000cP，傾點為-10℃至-30℃以及環烷烴含量為30 wt%至70 wt%。根據本發明之各種實施例，第III類基礎油包括30 wt%至70%的石蠟，或是31 wt%至69 wt%的石蠟，或是32 wt%至68 wt%的石蠟。根據本發明的各種實施例，輕型中性第III類基礎油可含有40 wt%至70 wt%、或45 wt%至70 wt%、或45 wt%至65 wt%的石蠟。根據本發明的各種實施例，中型中性第III類基礎油可含有35 wt%至65 wt%、或40 wt%至65 wt%、或40 wt%至60 wt%的石蠟。根據本發明的各種實施例，重型中性第III類基礎油可含有30 wt%至60 wt%、或30 wt%至55 wt%、或30 wt%至50 wt%、或30 wt%至45 wt%、或30 wt%至40 wt%的石蠟。

製程(process)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

下列描述的製程可用以製造本發明之組成上有利的第III類基礎油。通常，經由第一階段(stage)(其主要為加氫處理單元，該加氫處理單元提高黏度指數(VI)且移除硫與氮)，處理原料(例如，具有溶劑脫蠟油進料黏度指數為從至少45(較佳為至少55，且更佳為至少60至約150)的重真空氣體油原料)或是具有溶劑脫蠟油進料黏度指數為從至少45(較佳為至少55，且更佳為至少60至約150)的混合原料)。接下來是汽提部分，在此移除輕質油(light end)與柴油。而後較重的潤滑油餾分進入第二階段，其中進行加氫裂化、脫蠟和加氫精製(hydrofinishing)。原料與處理方式的這種組合製造具有獨特之組成特性的基礎油。在所製造的低、中與高黏度基礎油中，皆觀察到這些獨特的組成特性。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.

相較於習知的第III類基礎油，本發明的製程架構製造高品質第III類基礎油，其具有獨特的組成特性。可從組成物之多環環烷烴對單環環烷烴的比率得到組成上的優點。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.

本發明的製程可製造基礎油，該基礎油具有100℃時的運動黏度(KV100)為大於或等於2 cSt、或大於或等於4 cSt (例如從4 cSt至7 cSt)、或大於或等於6 cSt、或大於或等於8 cSt、或大於或等於10 cSt、或大於或等於12 cSt、或大於或等於14 cSt。使用本發明之製程所製造的基礎油可製造具有VI為至少120至約145 (例如120至140或120至133)的基礎油。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).

如本文所用，階段(stage)可相當於單一個反應器或是複數個反應器。任選地，可使用多個平行反應器以進行一或多個製程，或是在一階段中可使用多個平行反應器用於所有製程。每一個階段與/或反應器可包含一或多個催化劑床，該催化劑床含有加氫處理催化劑或是脫蠟催化劑。應注意，催化劑的「床」可指部分物理性催化床。例如，在反應器內的催化劑床可用加氫裂化催化劑局部填充並且可用脫蠟催化劑局部填充。為便於說明，即使兩種催化劑可在單一催化劑床中堆疊在一起，加氫裂化催化劑與脫蠟催化劑在概念上仍可各自稱為個別的催化劑床。

架構實例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

圖1顯示在本發明中適合用於製造基礎油的處理架構之實例。圖2顯示適合用於處理原料以製造基礎油的一般處理架構之實例。應注意，R1對應於圖2中的110；再者，R2、R3、R4與R5分別對應於圖2的120、130、140與150。可在美國專利申請案公開案第2015/715,555號中找到處理架構的細節。在圖2中，可將原料105引入第一反應器110中。反應器(例如第一反應器110)可包含饋送入口與流出物出口。第一反應器110可對應於加氫處理反應器、加氫裂化反應器、或其組合。任選地，可使用複數個反應器，用於不同條件的選擇。例如，如果第一反應器110與任選的第二反應器120皆包含於反應系統中，則第一反應器110可對應於加氫處理反應器，而第二反應器120可對應於加氫裂化反應器。亦可使用在反應器內配置反應器與/或催化劑之其他選擇以進行原料的初始加氫處理與/或加氫裂化。任選地，如果架構包含多個反應器於初始階段中，則在反應器之間可進行氣-液分離，以使得輕質油與污染物氣體之移除。在初始階段包含加氫裂化反應器的情況下，初始階段中的加氫裂化反應器可指額外的加氫裂化反應器。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.

而後，來自初始階段的最終反應器(例如反應器120)之經加氫處理之流出物125可進入分餾器130中或是進入另一種分離階段。分餾器130(或其他分離階段)可分離經加氫處理的流出物以形成一或多個燃料沸點範圍餾分(fuel boiling range fraction)137、輕質油餾分132、以及潤滑劑沸點範圍餾分135。潤滑劑沸點範圍餾分135通常可對應於來自分餾器130的底部餾分。潤滑劑沸點範圍餾分135可在第二階段加氫裂化反應器140中進一步進行加氫裂化。而後，來自第二階段加氫裂化反應器140的流出物145可進入至脫蠟/加氫精製反應器150中以進一步改良最終製造的潤滑劑沸點範圍產物之性質。在圖2所示的架構中，來自第二階段脫蠟/加氫精製反應器150的流出物155可經分餾160以從一或多個所欲之潤滑劑沸點範圍餾分155分離出輕質油152與/或燃料沸點範圍餾分157。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.

圖2中的架構可使得第二階段加氫裂化反應器140與脫蠟/加氫精製反應器150在甜(sweet)處理條件(相當於進料(至第二階段)的硫含量為100 wppm或更低的均等物)下操作。在此「甜」處理條件下，圖2中的架構結合使用高表面積、低酸性催化劑，可使得以製造具有降低或最小化的芳香族含量之加氫裂化的流出物。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.

在圖2所示之架構中，初始階段中的最終反應器(例如反應器120)可稱為與分餾器130的入口(或另一種分離階段的入口)直接流體連通。基於初始階段中的最終反應器所提供的間接流體連通，在初始階段中的其他反應器可稱為與分離階段的入口間接流體連通。基於直接流體連通或是間接流體連通，初始階段中的反應器通常可稱為與分離階段流體連通。在一些任選方面中，可包含一或多個回收迴路作為反應系統架構的一部分。回收迴路可使得反應器/階段之間流出物的淬熄(quenching)以及反應器/階段內的淬熄。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.

在一實施例中，在加氫處理條件下，將原料引入反應器中。而後，經加氫處理的流出物進入至分餾器中，其中流出物被分離為燃料沸點範圍餾分與潤滑劑沸點範圍餾分。而後，潤滑劑沸點範圍餾分進入至第二階段，在此進行加氫裂化、脫蠟與加氫精製步驟。而後，來自第二階段的流出物進入至分餾器，在此本發明的第III類基礎油被回收。

原料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

根據本發明，可對大範圍的石油和化學原料進行加氫處理。合適的原料包含全原油(whole petroleum crude)和蒸餾後的石油原油(reduced petroleum crudes)，例如Arab Light、extra Light、Midland Sweet、Delaware Basin、West Texas Intermediate、Eagle Ford、Murban and Mars原油、大氣油、循環油、氣體油(包含真空氣體油與焦化氣體油)、輕質至重質餾出液(包含原始初始餾出液)、加氫裂化產物、加氫處理油、石油衍生蠟(包含鬆蠟)、Fischer-Tropsch蠟、萃餘液(raffinate)、脫瀝青油、以及這些物質的混合物。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.

定義原料的一種方式是基於進料的沸點範圍(boiling range)。一種定義沸點範圍的選擇是使用進料的初始沸點與/或進料的最終沸點。另一種選擇是基於在一或多個溫度沸騰的進料的量以將進料定性。例如，進料的「T5」沸點/蒸餾點定義為5wt%的進料將沸騰的溫度。同樣地，「T95」沸點/蒸餾點為95wt%的進料將沸騰的溫度。可使用適當的ASTM測試方法(例如ASTM D2887、D2892、D6352、D7129和/或D86中描述的方法)決定沸點(包含分數重量沸點(fractional weight boiling point))。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).

典型的進料包含例如具有初始沸點為至少600℉(～316℃)的進料；同樣地，進料的T5與/或T10沸點可為至少600℉(～316℃)。此外抑或者，進料的最終沸點可為1100℉(～593℃)或更低；同樣地，進料的T95沸點與/或T90沸點亦可為1100℉(～593℃)或更低。作為一個非限制實例，典型進料可具有T5沸點為至少600℉(～316℃)與T95沸點為1100℉(～593℃)或更低。任選地，如果加氫處理亦用以形成燃料，則進料可包含較低的沸點範圍部分。例如，此進料可具有初始沸點為至少350℉(～177℃)與最終沸點為1100℉(～593℃)或更低。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.

在一些方面，(由UV-Vis吸收或均等方法(例如ASTM D7419 或ASTM D2007或均等方法)決定的)進料的芳香族含量可為至少20 wt%、或至少25 wt%、或至少30 wt%、或至少40 wt%、或至少50 wt%、或至少60 wt%，例如15至75 wt%或至多90 wt%。特別地，芳香族含量可為25 wt%至75 wt%、或25 wt%至90 wt%、或35 wt%至75 wt%、或35 wt%至90 wt%。在其他方面，進料可具有較低的芳香族含量，例如芳香族含量為35 wt%或更少、或25 wt%或更少，例如低至0 wt%。特別地，芳香族含量可為0 wt%至35 wt%、或0 wt%至25 wt%、或5.0 wt%至35 wt%、或5.0 wt%至25 wt%。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%.

可用於本發明之製程中的特別的原料成分包含真空氣體油原料(例如，中型真空氣體油進料(medium vacuum gas oil feeds，MVGO))，其具有溶劑脫蠟油進料黏度指數為從至少45、至少50、至少55、或至少60至150，例如從65至125、至少65至110，從65至100或65至90。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.

可用於本發明之製程中的其他特別的原料成分包含具有混合的真空氣體油進料(例如，中型真空氣體油進料(MVGO))與重型大氣氣體油進料之原料，其中混合原料具有溶劑脫蠟油進料黏度指數為從至少45、至少55、至少60至150，例如從65至145、從65至125、從65至100或65至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.

在加氫處理包含加氫處理製程與/或酸加氫裂化製程的方面，進料可具有硫含量為500 wppm至20000 wppm或更多、或500 wppm至10000 wppm、或500 wppm至5000 wppm。此外抑或者，此進料的氮含量可為20 wppm至4000 wppm、或50 wppm至2000 wppm。在一些方面，進料可相當為「甜(sweet)」進料，因而進料的硫含量為25 wppm至500 wppm與/或氮含量為1 wppm至100 wppm。

第一加氫處理階段-加氫處理與/或加氫裂化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

在各種方面，第一加氫處理階段可用以改良潤滑劑基礎油製造之原料的一或多種品質。原料的改良之實例可包含(但不限於)降低進料的雜原子含量、在進料上進行轉換以提供黏度指數上升、以及/或在進料上進行芳香族飽和反應。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.

關於雜原子移除，在初始加氫處理階段(加氫處理與/或加氫裂化)中的條件可足以將經加氫處理之流出物的硫含量降低至250 wppm或更少、或200 wppm或更少、或150 wppm或更少、或100 wppm或更少、或50 wppm或更少、或 25 wppm或更少、或10 wppm或更少。特別地，加氫處理之流出物的硫含量可為1 wppm至250 wppm、或1 wppm至50 wppm、或1 wppm至10 wppm。此外抑或者，在初始加氫處理階段中的條件可足以將氮含量降低至100 wppm或更少、或50 wppm或更少、或25 wppm或更少、或10 wppm或更少。特別地，氮含量可為1 wppm至100 wppm、或1 wppm至25 wppm、或1 wppm至10 wppm或更少。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.

在包含加氫處理作為初始加氫處理階段之一部分的方面，加氫處理催化劑可包括任何合適的加氫處理催化劑，例如包括第8-10族非貴金屬(例如選自Ni、Co及其組合)中的至少一者以及至少一個第6族金屬(例如選自Mo、W及其組合)之催化劑，任選地包含合適的支撐與/或填充劑材料(例如，包括氧化鋁、二氧化矽、二氧化鈦、氧化鋯或其組合)。根據本發明之方面的加氫處理催化劑可為鬆散催化劑(bulk catalyst)或經支撐的催化劑(supported catalyst)。製造經支撐的催化劑之技術在該技藝中是廣為人知的。製造鬆散金屬催化劑顆粒的技術為已知的，並且先前已經描述，例如在美國專利第6,162,350號，其併入本文作為參考。可經由所有金屬催化劑前驅物皆在溶液中的方法，或是經由該等前驅物中的至少一者是至少部分為固體形式而任選地但較佳為該等前驅物中的至少另一者是僅以溶液形式提供的方法，來製造鬆散金屬催化劑顆粒。例如，可藉由提供金屬前驅物的溶液(其亦包含溶液中的固體與/或沉澱的金屬)(例如懸浮顆粒的形式)而達成提供金屬前驅物至少部分為固體形式。作為說明，美國專利第6,156,695號、第6,162,350號、第6,299,760號、第6,582,590號、第6,712,955號、第6,783,663號、第6,863,803號、第6,929,738號、第7,229,548號、第7,288,182號、第7,410,924號、第7,544,632號與第8,294,255號、美國專利申請案公開案第2005/0277545號、第2006/0060502號、第2007/0084754號與第2008/0132407號以及國際專利申請案公開案WO 04/007646、WO 2007/084437、WO 2007/084438、WO 2007/084439與WO 2007/084471中的一或多個描述合適的加氫處理催化劑的一些實例。較佳的金屬催化劑包含鈷/鉬(1-10% Co氧化物、10-40% Mo氧化物)、鎳/鉬(1-10% Ni氧化物、10-40% Co氧化物)、或鎳/鎢(1-10% Ni氧化物、10-40% W氧化物)在氧化鋁上。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.

在各種方面，加氫處理條件可包含溫度為200℃至450℃、或315℃至425℃；壓力為250 psig(～1.8 MPag)至5000 psig(～34.6 MPag)或500 psig(～3.4 MPag)至3000 psig(～20.8 MPag)、或800 psig(～5.5 MPag)至2500 psig(～17.2 MPag)；每小時之液體空間速度(Liquid Hourly Space Velocity，LHSV)為0.2-10 hr-1 ；以及加氫處理速率為200 scf/B(35.6 m3 /m3 )至10,000 scf/B(1781 m3 /m3 )、或500(89 m3 /m3 )至10,000 scf/B(1781 m3 /m3 )。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 ).

加氫處理催化劑通常為含有第6族金屬以及第8-10族非貴金屬(亦即鐵、鈷與鎳)及其混合物的催化劑。這些金屬或金屬的混合物通常氧化物或硫化物形式存在於耐火性(refractory)金屬氧化物支撐物(support)上。合適的金屬氧化物支撐物包含低酸性氧化物，例如二氧化矽、氧化鋁或二氧化鈦，較佳為氧化鋁。在一些方面，較佳的氧化鋁可相當於多孔氧化鋁，如γ或η，其具有平均孔徑為50至200 Å、或75至150 Å；表面積為從100至300 m2 /g、或150至250 m2 /g；與/或孔體積為從0.25至1.0 cm3 /g、或0.35至0.8 cm3 /g。較佳不用鹵素(例如氟)促進支撐物，因為這通常會增加支撐物的酸性。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.

外表面積與微孔表面積是指定性催化劑之總表面積的一種方式。基於使用測量表面積之BET法的氮孔隙度測量(porosimetry)數據的分析，計算這些表面積。參閱例如Johnson, M. F. L., Jour. Catal., 52, 425(1978)。微孔表面積是指基於催化劑中沸石的一維孔洞而得到的表面積。催化劑中僅沸石將貢獻此部分的表面積。外表面積可歸因於催化劑內的沸石或結合劑(binder)。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.

或者，加氫處理催化劑可為鬆散金屬催化劑，或是經支撐的金屬催化劑與鬆散金屬催化劑之堆疊床的組合。對於鬆散金屬，它是指未受支撐的催化劑，其中基於鬆散催化劑顆粒的總重量(以金屬氧化物計算)，鬆散催化劑顆粒包括30-100 wt%的至少一種第8-10族非貴金屬以及至少一種第6族金屬，以及其中該鬆散催化劑顆粒具有表面積為至少10 m2 /g。再者，基於鬆散催化劑顆粒的總重量(以金屬氧化物計算)，較佳為本文所使用的鬆散金屬加氫處理催化劑包括50至100 wt%，且甚至較佳為70至100 wt%的至少一種第8-10族非貴金屬以及至少一種第6族金屬。可經由TEM-EDX而決定第6族與第8-10族非貴金屬的量。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.

較佳為包括一種第8-10族非貴金屬與兩種第6族金屬的鬆散催化劑組成物。已經發現在此情況下，鬆散催化劑顆粒為耐燒結性(sintering-resistant)。因此，在使用過程中，維持鬆散催化劑顆粒的活性表面積。第6族與第8-10族非貴金屬的莫耳比率範圍通常為從10：1至1：10，並且較佳為從3：1至1：3。在芯-殼結構的顆粒情況下，這些比例當然適用於殼中所含的金屬。如果鬆散催化劑顆粒含有超過一種第6族金屬，則不同的第6族金屬之比率通常不是關鍵的。當使用超過一種第8-10族非貴金屬時，同樣適用。當鉬與鎢存在為第6族金屬時，鉬：鎢比率範圍較佳為9：1至1：9。較佳地，第8-10族非貴金屬包括鎳與/或鈷。更較佳地，該第6族金屬包括鉬與鎢的組合。較佳地，使用鎳/鉬/鎢與鈷/鉬/鎢與鎳/鈷/鉬/鎢的組合。這些種類的沉澱物顯然為耐燒結的。因此，在使用過程中，維持沉澱物的活性表面積。該等金屬較佳以對應金屬之氧化的化合物形式存在，或是如果催化劑組成物已經被硫化，則為對應金屬之硫化的化合物。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.

在一些任選方面，本文所用的鬆散金屬加氫處理催化劑具有表面積為至少50 m2 /g，且較佳為至少100 m2 /g。在此等方面，亦期望鬆散金屬加氫處理催化劑的孔徑分布大致與習知的加氫處理催化劑的孔徑分布相同。藉由氮吸附決定鬆散金屬加氫處理催化劑可具有孔體積為0.05-5 ml/g、或0.1-4 ml/g、或0.1-3 ml/g或0.1-2 ml/g。較佳地，不存在小於1 nm的孔。鬆散金屬加氫處理催化劑可具有中位數直徑為至少50 nm、或至少100 nm。鬆散金屬加氫處理催化劑可具有中位數直徑為不超過5000 μm、或不超過3000 μm。在一實施例中，中位數顆粒直徑範圍落在0.1-50 μm，且最佳的範圍在0.5-50 μm。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.

合適的加氫處理催化劑之實例包含(但不限於) Albemarle KF 848、KF 860、KF 868、KF 870、KF 880、KF 861、KF 905、KF 907、以及Nebula；Criterion LH-21、LH-22與DN-3552；Haldor-Topsøe TK-560 BRIM、TK-562 HyBRIM、TK-565 HyBRIM、TK-569 HyBRIM、TK-907、TK-911與TK-951；Axens HR 504、HR 508、HR 526與HR 544。可藉由前述所列之催化劑中的一個催化劑或其組合來進行加氫處理。

第二階段處理-加氫裂化或轉換條件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

在各種方面，在轉換進料的第二(甜)反應階段中取代習知的加氫裂化催化劑，反應系統可包含文中所述之高表面積、低酸性轉換催化劑。在潤滑劑沸點範圍進料(例如相當於「甜」進料的進料)具有足夠低含量的雜原子之方面，進料可暴露至高表面積、低酸性轉換催化劑，如本文所述，而不必先進行加氫處理以移除雜原子。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.

在各種方面，經選擇用於潤滑劑基礎油製造的轉換條件可取決於所欲之轉換量、輸入進料至轉換階段之污染物的量、以及潛在的其他因子。例如，可選擇在單一階段或在多階段系統之第一階段與/或第二階段中的的加氫裂化與/或轉換條件，以達成反應系統中所欲之轉換量。加氫裂化與/或轉換條件可稱為酸(sour)條件或甜(sweet)條件，取決於存在於進料內與/或存在反應環境之氣相中的硫與/或氮的量。例如，具有100 wppm或更少的硫與50 wppm或更少的氮(較佳為少於25 wppm的硫與/或少於10 wppm的氮)之進料代表在甜條件下之用於加氫裂化與/或轉換的進料。可在酸條件下處理具有250 wppm或更多的硫含量之進料。具有中間量的硫之進料可在甜條件或酸條件下處理。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.

在包含加氫裂化作為酸條件下之初始加氫處理階段之一部分的方面，初始階段加氫裂化催化劑可包括任何合適的或標準的加氫裂化催化劑，例如選自於沸石β、沸石X、沸石Y、八面沸石(faujasite)、超穩Y沸石(ultrastable Y) (USY)、脫鋁Y沸石(Deal Y)、絲光沸石(Mordenite)、ZSM-3、ZSM-4、ZSM-18、ZSM-20、ZSM-48、及其組合的沸石基底(zeolitic base)，該沸石基底可有利地承載一或多種活性金屬(例如(i)第8-10族貴金屬，例如鉑與/或鈀，或是(ii)第8-10族非貴金屬，例如鎳、鈷、鐵、及其組合，以及第6族金屬，例如鉬與/或鎢)。在此討論中，沸石材料經定義為包含具有經認可的沸石骨架結構的材料，例如由國際沸石協會認可的骨架。此等沸石材料可相當於矽鋁酸鹽(silicoaluminate)、矽鋁磷酸鹽(silicoaluminophosphate)、鋁磷酸鹽(aluminophosphate)與/或可用以形成沸石骨架結構之原子的其他組合。除了沸石材料之外，其他種類的結晶狀酸性支撐材料亦可為合適的。任選地，沸石材料與/或其他結晶狀酸性的材料可混合或是與其他金屬氧化物(例如氧化鋁、二氧化鈦和/或二氧化矽)結合。可在US2015/715555中得到合適的加氫裂化催化劑之細節。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.

在一些任選的方面，本文所述之高表面積、低酸性轉換催化劑可任選地作為初始階段中的催化劑之一部分。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.

可於溫度為200℃至450℃、氫氣分壓為從250 psig至5000 psig(～1.8 MPag至～34.6 MPag)、每小時液體空間速度為從0.2 hr-1 至10 hr-1 以及加氫處理氣體速率為從35.6 m3 /m3 至1781 m3 /m3 (～200 SCF/B至～10,000 SCF/B)進行第一階段中(或者在酸條件下)的加氫裂解製程，通常，在大部分的情況下，條件可包含溫度範圍為300℃至450℃、氫氣分壓為從500 psig至2000 psig(～3.5 MPag至～13.9 MPag)、每小時液體空間速度為從0.3 hr-1 至5 hr-1 以及加氫處理氣體速率為從213 m3 /m3 至1068 m3 /m3 (～1200 SCF/B至 ～6,000 SCF/B)。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).

在多階段反應系統中，加氫裂化反應系統的第一反應階段可包含一或多種加氫處理與/或加氫裂化催化劑。而後，可在反應系統的第一與第二階段之間使用分離器，以移除氣相的硫與氮污染物。分離器的一個選擇是簡單地進行氣-液分離以移除污染物。另一個選擇是使用分離器，例如閃蒸分離器(flash separator)，其可在較高的溫度進行分離。例如，可使用此高溫分離器，以將進料分離成沸點低於溫度切割點(例如約350℉(177℃)或約400℉(204℃))的部分，以及沸點高於溫度切點的部分。在此種分離中，亦可移除來自第一反應階段之流出物的石腦油(naphtha)沸點範圍部分，因而降低在第二或其他後續階段中處理的流出物之體積。當然，來自第一階段的流出物中的任何低沸點污染物亦被分離至沸點低於溫度切割點的部分中。如果在第一階段中進行足夠的污染物移除，則第二階段可***作成為「甜」或低污染物階段。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.

另一種選擇可為在加氫處理反應系統的第一與第二階段之間使用分離器，其亦可對來自第一階段的流出物進行至少一部分的分餾。在這種方面，來自第一加氫處理階段的流出物可被至少分離為沸點低於餾出物(例如柴油)燃料範圍的部分、沸點在餾出物燃料範圍中的部分、以及沸點高於餾出物燃料範圍的部分。基於習知的柴油沸點範圍，可定義餾出物燃料範圍，例如具有下端切割點溫度為至少約350℉(177℃)或至少約400℉(204℃)至具有上端切割點溫度為約700℉(371℃)或更低、或650℉(343℃)或更低。任選地，例如藉由選擇下端切割點溫度為至少約300℉(149℃)，餾出物燃料範圍可延伸至包含額外的煤油(kerosene)。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).

在階段間分離器亦用以製造餾出物燃料餾分的方面，沸點低於餾出物燃料餾分的部分包含石腦油(naphtha)沸點範圍的分子、輕質油、以及污染物(例如H2 S)。可用任何方便的方法將這些不同的產物彼此分離。同樣地，如果需要，可從餾出物沸點範圍餾分形成一或多種餾出物燃料餾分。沸點高於餾出物燃料範圍的部分代表潛在的潤滑劑基礎油。在此等方面，沸點高於餾出物燃料沸點範圍的部分用以在第二加氫處理階段中進行進一步的加氫處理。沸點高於餾出物燃料沸點範圍的部分可相當於潤滑劑沸點範圍餾分，例如具有T5或T10沸點為至少約343℃的餾分。任選地，較輕的潤滑油餾分可在封閉操作中的催化劑脫蠟部分中蒸餾與操作，其中條件經調整以使每個潤滑油餾分(cut)的產率和性質最大化。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.

可在類似於用於酸加氫裂化製程中的條件下進行甜條件下的轉換方法，或是條件可為不同。在一實施例中，相較於在酸階段中加氫裂化處理，甜轉換階段的條件可具有較不嚴格的條件。非酸階段之合適的轉換條件可包含(但不限於)類似於第一或酸階段的條件。合適的轉換條件可包含溫度為約550℉(288℃)至約840℉(449℃)、氫氣分壓為從約1000 psia至約5000 psia(～6.9 MPa-a至34.6 MPa-a)、每小時液體空間速度為從0.05 hr-1 至10 hr-1 以及加氫處理氣體速率為從35.6 m3 /m3 至1781 m3 /m3 (200 SCF/B至10,000 SCF/B)。在其他實施例中，條件可包含溫度範圍為約600℉(343℃)至約815℉(435℃)、氫氣分壓為從約1000 psia至約3000 psia(～6.9 MPa-a至20.9 MPa-a)、以及加氫處理氣體速率為從約213 m3 /m3 至1068 m3 /m3 (1200 SCF/B至6,000 SCF/B)。LHSV可為從約0.25 hr-1 至約50 hr-1 、或從約0.5 hr-1 至約20 hr-1 ，並且較佳為從約1.0 hr-1 至約4.0 hr-1 。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 .

在另一方面，可使用相同的條件用於加氫處理、加氫裂化與/或轉換床或階段，例如使用加氫處理條件於所有床或階段、使用加氫裂化條件於所有床或階段、以及/或使用轉換條件於所有床或階段。在另一實施例中，用於加氫處理、加氫裂化、與/或轉換床或階段的壓力可為相同。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.

在另一方面，加氫處理反應系統可包含超過一種加氫裂化與/或轉換階段。如果存在多個加氫裂化與/或轉換階段，則至少一個加氫裂化階段可具有上述之有效的加氫裂化條件，包含氫氣分壓為至少約1000 psia(～6.9 MPa-a)。在這方面，在可包含較低氫氣分壓的條件下，可進行其他(後續的)轉換製程。用於其他轉換階段之合適的轉換條件可包含(但不限於)溫度為約550℉(288℃)至約840℉(449℃)、氫氣分壓為從約250 psia至約5000 psia(1.8 MPa-a至34.6 MPa-a)、每小時液體空間速度為從0.05 hr-1 至10 hr-1 、以及加氫處理氣體速率為從35.6 m3 /m3 至1781 m3 /m3 (200 SCF/B至10,000 SCF/B)。在其他的實施例中，用於其他轉換階段的條件可包含溫度範圍為約600℉(343℃)至約815℉(435℃)、氫氣分壓為從約500 psia至約3000 psia(3.5 MPa-a至20.9 MPa-a)、以及加氫處理氣體速率為從約213 m3 /m3 至約1068 m3 /m3 (1200 SCF/B至6000 SCF/B)。LHSV可為從約0.25 hr-1 至約50 hr-1 、或從約0.5 hr-1 至約20 hr-1 ，以及較佳為從約1.0 hr-1 至約4.0 hr-1 。

額外的第二階段處理-脫蠟與加氫精製/芳香族飽和(Aromatic Saturation)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

在各種方面，可包含催化性脫蠟成為第二與/或甜與/或後續處理階段(例如亦包含在高表面積、低酸性催化劑存在的轉換之處理階段)的一部分。較佳地，脫蠟催化劑為沸石(與/或沸石晶體)，其主要藉由異構化烴原料而進行脫蠟。更佳地，催化劑為具有一維孔隙結構的沸石。合適的催化劑包含10員環孔沸石，例如EU-1、ZSM-35(或鎂鹼沸石(ferrierite))、ZSM-11、ZSM-57、NU-87、SAPO-11、以及ZSM-22。較佳的材料為EU-2、EU-11、ZBM-30、ZSM-48、或ZSM-23。ZSM-48是最佳的。應注意，具有二氧化矽對氧化鋁之比率為從20：1至40：1的ZSM-23結構之沸石有時可稱為SSZ-32。與上述材料同等結構的其他沸石晶體包含Theta-1、NU-10、EU-13、KZ-1、以及NU-23。美國專利第7,625,478號、第7,482,300號、第5,075,269號與第4,585,747號進一步揭露可用在本發明的製程中脫蠟催化劑，上述美國專利案皆併入本文作為參考。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.

在各種實施例中，脫蠟催化劑可進一步包含金屬氫化成分。金屬氫化成分通常為第6族與/或第8-10族金屬。較佳地，金屬氫化成分為第8-10族貴金屬。較佳地，金屬氫化成分為Pt、Pd或其混合物。在另一較佳實施例中，金屬氫化成分可為非貴第8-10族金屬與第6族金屬的組合。合適的組合可包含Ni、Co或Fe與Mo或W，較佳為Ni與Mo或W。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.

可用任何方便的方法將金屬氫化成分加至脫蠟催化劑中。一種添加金屬氫化成分的技術是藉由初濕含浸法(incipient wetness)。例如，在組合沸石與結合劑之後，所組合的沸石與結合劑可被擠製成催化劑顆粒。這些催化劑顆粒而後可暴露至含有合適之金屬前驅物的溶液。或者，可藉由離子交換而將金屬加至催化劑，其中在擠出之前將金屬前驅物加至沸石(或沸石與結合劑)的混合物中。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.

在脫蠟催化劑中的金屬量基於催化劑可為至少0.1 wt%、或至少0.15 wt%、或至少0.2 wt%、或至少0.25 wt%、或至少0.3 wt%、或至少0.5 wt%。在催化劑中的金屬量基於催化劑可為20 wt%或更少、或10 wt%或更少、或5 wt%或更少、或2.5 wt%或更少、或1 wt%或更少。對於金屬為Pt、Pd、另一種金屬第8-10族貴金屬、或其組合的方面，金屬量可為從0.1至5 wt%，較加為從0.1至2 wt%、或0.25至1.8 wt%、或0.4至1.5 wt%。對於金屬為非貴第8-10族金屬與第6族金屬之組合的方面，金屬的組合量可為從0.5 wt%至20 wt%、或1 wt%至15 wt%、或2.5 wt%至10 wt%。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%.

較佳地，脫蠟催化劑可為具有二氧化矽對氧化鋁之低比率的催化劑。例如，對於ZSM-48，沸石中的二氧化矽對氧化鋁之比率可為小於200：1、或小於110：1、或小於100：1、或小於90：1、或小於80：1。特別地，二氧化矽對氧化鋁的比率可為從30：1至200：1、或60：1至110：1、或70：1至100：1。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.

脫蠟催化劑亦可包含結合劑。在一些實施例中，使用低表面積結合劑調配用於根據本發明之製程中的脫蠟催化劑，低表面積結合劑表示具有表面積為100 m2 /g或更小、或80 m2 /g或更小、或70 m2 /g或更小，例如低至40 m2 /g或再更小的結合劑。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.

或者，結合劑與沸石顆粒尺寸可經選擇以提供具有所欲之微孔表面積對總表面積的比率之催化劑。在根據本發明所使用的脫蠟催化劑中，微孔表面積相當於在脫蠟催化劑中的沸石的一維孔隙的表面積。總表面積相當於微孔表面積加上外表面積。在催化劑中使用的任何結合劑將不會貢獻至微孔表面積並且不會顯著增加催化劑的總表面積。外表面積表示總催化劑的表面積減去微孔表面積的結餘。結合劑與沸石皆可貢獻於外表面積的值。較佳地，脫蠟催化劑之微孔表面積對總表面積的比率將可等於或大於25%。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%.

可用任何方便的方式，組合沸石(或其他沸石材料)與結合劑。例如，可藉由以沸石與結合劑二者的粉末開始、將粉末與加入的水結合並且研磨以形成混合物，而後擠出該混合物以製造所欲尺寸的結合催化劑而製造結合催化劑(bound catalyst)。亦可使用擠出助劑(extrusion aid)以修飾沸石與結合劑混合物的擠出流體性質。任選地，亦可使用由兩種或更多種金屬氧化物組成的結合劑。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.

催化性脫蠟區中的處理條件可包含溫度為從200至450℃(較佳為270至400℃)、氫氣分壓為從1.8至34.6 MPag(～250至～5000 psi)(較佳為4.8至20.8 MPag)、每小時液體空間速度為從0.2至10 hr-1 (較佳為0.5至3.0 hr-1 )、以及氫循環速率為從35.6至1781 m3 /m3 (～200至 ～10,000 SCF/B)(較佳為178至890.6 m3 /m3 (～1000至～5000 scf/B))。此外抑或者，該條件可包含溫度範圍為600℉(～343℃)至815℉(～435℃)、氫氣分壓為從500 psig至3000 psig(～3.5 MPag至 ～20.9 MPag)、以及加氫處理氣體速率為從213 m3 /m3 至1068 m3 /m3 (～1200 SCF/B至～6000 SCF/B)。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).

在各種方面，亦可提供加氫精製與/或芳香族飽和製程。加氫精製與/或芳香族飽和製程可在脫蠟之前與/或脫蠟之後發生。加氫精製與/或芳香族飽和製程可在分餾之前或之後發生。如果加氫精製與/或芳香族飽和製程在分餾之後發生，則可在分餾產物的一或多個部分上進行加氫精製，例如在一或多個潤滑劑基礎油部分上進行。或者，可將來自最後轉換或脫蠟製程的全部流出物進行加氫精製與/或進行芳香族飽和。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.

在一些情況下，加氫精製製程與芳香族飽和製程可指使用相同催化劑的單一製程。或者，可提供一種催化劑或催化劑系統以進行芳香族飽和，而可使用第二催化劑或催化劑系統用於加氫精製。通常，由於實際原因，例如便於在加氫精製或芳香族飽和製程使用較低溫度，加氫精製與/或芳香族飽和過程將在個別的反應器中進行脫蠟或加氫裂化製程。然而，在加氫裂化或脫蠟製程之後但在分餾之前，概念上仍可將另一個加氫精製反應視為反應系統的第二階段的一部分。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.

加氫精製與/或芳香族飽和催化劑可包含具有第6族金屬、第8-10族金屬、及其混合物的催化劑。在一實施例中，較佳的金屬包含具有強的氫化功能之至少一種金屬硫化物。在另一實施例中，加氫精製催化劑可包含第8-10族貴金屬，例如Pt、Pd或其組合。金屬的混合物亦可存在為鬆散金屬催化劑，其中金屬量基於催化劑為30 wt% 或更大。合適的金屬氧化物支撐物包含低酸性氧化物，例如二氧化矽、氧化鋁、二氧化矽-氧化鋁或二氧化鈦，較佳為氧化鋁。用於芳香族飽和之較佳的加氫精製催化劑將包括至少一種在多孔支撐物上具有相對強的氫化功能之金屬。典型的支撐材料包含無定型或結晶狀氧化物材料，例如氧化鋁、二氧化矽、以及二氧化矽-氧化鋁。支撐材料亦可被修飾，例如藉由鹵化，或特別是氟化。催化劑的金屬含量，對於非貴金屬的含量通常是高達20重量百分比。在一實施例中，較佳的加氫精製催化劑可包含屬於M41S類或家族的催化劑之結晶材料。M41S家族的催化劑為具有高二氧化矽含量的中孔材料。實例包含MCM-41、MCM-48以及MCM-50。此類的較佳成員為MCM-41。如果對於芳香族飽和與加氫精製使用個別的催化劑，則可基於芳香族飽和的活性與/或選擇性而選擇芳香族飽和催化劑，而可基於用於改良產物規格(例如產物顏色與多環芳香族還原(polynuclear aromatic reduction))的活性而選擇加氫精製催化劑。美國專利第7,686,949號、第7,682,502號與第8,425,762號進一步揭露可用於本發明之製程的催化劑，該等專利皆併入本文作為參考。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.

加氫精製條件可包含溫度從125℃至425℃(較佳為180℃至280℃)、總壓力從500 psig(～3.4 MPag)至3000 psig(～20.7 MPag)(較佳為1500 psig(～10.3 MPag)至2500 psig(～17.2 MPag))、以及每小時液體空間速度(LHSV)為從0.1 hr-1 至5 hr-1 (較佳為0.5 hr-1 至1.5 hr-1 )。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 ).

在第二或後續的階段之後，在一或多個位置可進行第二分餾或分離。在一些方面，在甜條件下，在USY催化劑存在下，於第二階段中在加氫裂化之後，可進行分餾。而後，可將第二階段加氫裂化流出物中的至少一個潤滑劑沸點範圍部分傳送至脫蠟與/或加氫精製反應器以供進一步處理。在一些方面，可在第二分餾之前，進行加氫裂化與脫蠟。在一些方面，可在第二分餾之前進行加氫精製、脫蠟、以及芳香族飽和。任選地，可在第二分餾之前、第二分餾之後、或在第二分餾之前與之後，進行芳香族飽和與/或加氫精製。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.

如果潤滑劑基礎油產物是期望的，則可將潤滑劑基礎油產物進一步分餾以形成複數個產物。例如，潤滑劑基礎油產物可製成黏度相當於2 cSt的餾分(cut)、4 cSt的餾分、6 cSt的餾分、與/或大於6 cSt的餾分。例如，具有黏度為至少2 cSt的潤滑劑基礎油餾分可為適合用於低傾點應用(例如變壓器油(transformer oil)、低溫液壓油(low temperature hydraulic oil)、或自動變速器油(automatic transmission fluid))的餾分。具有黏度為至少4 cSt的潤滑劑基礎油餾分可為具有受制的揮發性與低傾點的餾分，因而該餾份適合用於根據SAE J300而製造的0W-或5W-或10W等級的機油。此分餾可在柴油(或其他燃料)產物從第二階段自潤滑劑基礎油產物分離之時進行，或是該分餾可在之後發生。任何加氫精製與/或芳香族飽和可發生在分餾之前或之後。在分餾之後，潤滑劑基礎油產物餾分可與適當的添加劑組合作為機油或其他潤滑劑用途。美國專利第8,992,764號、第8,394,255號、美國專利申請案公開案第2013/0264246號與美國專利申請案公開案第2015/ 715,555號揭露可用於本發明中的說明性的製程流程方案，該等揭露內容之全文併入本文作為參考。

潤滑油添加劑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

基礎油構成本發明之引擎或其他機械組件之油潤滑劑組成物的主要成分，並且通常存在量基於組成物的總重量而為從約50至約99重量百分比，較佳為從約70至約95重量百分比，以及更佳為從約85至約95重量百分比。如本文所述，添加物構成本發明之引擎或其他機械組件之油潤滑劑組成物的次要成分，並且通常存在量範圍基於組成物的總重量而為從約小於50重量百分比，較佳為小於約30重量百分比，且更佳為小於約15重量百分比。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.

若需要，可使用基礎油的混合物，例如，基礎油成分與共基礎油(co-base stock)成分。在本發明的潤滑油中，基於組成物的總重量，共基礎油成分的量是從約1至約99重量百分比，較佳為從約5至約95重量百分比，以及更佳為從10至約90重量百分比。在本發明的較佳方面，以基礎油混合物形式的使用低黏度與高黏度基礎油，其包括從5至95 wt%的低黏度基礎油與從5至95 wt%的高黏度基礎油。較佳的範圍包含從10至90 wt%的低黏度基礎油與從10至90 wt%的高黏度基礎油。基於油潤滑劑組成物的總重量，在引擎或其他機械組件之油潤滑劑組成物中，基礎油混合物可包含從15至85 wt%的低黏度基礎油與從15至85 wt%的高黏度基礎油，較佳為從20至80 wt%的低黏度基礎油與從20至80 wt%的高黏度基礎油，以及更佳為從25至75 wt%的低黏度基礎油與從25至75 wt%的高黏度基礎油。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.

在本發明的一方面，基於組成物的總重量，在引擎或其他機械組件之油潤滑劑組成物中，低黏度、中黏度與/或高黏度基礎油存在量為從約50至約99重量百分比，較佳為從約70至約95重量百分比，以及更佳為從約85至約95重量百分比。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.

可用於本發明之經調配的潤滑油可含有一或多種其他常用的潤滑油效能添加劑，其包含(但不限於)抗磨損添加劑、清潔劑、分散劑、黏度改質劑、腐蝕抑制劑、防鏽劑、金屬鈍化劑、極壓添加劑、防卡劑(anti-seizure)、蠟改質劑、其他黏度改質劑、流體損失添加劑(fluid-loss additive)、密封相容劑、潤滑劑、防污劑、發色劑(chromophoric agent)、消泡劑、去乳化劑(demulsifier)、乳化劑、增稠劑、潤濕劑、膠凝劑(gelling agent)、黏附劑(tackiness agent)、著色劑等。關於許多常用的添加劑之評論，參閱“Lubricant Additives, Chemistry and Applications”, Ed. L. R. Rudnick, Marcel Dekker, Inc. 270 Madison Ave. New York, N.J. 10016, 2003、以及Klamann in Lubricants and Related Products, Verlag Chemie, Deerfield Beach, FL；ISBN 0-89573-177-0。亦參考“Lubricant Additives” by M. W. Ranney, published by Noyes Data Corporation of Parkridge, NJ(1973)；亦參閱美國專利第7,704,930號，該揭露之全文併入本文作為參考。這些添加劑通常與不同量的稀釋油一起遞送，稀釋油的量範圍可為從5重量百分比至大於90重量百分比。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.

可用於本發明的添加劑非必須可溶於潤滑油中。不溶性添加劑(例如油中的硬脂酸鋅)可分散在本發明的潤滑油中。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.

當潤滑油組成物包含一或多種添加劑時，將添加劑以足以使其進行其應有的功能的量混合至組成物中。如上所述，添加劑通常存在於潤滑油組成物中作為次要成分，基於組成物的總重量，其含量通常為小於50重量百分比，較佳為小於約30重量百分比，以及更佳為小於約15重量百分比。最常添加至潤滑油組成物中的添加劑的量為至少0.1重量百分比，較佳為至少1重量百分比，更佳為至少5重量百分比。可用於本發明中的此等添加劑之通常量係如下列表1所示。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.

應注意，添加劑中的許多是由添加劑製造商運輸作為濃縮物，含有一或多種添加劑與某些量的基礎油稀釋劑。據此，下列表1中的重量含量以及本文所提及的其他量是指活性成分的量(亦即成分的非稀釋劑部分)。下列指示的重量百分比(wt%)是基於潤滑油組成物的總重量。
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.

前述添加劑皆為市售可得之材料。可分別添加這些添加劑，但這些添加劑通常預先組合在包裝中，其可從潤滑劑油添加劑供應商獲得。可取得具有各種成分、比例與特性的添加劑包裝，並且考慮最終組成物的必要用途而選擇適當的包裝。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.

相對於包含第III類基礎油的習知的潤滑劑組成物，包含本發明之基礎油的潤滑劑組成物具有改良的氧化穩定性。經調配的潤滑劑中的潤滑油基礎油的低溫與氧化效能由MRV(微型旋轉黏度計)測定，根據ASTM D4684量測低溫效能，或藉由壓差掃描熱量測定法(CEC-L-85，其相當於ASTM D6186)測量氧化穩定性時間而測量的氧化效能。本發明的潤滑油對於作為客車機油(passenger vehicle engine oil，PVEO)產品特別有利。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.

相較於一般習知的潤滑油基礎油，本發明之潤滑油基礎油提供一些優點，包含(但不限於)在機油中之改良的氧化效能，例如由壓差掃描熱量測量定法(CEC-L-85，其相當於ASTM D6186)所測量的氧化誘導時間。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).

本發明之潤滑劑組成物可用於各種與潤滑劑相關的最終用途，例如潤滑油或潤滑脂，用於移動與/或相互作用的機械部件、組件或表面需要潤滑的裝置或設備。可用的設備包含引擎與機械。本發明之潤滑基礎油適合用於調配汽車曲軸箱潤滑油、汽車齒輪油、傳動油(transmission oil)、許多工業潤滑劑(包含循環潤滑劑、工業齒輪潤滑劑、潤滑脂、壓縮機油、泵油、冷凍潤滑劑、液壓潤滑劑和金屬加工液體。再者，本發明的潤滑基礎油可得自於再生資源；此等基礎油可符合永續產品的要求，並且可滿足工業團體或政府法規規定的「永續性(sustainability)」標準。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.

提供下列非限制性實例，以說明本發明。

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

Examples

對於實例1和2，根據本文與圖1中描述的方法，處理進料A與B。特別地，具有表3所述性質的進料經處理以製造本發明之第III類基礎油。在階段1加氫處理之後，具有表4所述性質的中間進料進行階段2加氫處理以製造本發明的第III類基礎油。進料A代表具有～67 VI的萃餘物(raffinate)進料，且進料B代表具有～92 VI的高品質VGO進料。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.

使用5種不同的催化劑於實例1與2中的處理，細節如下所述。對於該兩個實例，階段1加氫處理使用催化劑A與B，且階段2加氫處理使用催化劑C、D與E。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.

催化劑A：市售的加氫處理催化劑，其由經Al2 O3 支撐的NiMo組成，例如Criterion KF-868。Catalyst A: A commercially available hydrotreating catalyst consisting of NiMo supported by Al 2 O 3 , such as Criterion KF-868.

催化劑B：市售的加氫處理催化劑，其由鬆散NiMoW氧化物組成，例如ExxonMobil Nebula-20。Catalyst B: A commercially available hydrotreating catalyst consisting of loose NiMoW oxides, such as ExxonMobil Nebula-20.

催化劑C：在USY上0.6wt%的Pt，與Versal-300氧化鋁結合。USY具有二氧化矽對氧化鋁的比率(SiO2 : Al2 O3 )約為75：1。USY是具有12員環孔通道的沸石。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.

催化劑D：市售的脫蠟催化劑，其由經ZSM-48支撐的Pt組成，例如ExxonMobil MSDW。Catalyst D: A commercially available dewaxing catalyst consisting of Pt supported by ZSM-48, such as ExxonMobil MSDW.

催化劑E：市售的加氫精製催化劑，其由經MCM-41支撐的Pt/Pd組成，例如ExxonMobil MaxSat。

實例1：Catalyst E: A commercially available hydrorefining catalyst consisting of Pt / Pd supported by MCM-41, such as ExxonMobil MaxSat.

Example 1:

進料A性質如表3所示。將進料以兩種轉換程度(即17%和33%)進行加氫處理，而後混合(44.6/55.4)以得到具有表3所示性質的產物。關於乾蠟量，基於-0.33wt%/℃的傾點的校正，將乾蠟的量校正至傾點為-18℃的預期值。關於黏度指數，基於0.33 VI/℃的傾點的校正，將黏度指數校正至傾點為-18℃的預期值。

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.

經由第一階段(其主要是提升黏度指數(VI)且移除琉與氮的加氫處理單元)處理進料A (具有溶劑脫蠟油進料黏度指數為約67)。催化劑A與B皆裝載於相同的反應器中，進料先接觸催化劑A。經加氫處理的進料之後進入汽提部分，在此移除輕質油與柴油。在階段1加氫處理過程中，進料A被分開且於兩種不同程度(標示為「低」與「高」轉換)進行轉換。中間進料(A1與A2)的性質如表4中所示。來自A1與A2的較重潤滑劑餾分而後進入第二階段，在此進行加氫裂化、脫蠟與加氫精製。使用這些步驟(描述如下)中的每一個的各種處理條件以製造五種第III類基礎油料A1至A6，其性質如表6 (4-5 cSt)、7 (5-7 cSt)與8 (8-11 cSt)所示。已經發現進料和製程的這種組合可製造具有獨特組成特性的第III類基礎油。在所製造的較低與較高黏度基礎油中，皆觀察到這些獨特的組成特性，如圖3與4所示。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.

基於最終基礎油產物之所欲的轉換率與VI，調整上述步驟(加氫處理、加氫裂化、催化性脫蠟與加氫精製)中的每一個的處理條件。用於製造本發明之標的的第III類基礎油的條件可在表5中找到。在第一加氫處理階段中的700℉+轉換率程度範圍從20至40%，並且第一階段中的處理條件包含溫度從635℉至725℉；氫氣分壓從500 psig至3000 psig；每小時液體空間速度從0.5 hr-1 至1.5 hr-1 ；以及氫循環速率從3500 scf/bbl至6000 scf/bbl。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.

在具有氫氣分壓為300 psig至5000 psig、氫循環速率從1000 scf/bbl至6000 scf/bbl的單一反應器中進行由加氫裂化、催化性脫蠟與加氫精製組成的第二階段。催化劑C、D與E裝載於第二階段中相同的反應器中，其與進料接觸的順序為C、D、E。調整製程參數以達到所欲之700℉+轉換率為15-70%。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%.

在加氫裂化步驟中的處理條件包含溫度從250℉至700℉；每小時液體空間速度為0.5 hr-1 至1.5 hr-1 。催化性脫蠟步驟中的處理條件包含溫度從250℉至660℉；以及每小時液體空間速度從1.0 hr-1 至3.0 hr-1 。加氫處理步驟中的處理條件包含溫度從250℉至480℉；以及每小時液體空間速度從0.5 hr-1 至1.5 hr-1 。

實例2：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:

進料B的性質如表3所示。經由第一階段加氫處理單元(其提升黏度指數(VI)且移除硫與氮)處理進料B。經加氫處理的進料而後進入汽提部分，在此移除輕質油與柴油。催化劑A與B皆裝載於相同的反應器中，進料先接觸催化劑A。在階段1加氫處理過程中，進料B進行一個轉換並且顯示如表4所示的性質。來自此中間物之較重的潤滑油餾分而後進入第二階段，在此進行加氫裂化、脫蠟與加氫精製。使用這些步驟中的每一個的各種處理條件(如表4所示)以製造六種第III類基礎油料B1至B6，如表6至8所示。已經發現進料和製程的這種組合可製造具有獨特組成特性的基礎油。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.

基於最終基礎油產物之所欲的轉換率與VI，調整上述步驟(加氫處理、加氫裂化、催化性脫蠟與加氫精製)中的每一個的處理條件。用於製造本發明之標的的第III類基礎油的條件可在表5中找到。在第一加氫處理階段中的700℉+轉換率程度範圍從20至40%，並且第一階段中的處理條件包含溫度從635℉至725℉；氫氣分壓從500 psig至3000 psig；每小時液體空間速度從0.5 hr-1 至1.5 hr-1 (較佳為從0.5 hr-1 至1.0 hr-1 ，最佳為從0.7 hr-1 至0.9 hr- )；以及氫循環速率從3500 scf/bbl至6000 scf/bbl。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.

在具有氫氣分壓為300 psig至5000 psig、氫循環速率從1000 scf/bbl至6000 scf/bbl的單一反應器中進行由加氫裂化、催化性脫蠟與加氫精製組成的第二階段。催化劑C、D與E裝載於第二階段中相同的反應器中，其與進料接觸的順序為C、D、E。調整製程參數以達到所欲之700℉+轉換率為15-70%，較佳為15-55%。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%.

在加氫裂化步驟中的處理條件包含溫度從250 ℉至700℉；且每小時液體空間速度為0.5 hr-1 至1.5 hr-1 。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 .

催化性脫蠟步驟中的處理條件包含溫度從250℉至660℉；以及每小時液體空間速度從1.0 hr-1 至3.0 hr-1 。加氫處理步驟中的處理條件包含溫度從250℉至480℉；以及每小時液體空間速度從0.5 hr-1 至1.5 hr-1 。



實例3(比較例)：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):

根據圖1所示之習知基礎油加氫處理方案，處理高品質真空氣體油原料。此習知的加氫處理方案廣泛使用市售的催化劑，並且是習知之經加氫處理的第III類基礎油的代表。藉由此方法製造的基礎油在表與圖式中以K1與K2表示。此外，一些市售的基礎油之性質可在下列表與圖式中找到並且標示為市售比較實例。市售比較基礎油皆為廣泛可市售獲得，並且為現今市場上所提供第III類產品之範圍的代表。總之，這些市售基礎油與基礎油K1及K2用以說明本發明之基礎油(本發明之標的)的獨特性。

測量程序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

使用先進的分析技術(包含氣相層析質譜(gas chromatography mass spectrometry，GCMS)、超臨界流體層析法(supercritical fluid chromatography，SFC)與碳-13核磁共振(13 C NMR))的組合，測定潤滑油基礎油組成物。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.

根據ASTM方法D2270，測定黏度指數(VI)。VI是關於使用ASTM方法D445於40℃與100℃所測量的運動黏度(kinematic viscosity)。注意，這些將簡稱為KV100與KV40。藉由ASTM D5950測量傾點。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.

使用氣相色層分析蒸餾(gas chromatograph distillation，GCD)的結果和先前建立的關鍵沸點與使用ASTM D5800測得的Noack之間的相關性來估計Noack揮發性。已發現此相關性可預測在ASTM D5800的再現性內之測量結果。同樣地，使用Walther方程式估計於-35℃的冷啟動模擬器(cold cranking simulator，CCS)。輸入方程式的是於40℃與100℃(ASTM D445)實驗測得的運動黏度以及於15.6℃(ASTM D4052)測得的密度。平均而言，在-35℃的這些估計的CCS結果與ASTM D5293的再現性內的其他基礎油的測量結果相匹配。使用上述方法估計表6至8中所示的Noack和CCS之所有結果，因此可將它們相互比較。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.

可藉由GCMS測定的環烷烴、支鏈碳、直鏈碳和末端碳的量與分佈來確定本發明的潤滑油基礎油料的獨特組成特性，如圖5至8所示。較佳地，藉由SFC校正GCMS結果；然而，發現無論是否藉由SFC校正GCMS結果，2R+N/1RN比率是相同的。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.

在市售超臨界流體色層分析系統上進行SFC。該系統配備以下組件：用於遞送超臨界二氧化碳移動相的高壓泵；溫度受控的管柱烤箱(temperature controlled column oven)；具有高壓液體注射閥的自動取樣器(用於遞送樣品材料至移動相中)；火焰離子化偵測器；移動相分離器(低無效體積三通管(low dead volume tee))；背壓調節器(以維持CO2 於超臨界相中)；以及計算機與數據系統(用於控制組件且記錄數據訊號)。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).

關於分析，將～75mg樣品稀釋在2 mL甲苯中並裝入標準墊片(septum)蓋自動取樣瓶中。經由高壓取樣閥，引入樣品。使用多個串聯連接(長度為250 mm且2 mm或4 mm內徑)的市售矽膠填充管柱(5μm，具有60或30Å孔)進行SFC分離。管柱溫度通常維持在35或40℃。關於分析，管柱頭壓力通常為250 bar。對於2 mm內徑(inner diameter，i.d.)管柱，液體CO2 流速通常為0.3 mL/分鐘，或對於4 mm i.d.管柱為2.0 mL/分鐘。運行的樣品主要是在溶劑(在本文為甲苯)之前洗提出的所有飽和化合物。SFC FID訊號整合成石蠟(paraffin)與環烷烴(naphthene)區域。使用色層分析法分析潤滑基礎油之總石蠟與總環烷烴的分離峰(split)。使用各種標準材料，校準石蠟/環烷烴比率。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.

在市售超臨界流體色層分析系統上進行SFC。該系統配備以下組件：用於遞送超臨界二氧化碳移動相的高壓泵；溫度受控的管柱烤箱(temperature controlled column oven)；具有高壓液體注射閥的自動取樣器(用於遞送樣品材料至移動相中)；火焰離子化偵測器；移動相分離器(低無效體積三通管(low dead volume tee))；背壓調節器(以維持CO2 於超臨界相中)；以及計算機與數據系統(用於控制組件且記錄數據訊號)。關於分析，將～75mg樣品稀釋在2 mL甲苯中並裝入標準墊片蓋自動取樣瓶中。經由高壓取樣閥，引入樣品。使用多個串聯連接(長度為250 mm且2 mm或4 mm內徑)的市售矽膠填充管柱(5μm，具有60或30Å孔)進行SFC分離。管柱溫度通常維持在35或40℃。關於分析，管柱頭壓力通常為250 bar。對於2 mm內徑(inner diameter，i.d.)管柱，液體CO2 流速通常為0.3 mL/分鐘，或對於4 mm i.d.管柱為2.0 mL/分鐘。運行的樣品主要是在溶劑(在本文為甲苯)之前洗提出的所有飽和化合物。SFC FID訊號整合成石蠟(paraffin)與環烷烴(naphthene)區域中。使用色層分析法分析潤滑基礎油之總石蠟與總環烷烴的分離峰(split)。使用各種標準材料，校準石蠟/環烷烴比率。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.

關於本文所使用的GCMS，添加將近50毫克的基礎油樣品至標準2微升自動取樣瓶(vial)中，並且用二氯甲烷溶劑稀釋以填充小瓶。用墊片蓋密封小瓶。使用配備有自動取樣器的Agilent 5975C GCMS(氣相色層分析質譜儀)運行樣品。使用非極性GC管柱來模擬GC的蒸餾或碳數洗提特性。所使用的GC管柱為Restek Rxi-1ms。管柱尺寸為長度30公尺×內徑0.32 mm，固定相塗層具有0.25微米膜厚度。GC管柱連接至GC的分流(split)/不分流(split-less)注射埠(維持在360℃並且以不分流模式操作)。將恆壓模式的氦氣(～7 PSI)用於GC載體相。GC管柱的出口經由保持在350℃的轉移管線而進入質譜儀。GC管柱的溫度程序如下：在100℃維持2分鐘，每分鐘5℃升溫，在350℃維持30分鐘。使用電子衝擊離子化來源(維持在250℃)操作質譜儀，並且使用標準條件(70 eV離子化)操作。使用Agilent Chemstation軟體獲得儀器控制和質譜數據採集。使用供應商提供的基於儀器自動調諧功能的標準來驗證質量校準和儀器調諧效能。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.

基於對含有已知直鏈石蠟(normal paraffin)的標準樣品的分析，測定樣品之相對於直鏈石蠟的遲滯時間的GCMS遲滯時間。而後，將質譜平均。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.

藉由將25-30 wt%的樣品溶解在CDCl3 中並添加7% Cr(III)-乙醯丙酮化物(Cr(III)-acetylacetonate)作為弛緩劑來製備用於13 C NMR的樣品。在JEOL ECS NMR光譜儀上進行NMR實驗，質子共振頻率為400 MHz。在27℃下使用反向門控去耦實驗(inverse gated decoupling experiment)進行定量13 C NMR實驗，其具有45°翻轉角、脈衝之間6.6秒、64k數據點以及2400次掃描。所有光譜均參考在0 ppm的三甲基矽氧烷(trimethylsiloxane，TMS)。用0.2-1 Hz的譜線加寬(line broadening)處理光譜，並在手動積分之前應用基線校正。對整個光譜積分以確定不同積分區域的mole%如下：32.19-31.90 ppm的γ碳、30.05-29.65 ppm的ε碳；29.65-29.17 ppm的δ碳；22.96-22.76 ppm的β碳；22.76-22.50 ppm的懸垂(pendant)和末端甲基；19.87-18.89 ppm的懸垂甲基；14.73-14.53 ppm的懸垂丙基；14.53-14.35 ppm的末端丙基；14.35-13.80 ppm的α碳；11.67-11.22 ppm的末端乙基；以及11.19-10.57 ppm的懸垂乙基。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.

關於本文的分析，直鏈碳被定義為α、β、γ、δ和ε峰的總和。支鏈碳被定義為懸垂甲基、懸垂乙基、以及懸垂丙基的總和。末端碳被定義為末端甲基、末端乙基、以及末端丙基的總和。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.

本發明之第III類低黏度潤滑油基礎油且具有在4-5 cSt範圍中的KV100的實例如表6中所示。例如，比較本發明之低黏度潤滑油基礎油與具有相同黏度範圍之典型第III類低黏度基礎油。具有由先進加氫裂化製程製造的獨特組成物的第III類基礎油料呈現4 cSt至12 cSt的基礎油KV100的範圍。組成物的差異包含多環環烷烴對單環環烷烴的比率(2R+N/1RN)、支鏈碳對直鏈碳的比率(BC/SC)以及支鏈碳對末端碳的比率(BC/TC)的差異，如表6至8以及圖3至8所示。









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.









圖5與6以及表6至8說明由本發明的輕型中性(LN)基礎油劃分的組成空間之獨特區域。圖5描述環烷烴比率(由GCMS測量)與分支程度(由NMR測量)，並且說明本發明的基礎油佔據圖表的獨特區域。由虛線標示的此區域發生在環烷烴比率數值≤ 0.52且分支程度≤ 0.21。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.

使用圖6進行類似的情況，其描述了環烷烴比率(由GCMS測量)與分支的本質(由NMR測量)。短語「分支的本質」表示支鏈碳對末端碳的比率，其中較高的比率表示較多的內部分支。在本文中較低的比率表示接近分子的端點(末端C)有較多的分支。與圖5中的情況一樣，圖6中的本發明的基礎油佔據由虛線表示的圖表的獨特區域。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.

與LN基礎油的情況一樣，圖7與8以及表6至8說明由MN基礎油劃分的組成空間的獨特區域。圖7說明環烷烴比率(由GCMS測量)與分支程度(由NMR測量)，並且說明本發明的基礎油佔據圖表的獨特區域。由虛線標示的此區域發生在環烷烴比率數值＜ 0.59且分支程度≤ 0.216。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.

圖8說明環烷烴比率(由GCMS測量)與分支程度(由NMR測量)。短語「分支的本質」表示支鏈碳對末端碳的比率，其中較高的比率表示較多的內部分支。較低的比率表示接近分子的端點(末端C)有較多的分支。由虛線標示的區域發生在環烷烴比率數值＜ 0.59且分支程度＜0.23。與圖7不同，本發明的基礎油現在佔據由線(而不是框)表示的圖之區域。

實例4Figure 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

關於測試第III類MN基礎油，使用10W-40重型機油(heavy-duty engine oil，HDEO)配方作為「主體」配方。所選擇的配方使用添加劑包裝，其是為ACEA E6、9 SSI苯乙烯-異戊二烯VM、以及輕型中性共基礎油而調配。為此目的亦選擇Yubase 4。表9中提供配方，圖5中提供低溫結果。一旦混合，根據ASTM D4684，於-30℃使用微型旋轉黏度計(mini-rotary viscometer，MRV)測試HDEO的低溫效能。表9說明用以測試在HDEO中的第III類MN基礎油之配方。低溫效能數據(MRV)如表5中所示。
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.

中型中性(MN)基礎油的傾點相較於分支的本質，亦即由NMR量測的支鏈C/末端C比率。用本發明之第III類基礎油製備的潤滑劑顯示出與習知之經加氫處理的基礎油幾乎正交(無關)的行為。在混合至10W-40 HDEO中的中型中性(MN)基礎油的MRV行為中可以看到類似的趨勢。

實例5The 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

關於在完全調配的客車機油(passenger car motor oil，PCMO)中的測試，選擇「主體」0W-20配方，其使用市場通用的GF-5添加劑包裝、50 SSI高乙烯烯烴共聚物(high ethylene olefin copolymer，HE OCP) VM、聚甲基丙烯酸酯(polymethacrylate，PMA)PPD。下列表10提供配方。配方策略使得所有非基礎油成分在混合物之間保持固定；僅第III類基礎油改變。一旦混合，測試PCMO於-40℃(ASTM D4684)在MRV中的低溫效能。

實例 6For 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

關於測試具有第III類MN基礎油的潤滑劑組成物，使用類似的策略，但使用10W-40 重型機油(HDEO)配方而不是PCMO配方。所選的配方使用添加劑包裝，其是為了ACEA E6和9 SSI苯乙烯-異戊二烯VM而調配。與用以測試LN基礎油的0W-20 PCMO不同，用以測試MN基礎油的10W-40 HDEO需要使用LN共基礎油。為此目的亦選擇Yubase 4。上述表9中提供配方。一旦混合，測試HDEO於-30℃(ASTM D4684)在MRV中的低溫效能。結果如上述表6中所示。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.

圖9說明用輕型中性(LN)基礎油混合至0W-20 PCMO中所製備的潤滑組成物之MRV行為與傾點大致無關。一個值得注意的例外是具有相對高傾點(-8℃)的樣品，其顯示在測試溫度下基本上為固體(＞400,000 mPa.s)的MRV結果。為清楚起見，圖9中省略了這點。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.

圖10顯示用輕型中性(LN)基礎油混合至0W-20 PCMO中所製備的潤滑組成物之與環烷烴比率相關的MRV行為。與MRV黏度相對於傾點之作圖不同，對於用本發明之基礎油製備的潤滑組成物與用習知之經加氫處理的基礎油製備的潤滑組成物，環烷烴比率顯示明顯不同。圖10中的線之方程式為：
本發明組成物的線：VI = 89582-167956*(2R+N/1RN)
習知HDP的線：VI =-8840 + 49814*(2R+N/1RN)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)

圖11顯示用中型中性(MN)基礎油混合至10W-40 HDEO中所製備的潤滑組成物之MRV行為與傾點大致無關。這與LN基礎油達成的結論類似。同樣地，圖12顯示用中型中性(MN)基礎油混合至10W-40 HDEO中所製備的潤滑組成物之與環烷烴比率相關的MRV行為。與MRV黏度相對於傾點之作圖不同，對於用本發明之基礎油製備的潤滑組成物與用習知之經加氫處理的基礎油製備的潤滑組成物，環烷烴比率顯示明顯不同。值得注意的是，在兩種黏度等級的基礎油中觀察到相同的趨勢：用本發明之基礎油製備的潤滑組成物顯示MRV黏度和環烷烴比率之間的負相關性，而用習知之經加氫處理的基礎油製備的潤滑組成物顯示正相關性。這可以藉由圖10和12的類似外觀看出。圖12中的線之方程式為：
本發明組成物的線：VI = 39054-44125*(2R+N/1RN)
習知組成物的線：VI =-1480 + 28197*(2R+N/1RN)

實例7FIG. 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

使用藉由壓差掃描熱量分析法(CEC-L-85)測量的氧化誘導時間(oxidation induction time，OIT)測試上述實例4中製備的HDEO潤滑劑組成物的氧化性能。CEC-L-85的ASTM均等物為D6186。藉由將樣品溫度在175℃維持固定2小時而測量OIT，在此時終止測試。在兩小時測試期間未氧化的樣品在表11的「OIT」欄中用「＞120」表示。
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.

圖13與14為說明氧化誘導時間(OIT)與黏度指數(VI)的圖式。圖14使用與圖13相同的數據，但具有較小的y軸範圍。數字越大(對應於較長的OIT)表示較好的氧化效能。測試在120分鐘終止(因此120分鐘是最大可能值)。圖14顯示OIT通常隨著VI的增加而改善，但圖13顯示單獨的VI無法解釋本發明之潤滑組成物的顯著效能差異。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.

圖15與16為說明OIT相對於2R+N/1RN (由SFC校正的GCMS測量)的圖式。圖16使用與圖15相同的數據，但具有較小的y軸範圍。相較於用其它基礎油製備的潤滑組成物，兩個圖式皆指示本發明的潤滑組成物在OIT的表現得更好。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與EP條款PCT and EP clauses

1. 一種潤滑組成物，其包括：第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度(KV100)為4.0 cSt至12.0 cSt、黏度指數為120至133、以及多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.43；以及有效量的一或多種潤滑劑添加劑；其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如第1條的組成物，其中該基礎油具有從4.0 cSt至5.0 cSt的KV100。2. The composition as in clause 1, wherein the base oil has a KV100 from 4.0 cSt to 5.0 cSt.

3. 如第1條的組成物，其中該基礎油具有從5.0 cSt至7.0 cSt的KV100。3. The composition as in clause 1, wherein the base oil has a KV100 of from 5.0 cSt to 7.0 cSt.

4. 如第1或2條的組成物，其中該黏度指數為120至133，並且小於或等於142*(1-0.0025 exp(8*(2R+ N/1RN)))。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. 如第1或3條的組成物，其中該黏度指數為120至133，並且小於或等於150.07*(1-0.0106*exp (4.5*(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. 一種客車機油組成物，其包括：第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度為4.0 cSt至5.0 cSt、黏度指數為從120至小於140、多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.45；以及有效量的一或多種潤滑劑添加劑；其中該油組成物的氧化誘導時間為大於120分鐘。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. 如第6條的組成物，其中該黏度指數為120至140，並且小於或等於142*(1-0.0025 exp(8*(2R+ N/1RN)))。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. 一種重型柴油引擎潤滑油組成物，其包括：第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度為5.5 cSt至7.0 cSt、黏度指數為從120至小於144、以及多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.56；以及有效量的一或多種潤滑劑添加劑；其中該潤滑油組成物的氧化誘導時間為大於120分鐘。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. 如第8條的組成物，其中該黏度指數為120至144，並且小於或等於142*(1-0.0025 exp(8*(2R+ N/1RN)))。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. 一種潤滑組成物，其包括：第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度為4.0 cSt至5.0 cSt、黏度指數為120至140、多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.52、以及支鏈碳對直鏈碳的比率(BC/SC)小於或等於0.21；以及有效量的一或多種潤滑劑添加劑；其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如第10條的潤滑組成物，其中該基礎油之支鏈碳對末端碳的比率(BC/TC)小於或等於2.1。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. 一種潤滑組成物，其包括：第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度為5.0 cSt至12.0 cSt、黏度指數為120至140、多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.59、以及支鏈碳對直鏈碳的比率(BC/SC)小於或等於0.26；以及有效量的一或多種潤滑劑添加劑；其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如第12條的潤滑組成物，其中該基礎油之多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.59，且BC/TC≤ 2.3。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. 一種潤滑組成物，其包括：第III類基礎油，其具有：至少90 wt%的飽和烴；100℃時的運動黏度(KV100)為4.0 cSt至5.0 cSt；黏度指數為從120至140；多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.45；以及有效量的一或多種潤滑劑添加劑；其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如第14條的組成物，其中該基礎油的KV100為4.0至4.7。15. The composition according to clause 14, wherein the KV100 of the base oil is 4.0 to 4.7.

16. 一種潤滑組成物，其包括第III類基礎油，該基礎油具有：至少90 wt%的飽和烴；100℃時的運動黏度(KV100)為5.0 cSt至12.0 cSt；黏度指數為從120至144；多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.56；以及有效量的一或多種潤滑劑添加劑；其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如第16條的組成物，其中該基礎油的KV100為5.5至7.0。17. The composition according to clause 16, wherein the base oil has a KV100 of 5.5 to 7.0.

本文所引用的所有專利和專利申請案、測試程序(例如ASTM方法、UL方法等)和其他文獻皆藉由引用完全併入本案，只要此等揭露與本發明內容一致，並且適用於允許此類合併的所有司法管轄區。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.

當本文列出數值下限和數值上限時，涵蓋從任何下限到任何上限的範圍。儘管已經特別地描述了本發明的說明性實施例，但是應該理解，在不脫離本發明的精神和範圍下，本技藝的技術人士將明白並且可以容易地進行各種其他修改。據此，並非旨在將所申請專利範圍的範圍限於本文闡述的實例和說明，而是將申請專利範圍解釋為包含本發明中的可專利的新穎性之所有特徵，包含本技藝中的技術人士將視為其等同物的所有特徵。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.

本發明已經描述於以上參考許多實施例和具體實例。鑑於以上詳細說明，本技藝中的技術人士將想到許多變化。所有這些明顯的變化都在所附申請專利範圍的全部預期範圍內。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‧‧‧原料105‧‧‧ raw materials

110‧‧‧第一反應器 110‧‧‧first reactor

120‧‧‧第二反應器 120‧‧‧second reactor

125‧‧‧加氫處理之流出物 125‧‧‧Hydrotreated effluent

130‧‧‧分餾器 130‧‧‧ Fractionator

132‧‧‧輕質油餾分 132‧‧‧ light oil fraction

135‧‧‧潤滑劑沸點範圍餾分 135‧‧‧ Lubricant boiling range fraction

137‧‧‧燃料沸點範圍餾分 137‧‧‧ Fuel boiling point range fraction

140‧‧‧第二階段加氫裂化反應器 140‧‧‧Second stage hydrocracking reactor

145‧‧‧流出物 145‧‧‧effluent

150‧‧‧加氫精製反應器 150‧‧‧hydrorefining reactor

152‧‧‧輕質油 152‧‧‧ light oil

157‧‧‧燃料沸點範圍餾分 157‧‧‧ Fuel boiling point range fraction

155‧‧‧流出物 155‧‧‧ effluent

160‧‧‧經分餾 160‧‧‧ fractionated

圖1為根據本發明之實施例的多階段(stage)反應系統。FIG. 1 is a multi-stage reaction system according to an embodiment of the present invention.

圖2顯示適合用於製造本發明之第III類基礎油的處理架構之實例。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.

圖3為說明相較於其他第III類基礎油，本發明之輕型中性第III類基礎油(light neutral Group III base stock)之具有多環環烷烴之分子對具有單環環烷烴之分子的比率(2R+N/1RN)和黏度指數之間的關係之圖式。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.

圖4為說明相較於其他第III類基礎油，本發明之中型中性第III類基礎油(medium neutral Group III base stock)之具有多環環烷烴之分子對具有單環環烷烴之分子的比率(2R+N/1RN)和黏度指數之間的關係之圖式。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.

圖5為說明相較於其他第III類基礎油，本發明之輕型中性第III類基礎油之具有多環環烷烴之分子對具有單環環烷烴之分子的比率(2R+N/1RN)和分支程度(支鏈碳/直鏈碳)之間的關係之圖式。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).

圖6為說明相較於其他第III類基礎油，本發明之輕型中性第III類基礎油之具有多環環烷烴之分子對具有單環環烷烴之分子的比率(2R+N/1RN)和分支的本質(支鏈碳/末端碳)之間的關係之圖式。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).

圖7為說明相較於其他第III類基礎油，本發明之中高型中性第III類基礎油(medium and high neutral Group III base stock)之具有多環環烷烴之分子對具有單環環烷烴之分子的比率(2R+N/1RN)和分支程度(支鏈碳/直鏈碳)之間的關係之圖式。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).

圖8為說明相較於其他第III類基礎油，本發明之中重型中性第III類基礎油之具有多環環烷烴之分子對具有單環環烷烴之分子的比率(2R+N/1RN)和分支的本質(支鏈碳/末端碳)之間的關係之圖式。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).

圖9為說明相較於其他第III類基礎油，根據本發明所製備的經調配的輕型中性第III類基礎油的傾點(pour point)和微旋轉黏度(mini-rotary viscosity，MRV)行為之間的關係之圖式。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.

圖10為說明相較於其他第III類基礎油，根據本發明所製備的經調配的輕型中性第III類基礎油的具有多環環烷烴之分子對具有單環環烷烴之分子的比率(2R+N/1RN)和微旋轉黏度(MRV)行為之間的關係之圖式。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.

圖11為說明相較於其他第III類基礎油，根據本發明所製備的經調配的中型中性第III類基礎油的傾點和微旋轉黏度(MRV)行為之間的關係之圖式。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.

圖12為說明相較於其他第III類基礎油，根據本發明所製備的經調配的中型中性第III類基礎油的具有多環環烷烴之分子對具有單環環烷烴之分子的比率(2R+N/1RN)和微旋轉黏度(MRV)行為之間的關係之圖式。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.

圖13為根據一實施例之基礎油的氧化誘導時間與黏度指數之作圖。FIG. 13 is a graph of oxidation induction time and viscosity index of a base oil according to an embodiment.

圖14為根據一實施例之基礎油的氧化誘導時間與黏度指數之作圖。FIG. 14 is a graph of oxidation induction time and viscosity index of a base oil according to an embodiment.

圖15為根據一實施例之基礎油的氧化誘導時間與(藉由SFC校正的GCMS所測量的)2R+N/1RN之作圖。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.

圖16為根據一實施例之基礎油的氧化誘導時間與(藉由SFC校正的GCMS所測量的)2R+N/1RN之作圖。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)

一種潤滑組成物，其包括： 第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度(KV100)為4.0 cSt至12.0 cSt、黏度指數為120至133、以及多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.43；以及 有效量的一或多種潤滑劑添加劑； 其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如申請專利範圍第1項之組成物，其中該基礎油具有從4.0 cSt至5.0 cSt的KV100。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. 如申請專利範圍第1項之組成物，其中該基礎油具有從5.0 cSt至7.0 cSt的KV100。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. 如申請專利範圍第1或2項之組成物，其中該黏度指數為120至133，並且小於或等於142*(1-0.0025 exp(8*(2R+ N/1RN)))。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))). 如申請專利範圍第1或3項之組成物，其中該黏度指數為120至133，並且小於或等於150.07*(1-0.0106*exp(4.5* (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))). 一種客車機油組成物，其包括： 第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度為4.0 cSt至5.0 cSt、黏度指數為從120至小於140、多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.45；以及 有效量的一或多種潤滑劑添加劑； 其中該油組成物的氧化誘導時間為大於120分鐘。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. 如申請專利範圍第6項之組成物，其中該黏度指數為120至140，並且小於或等於142*(1-0.0025 exp(8*(2R+ N/1RN)))。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))). 一種重型柴油引擎潤滑油組成物，其包括： 第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度為5.5 cSt至7.0 cSt、黏度指數為從120至小於144、以及多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.56；以及 有效量的一或多種潤滑劑添加劑； 其中該潤滑油組成物的氧化誘導時間為大於120分鐘。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. 如申請專利範圍第8項之組成物，其中該黏度指數為120至144，並且小於或等於142*(1-0.0025 exp(8*(2R+ N/1RN)))。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))). 一種潤滑組成物，其包括： 第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度為4.0 cSt至5.0 cSt、黏度指數為120至140、多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.52、以及支鏈碳對直鏈碳的比率(BC/SC)小於或等於0.21；以及 有效量的一或多種潤滑劑添加劑； 其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如申請專利範圍第10項之潤滑組成物，其中該基礎油之支鏈碳對末端碳的比率(BC/TC)小於或等於2.1。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. 一種潤滑組成物，其包括： 第III類基礎油，該第III類基礎油具有至少90 wt%的飽和烴、100℃時的運動黏度為5.0 cSt至12.0 cSt、黏度指數為120至140、多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.59、以及支鏈碳對直鏈碳的比率(BC/SC)小於或等於0.26；以及 有效量的一或多種潤滑劑添加劑； 其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如申請專利範圍第12項之潤滑組成物，其中該基礎油之多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.59，且BC/TC≤ 2.3。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. 一種潤滑組成物，其包括： 第III類基礎油，其具有： 至少90 wt%的飽和烴； 100℃時的運動黏度(KV100)為4.0 cSt至5.0 cSt；黏度指數為從120至140； 多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.45；以及 有效量的一或多種潤滑劑添加劑； 其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如申請專利範圍第14項之組成物，其中該基礎油的KV100為4.0至4.7。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. 一種潤滑組成物，其包括第III類基礎油，該基礎油具有： 至少90 wt%的飽和烴； 100℃時的運動黏度(KV100)為5.0 cSt至12.0 cSt； 黏度指數為從120至144； 多環環烷烴對單環環烷烴的比率(2R+N/1RN)小於0.56；以及 有效量的一或多種潤滑劑添加劑； 其中該潤滑組成物的氧化誘導時間為大於120分鐘。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. 如申請專利範圍第16項之組成物，其中該基礎油的KV100為5.5至7.0。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.
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