CN102575143B - 使用气变液基础油料配制密封液 - Google Patents
使用气变液基础油料配制密封液 Download PDFInfo
- Publication number
- CN102575143B CN102575143B CN201080047637.6A CN201080047637A CN102575143B CN 102575143 B CN102575143 B CN 102575143B CN 201080047637 A CN201080047637 A CN 201080047637A CN 102575143 B CN102575143 B CN 102575143B
- Authority
- CN
- China
- Prior art keywords
- base oil
- sealing liquid
- lubricant base
- liquid
- molecule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/16—Sealings between relatively-moving surfaces
- F16J15/34—Sealings between relatively-moving surfaces with slip-ring pressed against a more or less radial face on one member
- F16J15/3404—Sealings between relatively-moving surfaces with slip-ring pressed against a more or less radial face on one member and characterised by parts or details relating to lubrication, cooling or venting of the seal
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/16—Sealings between relatively-moving surfaces
- F16J15/34—Sealings between relatively-moving surfaces with slip-ring pressed against a more or less radial face on one member
- F16J15/3464—Mounting of the seal
- F16J15/348—Pre-assembled seals, e.g. cartridge seals
- F16J15/3484—Tandem seals
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine salts thereof
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
-
- 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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/74—Noack Volatility
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/34—Lubricating-sealants
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Lubricants (AREA)
- Sealing Material Composition (AREA)
- Structures Of Non-Positive Displacement Pumps (AREA)
Abstract
本发明确定,包含得自费托蜡的润滑剂油的密封液制剂展示了与包含得自聚α烯烃(PAO)的润滑剂的密封液相当的性能。本发明的密封液能够提供与PAO基密封液所提供的优异性能类似优异性能,但成本更低。
Description
发明领域
本发明涉及一种由气变液(GTL)或煤变液体类进料制剂如费托蜡来制备密封液的方法,所述密封液用于涡轮机中以作为阻挡液或缓冲液。
发明背景
密封液、更具体地阻挡液和缓冲液为用于湿法密封中的外部流体以防止工艺流体泄露至环境中。将其用于其中工艺流体的压力增大的装置如泵、压缩机和其他类型的涡轮机中。也将阻挡液用作缓冲液。可将阻挡液保持在高于工艺流体压力的压力下,而将缓冲液保持在等于或低于工艺流体压力的压力下。所使用的压力取决于机器中使用的密封类型。
使用密封液有几种目的,包括:
(a)隔绝不应排放至环境中的有害工艺流体;
(b)减少污染问题;
(c)减少泄露和昂贵产物的浪费;以及
(d)降低计划外的停机时间。
密封液应为:
(a)与通过机器所实施的工艺相容;
(b)与密封材料相容;
(c)用于密封面的良好润滑剂和传热介质;以及
(d)对环境和工人友好。
密封液通常选自包含矿物油、聚α-烯烃(PAO)、煤油或柴油、二醇、醇和水的集合。PAO基密封液在氧化稳定性、高温性能和低温性能方面提供比矿物油柴油更优异的性能。然而,PAO基流体昂贵。已经开发了GTL基制剂,其在降低成本下提供了优异的性能。GTL基和CTL基制剂具有高粘度指数和低的倾点,并使用大量基础油(参见表1)制得,所述基础油很快将以相对于常规的II类和III类基础油有竞争力的价格容易地获得。
发明概述
使用与表2中所示的添加剂共混的GTL XXL和GTX XL(参见表1)作为润滑剂,开发了适合用作涡轮机中的密封液的两种流体制剂。相对于得自聚α烯烃的密封液对这些产物的性能进行了评价(表2)。已经发现,GTL和CTL基制剂能够提供相当的性能。典型地,PAO基密封液的成本高。GTL和CTL基密封液能够提供与PAO基流体所提供的优异性能类似的优异性能,但成本更低。
本发明公开了一种流体,其适合在涡轮机中用作密封液。其包含:具有大于320但不大于375的平均分子量、大于118的粘度指数和大于97wt%的链烷属碳的润滑剂基础油。本发明的密封液具有低于-60℃的倾点和小于30ml的由ASTM D 892-03确定的序列II起泡倾向。
我们已经发明了制备具有非常低的倾点和提高的起泡倾向的密封液的方法。所述方法包括如下步骤:a)选择具有大于75wt%的正链烷烃和小于25ppm的总共合计的氮和硫的蜡质进料;b)对所述蜡质进料进行加氢异构化脱蜡以制造润滑剂基础油;c)将所述润滑剂基础油分馏成一种或多种馏分;d)选择具有大于320的平均分子量、大于118的粘度指数、小于25wt%的烯烃的一种或多种馏分;以及e)将所述一种或多种选择的馏分与油添加剂共混。所述密封液具有低于-60℃的倾点、至少129的粘度指数和小于30ml的由ASTM D 892-03确定的序列II起泡倾向。
附图简述
附图显示了向泵中添加阻挡液的方式和将其用于防止泵送流体泄露的用途。
发明详述
在该整个说明书中使用的试验方法和术语是常规的且对于润滑领域中的技术人员是可理解的。在如下段落中简单提及了少数方法和术语。
将Noack挥发性定义为用恒定空气流提取在250℃下加热的油60分钟时损失的以wt%表示的油的质量,根据ASTM D5800-05的程序B测量。
“具有环烷属官能团的分子”是指为单环或稠合多环饱和烃基团的任意一种分子或含有单环或稠合多环饱和烃基团作为一个或多个取代基的任意一种分子。
“具有单环烷属官能团的分子”是指为3~7个环碳的单环饱和烃基团的任意一种分子或被3~7个环碳的单个单环饱和烃基取代的任意一种分子。
“具有多环烷属官能团的分子”是指为两个以上稠环的稠合多环饱和烃环基团的任意一种分子、被两个以上稠合环的一个或多个稠合多环饱和烃环基团取代的任意一种分子或利用超过一个的3~7个环碳的单环饱和烃基取代的任意一种分子。
具有环烷属官能团的分子、具有单环烷属官能团的分子和具有多环烷属官能团的分子以重量百分比的方式报道并通过场离子化质谱(FIMS)、用于芳族的HPLC-UV和用于烯烃的质子NMR的组合来确定。
氧化器BN测量了润滑油在模拟应用中的响应。高值或吸收一升氧气耗时长,表明良好的稳定性。通过Dornte型氧气吸收设备(R.W.Dornte″Oxidation of White Oils,″Industrial and Engineering Chemistry,Vol.28,p26,1936)能够测量氧化器BN,在340°F下的1大气压的纯氧气下,报道了100g油吸收1000 ml O2的时间。在氧化器BN试验中,每100克油使用0.8ml催化剂。所述催化剂为模拟用过的曲轴箱油的平均金属分析的可溶性金属环烷酸盐的混合物。添加剂包装为每100克油为80毫摩尔的二聚丙烯苯基二硫代磷酸锌。
通过本领域中已知的方法能够实施分子表征,包括场离子化质谱(FIMS)和n-d-M分析(采用归一化的ASTM D 3238-95(2005年再颁))。在FIMS中,将基础油表征为烷烃和具有不同不饱和数的分子。具有不同不饱和数的分子包含环烷烃、烯烃和芳烃、如果存在大量的芳烃,则将其识别为4-不饱和。当存在大量的烯烃时,将其识别为1-不饱和。源自FIMS分析的1-不饱和、2-不饱和、3-不饱和、4-不饱和、5-不饱和和6-不饱和的总和,减去由质子NMR确定的wt%烯烃并减去通过HPLC-UV确定的wt%芳烃,得到具有环烷属官能团的分子的总重量百分数。如果不测量芳烃的含量,则假定其小于0.1wt%并不包括在具有环烷属官能团的分子的总重量百分数的计算中。具有环烷属官能团的分子的总重量百分数为具有单环烷属官能团的分子的重量百分数和具有多环烷属官能团的分子的重量百分数的加和。
通过ASTM D2503-92(2007年再颁)确定分子量。所述方法使用蒸气压(VPO)的热电测量。在试样体积不足的情况中,可使用ASTMD2502-04作为替代方法;且在使用该方法的情况中,对其进行了指出。
通过ASTM D 2369-07测量了挥发性有机物含量(VOC)。优选低值。
通过ASTM D 92-05测量了Cleveland开口杯(COC)闪点。
使用自动倾斜法,通过ASTM D5950-02(2007再颁)测量了倾点。
苯胺点试验显示,油是否易于使得与所述油接触的弹性体(橡胶化合物)溶胀或收缩。将苯胺点称作“苯胺点温度”,其为等体积的苯胺(C6H5NH2)和油形成单相的最低温度(°F或℃)。苯胺点(AP)是芳族烃在油试样中的量的指示。低AP表示芳族烃含量较高,而高AP表示芳族烃含量较低。通过ASTM D611-07确定苯胺点。在某些实施方案中,得自高度链烷烃蜡如费托蜡的润滑剂基础油馏分具有相对低的苯胺点。这能够归因于,润滑剂基础油的具有单环烷属官能团的分子与具有多环烷属官能团的分子的比例高。因此,衍生自具有低苯胺点的高度链烷烃蜡的润滑剂基础油馏分展示了良好的弹性体相容性。
在ASTM D-4172-94(2004年再颁)中提出了测量抗磨损性能的四球磨损试验(4-球磨损)。在飞来克斯(Falex)变量驱动四球磨损试验机上实施所述试验。将四个球排列在等边四面体上。将下面的三个球牢固夹在装满润滑剂的试验杯中并通过电动机驱动的卡盘夹住上面的球。上面的球相对于固定的下面的球旋转。通过重量/杠杆臂***在向上的方向上施加载荷。通过连续可变的气动施加载荷***来施加载荷。加热器使得在升高的油温下运行。将三个静止的钢球浸入10ml试验试样中,并以“点对点接触”的方式在三个静止球的顶上旋转第四个钢球。在20kg载荷和1800rpm的旋转速度下将机器在75℃下运行1小时。试验的润滑油通常含有在工业油中一般存在的所有添加剂。
根据本发明的方法制备润滑剂基础油所使用的进料为含有大于75wt%正链烷烃、优选至少85wt%正链烷烃且最优选至少90wt%正链烷烃的蜡质进料。所述蜡质进料可以为常规的石油衍生的进料如疏松蜡,或其可得自合成进料如由费托合成制备的进料。所述进料的主要部分应在650°F以上沸腾。优选地,至少80wt%的进料应在650°F以上沸腾,最优选至少90wt%的进料应在650°F以上沸腾。用于实施本发明的高度链烷属进料典型具有超过0℃、更通常超过10℃的初始倾点。
通过润滑油馏分的加氢裂化或溶剂精炼,疏松蜡能够得自常规的石油衍生的原料。典型地,从通过这些方法之一制备的溶剂脱蜡原料中回收疏松蜡。通常优选加氢裂化,因为加氢裂化也会将氮含量降至低值。利用得自溶剂精炼油油的疏松蜡,可使用脱油以降低氮含量。能够使用疏松蜡的加氢处理以降低氮和硫的含量。疏松蜡具有非常高的粘度指数,通常为约140~200,这取决于油含量和制备疏松蜡的起始材料。因此,疏松蜡适用于制备具有非常高粘度指数的润滑剂基础油。
用于本发明中的蜡质进料具有小于25ppm的总共合并的氮和硫。通过ASTM D 4629-96将蜡质进料熔化然后氧化燃烧和进行化学发光检测来测量氮。在美国专利6,503,956中对试验方法作了进一步描述,通过参考并入本文中。通过ASTM D 5453-00将蜡质进料熔化然后进行紫外荧光来测量硫。在美国专利6,503,956中对试验方法作了进一步描述,通过参考并入本文中。
随着大规模费托合成工艺付诸生产,用于本发明中的蜡质进料预期在不远的将来会是大量且相对具有成本竞争性。所述蜡质进料可使用费托法由任意一种合成气如在GTL或CTL法中制得的合成气得到。进料至费托法的合成气可由宽范围的烃制得,包括废塑料或其他聚合物、生物质、纤维素、植物、农业废物、废纸或纸板、木材、天然气、页岩或煤。由费托法制备的合成原油包含各种固体、液体和气体烃的混合物。在润滑剂基础油范围内沸腾的那些费托产物含有高比例的蜡,使其成为加工成润滑剂基础油的理想候选者。因此,费托蜡代表了根据本发明的方法用于制备高品质润滑剂基础油的优异进料。费托蜡在室温下通常为固体,因此展示了差的低温性能如倾点和浊点。然而,在蜡的加氢异构化之后,可制备具有优异低温性能的费托衍生的润滑剂基础油。在美国专利5,135,638和5,282,958以及美国专利申请20050133409中可发现加氢异构化脱蜡方法的一般性描述。
在加氢异构化条件下在异构化区域中通过将蜡质进料与加氢异构化催化剂接触可实现加氢异构化。在一个实施方案中,加氢异构化催化剂优选包含择形中等孔径的分子筛、贵金属加氢组分以及耐火氧化物载体。在一个实施方案中,择形中等孔径的分子筛优选选自SAPO-11、SAPO-31、SAPO-41、SM-3、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57、SSZ-32、菱钾铝矿、镁碱沸石及其组合。有时更优选SAPO-11、SM-3、SSZ-32、ZSM-23及其组合。在一个实施方案中,贵金属加氢组分为铂、钯或其组合。
加氢异构化条件取决于所使用的蜡质进料、所使用的加氢异构化催化剂、是否对催化剂进行硫化、期望的收率以及润滑剂基础油的期望性能。在一个实施方案中,加氢异构化条件包括260℃~约413℃(500~约775°F)的温度、15~3000psig的总压力和约0.5~30MSCF/bbl或约1~约10MSCF/bbl的氢气与进料之比。在某些实施方案中,将氢气与产物分离并再循环至异构化区域中。
在一个实施方案中,调整加氢异构化条件以制造具有单环烷属官能团的分子大于5wt%或具有单环烷属官能团的分子大于10wt%的一种或多种馏分。在一个实施方案中,所述馏分具有大于140的粘度指数和低于0℃的倾点。在某些实施方案中,倾点为小于-10℃。
任选地,可对通过加氢异构化脱蜡制造的润滑剂基础油进行加氢精制。可在将润滑剂基础油分馏成一种或多种馏分之前或之后,在一个或多个步骤中进行加氢精制。通过除去芳烃、烯烃、有色体和溶剂,可期望加氢精制提高产物的氧化稳定性、UV稳定性以及外观。在美国专利3,852,207和4,673,487中可发现加氢精制的一般性描述,并入本文中。需要加氢精制步骤以将润滑剂基础油中烯烃的重量百分比降至小于10、优选小于5、更优选小于1且最优选小于0.5。也需要加氢精制步骤将芳烃的重量百分比降至小于0.3、优选小于0.06、更优选小于0.02且最优选小于0.01。
在一个实施方案中,调整本发明方法中的加氢异构化和加氢精制条件以制造芳烃小于0.06wt%、烯烃小于5wt%且具有环烷属官能团的分子大于5wt%的润滑剂基础油的一种或多种所选馏分。
在一个实施方案中,润滑剂基础油馏分具有非常高的粘度指数,通常大于118,但其还可具有甚至更高的粘度指数如大于由如下方程计算的量:粘度指数=28*Ln(在10℃下的运动粘度,单位为cSt)+95;其中Ln是指底为“e”自然对数。通过ASTM D 2270-04确定粘度指数。
润滑剂基础油馏分具有通过FIMS(场离子化质谱)测量的可测量量的不饱和分子。在一个实施方案中,其具有大于5wt%的具有单环烷属官能团的分子,在另一个实施方案中,其具有大于10wt%的具有单环烷属官能团的分子。在一个实施方案中,其中具有单环烷属官能团的分子的重量百分比与具有多环烷属官能团的分子的重量百分比之比为大于2.1、大于6、大于15、大于40或大于100。在润滑剂基础油馏分中具有单环烷属官能团的分子的占优势的存在提供了优异的氧化稳定性以及期望的添加剂溶解度和弹性体相容性。在一个实施方案中,润滑剂基础油馏分具有小于10wt%、小于5wt%、小于1wt%或小于0.5wt%的烯烃。所述润滑剂基础油馏分具有小于0.3wt%、小于0.06wt%或小于0.02wt%的芳烃。
在一个实施方案中,润滑剂基础油馏分每100个碳具有低水平的烷基分支如每100个碳小于8个或小于7个的烷基分支。所述分支为烷基分支且在一个实施方案中,其主要为甲基分支(-CH3)。另外,通过C-13NMR在各种分支碳共振上对烷基分支进行定位。低水平的主要的甲基分支赋予润滑基础油和由其制造的密封油以高粘度指数和良好的生物降解能力。
在一个实施方案中,本发明的润滑剂基础油馏分具有小于180°F如50°F~小于180°F或90~小于150°F的T90-T10沸点分布。
在某些实施方案中,在烯烃和芳烃含量在密封液的润滑剂基础油馏分中明显低的情况中,润滑剂基础油的氧化器BN大于25小时,优选大于35小时,更优选大于40小时。氧化器BN是测量润滑基础油的氧化稳定性的便捷方式。在Stangeland等人的美国专利3,852,207中对氧化器BN试验进行了描述。氧化器BN利用Dornte型氧气吸收装置测量了对氧化的抵抗性。参见R.W.Dornte″Oxidation of WhiteOils,″Industrial and Engineering Chemistry,Vol.28,p26,1936。通常,条件为在340°F下一个大气压的纯氧气。以小时为单位报道了100g油吸收1000ml O2的结果。在氧化物BN试验中,每100g油使用0.8ml催化剂且在油中包括添加剂包。所述催化剂为可溶性金属环烷酸盐在煤油中的混合物。可溶性金属环烷酸盐的混合物模拟了用过的曲轴箱油的平均金属分析。催化剂中的金属含量如下:铜=6927ppm;铁=4083ppm;铅=80208ppm;镁=350ppm;锡=3565ppm。添加剂包为每100g油80mmol的二聚丙烯苯基二硫代磷酸锌,或约1.1g的OLOA 260。氧化器BN试验测量了润滑基础油在模拟应用中的响应。
高值或用于消耗1升氧气的时间长表明良好的氧化稳定性。传统认为,氧化器BN应超过7小时,但本发明润滑剂基础油馏分的氧化器BN优选高得多。
OLOA是奥伦耐润滑油添加剂[R]的首字母缩写,其为雪佛龙奥伦耐的注册商标。
实施例
实施例1
对使用Fe基费托催化剂制备的加氢处理的费托蜡试样进行分析并发现具有如表I中所示的性质。
在具有氧化铝粘接剂的Pt/SAPO-11催化剂上对费托蜡进行加氢异构化。运行条件包括625°F~695°F(329℃~399℃)的温度、0.6~1.0小时-1的LHSV、300~400psig的反应器压力和4~6MSCF/bbl的单程氢气速率。反应器流出物直接传递至第二反应器,所述第二反应器含有在1000psig下运行的在二氧化硅-氧化铝上的Pt/Pd加氢精制催化剂。第二反应器中的条件包括约450°F(232℃)的温度、1.0小时-1的LHSV和约5~7MSCF/bbl的单程氢气流量。
通过真空蒸馏对沸点超过650°F的产物进行分馏以制造不同粘度等级的蒸馏馏分,如下表1中所示。
表1
实施例2
将上面制备的并示于表1中的费托衍生的润滑剂基础油与添加剂共混,制得本发明的密封液,将其示于表2的列2和3中,所述添加剂包含抗氧化剂、抗磨损剂、泡沫抑制剂、倾点抑制剂和金属减活化剂。
表2
阻挡液的比较
阻挡液A是PAO基密封液,其含有抗磨损剂、抗氧化剂、金属减活化剂和消泡剂。所述PAO密封液不含泡沫抑制剂或倾点抑制剂。阻挡液B和C为GTL基阻挡液。Royal Purple是工业合成的PAO基密封液。
全部GTL基密封液明显比PAO基密封液廉价得多,同时提供相当的性能。
Claims (13)
1.一种涡轮机密封液,其包含:
a.润滑剂基础油,具有:
i.320和375之间的平均分子量;
ii.大于118的粘度指数;
iii.小于25wt%的烯烃;和
b.选自抗氧化剂、抗磨损剂、倾点抑制剂、泡沫抑制剂、金属减活化剂和多元醇酯中的添加剂,
其中所述涡轮机密封液的倾点不高于-60℃并且所述涡轮机密封液包含至少94wt%的润滑剂基础油。
2.权利要求1的密封液,其为阻挡液或缓冲液。
3.权利要求1的密封液,其中所述润滑剂基础油是费托衍生的。
4.权利要求1的密封液,其中所述润滑剂基础油在分子中的平均支化度小于10个烷基分支每100个碳原子。
5.权利要求1的密封液,其中所述润滑剂基础油具有大于14wt%的具有环烷属官能团的分子,且其中所述润滑剂基础油的具有单环烷属官能团的分子的重量百分比与具有多环烷属官能团的分子的重量百分比之比为大于13。
6.权利要求1的密封液,其中所述润滑剂的KV40大于6cSt,且KV100大于2cSt。
7.权利要求1的密封液,其中所述润滑剂基础油,根据n-d-M结果,包含大于97%的链烷属碳含量和大于2%的环烷属碳含量。
8.权利要求1的密封液,其中所述润滑剂基础油另外具有大于168℃的Cleveland开口杯闪点。
9.权利要求1的密封液,其具有41的API比重。
10.权利要求1的密封液,其具有等于或高于25的赛波特色度。
11.权利要求1的密封液,其具有明亮且清澈的外观。
12.权利要求1的密封液,其具有在40℃下至少6cSt的运动粘度,在100℃下至少2cSt的运动粘度和至少129的VI。
13.一种制备密封液的方法,所述方法包括:
a.选择蜡质进料,所述蜡质进料具有:
i.大于75wt%的正链烷烃;和
ii.小于25ppm的总的合并的氮和硫;
b.对所述蜡质进料进行加氢异构化脱蜡以制造润滑剂基础油;
c.将所述润滑剂基础油分馏成一种或多种馏分;
d.选择具有如下性质的一种或多种馏分:
i.320和375之间的平均分子量;
ii.大于或等于118的粘度指数;
iii.小于25wt%的烯烃;以及
e.将所述一种或多种选择的馏分与包含增稠剂的添加剂包共混以制造具有至少120VI和倾点不高于-60℃的密封液,其中所述密封液包含至少94wt%的润滑剂基础油。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/605,153 | 2009-10-23 | ||
US12/605,153 US8663454B2 (en) | 2009-10-23 | 2009-10-23 | Formulating a sealant fluid using gas to liquid base stocks |
PCT/US2010/053002 WO2011049847A2 (en) | 2009-10-23 | 2010-10-18 | Formulating a sealant fluid using gas to liquid base stocks |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102575143A CN102575143A (zh) | 2012-07-11 |
CN102575143B true CN102575143B (zh) | 2015-03-18 |
Family
ID=43897286
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201080047637.6A Expired - Fee Related CN102575143B (zh) | 2009-10-23 | 2010-10-18 | 使用气变液基础油料配制密封液 |
Country Status (7)
Country | Link |
---|---|
US (2) | US8663454B2 (zh) |
CN (1) | CN102575143B (zh) |
BR (1) | BR112012008973A2 (zh) |
CA (1) | CA2777981A1 (zh) |
DE (1) | DE112010004112T5 (zh) |
MX (1) | MX2012004178A (zh) |
WO (1) | WO2011049847A2 (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2617170C1 (ru) * | 2016-04-27 | 2017-04-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Герметизирующая жидкость |
CN109563933B (zh) * | 2016-06-10 | 2021-02-26 | 约翰起重机英国有限公司 | 减少排放气体密封件 |
US11796064B2 (en) | 2016-06-10 | 2023-10-24 | John Crane Uk Limited | Reduced emission gas seal |
CN110569518B (zh) * | 2019-03-29 | 2021-07-20 | 哈尔滨理工大学 | 一种组合密封油膜厚度求解方法 |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3852207A (en) | 1973-03-26 | 1974-12-03 | Chevron Res | Production of stable lubricating oils by sequential hydrocracking and hydrogenation |
US4673487A (en) | 1984-11-13 | 1987-06-16 | Chevron Research Company | Hydrogenation of a hydrocrackate using a hydrofinishing catalyst comprising palladium |
US5660481A (en) * | 1987-05-29 | 1997-08-26 | Ide; Russell D. | Hydrodynamic bearings having beam mounted bearing pads and sealed bearing assemblies including the same |
JP2907543B2 (ja) | 1989-02-17 | 1999-06-21 | シェブロン リサーチ アンド テクノロジー カンパニー | シリコアルミノフオスフェイト・モレキュラーシープ触媒を用いるワックス状潤滑油および石油ワックスの異性化 |
US5249812A (en) * | 1990-03-12 | 1993-10-05 | John Crane Inc. | Barrier seal systems |
US5282958A (en) | 1990-07-20 | 1994-02-01 | Chevron Research And Technology Company | Use of modified 5-7 a pore molecular sieves for isomerization of hydrocarbons |
US5529315A (en) * | 1994-02-14 | 1996-06-25 | John Crane Inc. | Tandem seal arrangement for mechanical face seals |
US6475960B1 (en) * | 1998-09-04 | 2002-11-05 | Exxonmobil Research And Engineering Co. | Premium synthetic lubricants |
US6103099A (en) * | 1998-09-04 | 2000-08-15 | Exxon Research And Engineering Company | Production of synthetic lubricant and lubricant base stock without dewaxing |
US7067049B1 (en) * | 2000-02-04 | 2006-06-27 | Exxonmobil Oil Corporation | Formulated lubricant oils containing high-performance base oils derived from highly paraffinic hydrocarbons |
US6703356B1 (en) * | 2000-03-23 | 2004-03-09 | Exxonmobil Research And Engineering Company | Synthetic hydrocarbon fluids |
US6503956B2 (en) | 2001-01-11 | 2003-01-07 | Chevron U.S.A. Inc. | Determination of heteroatom content in Fischer-Tropsch wax |
US6655693B2 (en) * | 2001-04-26 | 2003-12-02 | John Crane Inc. | Non-contacting gas compressor seal |
US7083713B2 (en) * | 2003-12-23 | 2006-08-01 | Chevron U.S.A. Inc. | Composition of lubricating base oil with high monocycloparaffins and low multicycloparaffins |
US7282134B2 (en) * | 2003-12-23 | 2007-10-16 | Chevron Usa, Inc. | Process for manufacturing lubricating base oil with high monocycloparaffins and low multicycloparaffins |
US7402236B2 (en) * | 2004-07-22 | 2008-07-22 | Chevron Usa | Process to make white oil from waxy feed using highly selective and active wax hydroisomerization catalyst |
US7674364B2 (en) * | 2005-03-11 | 2010-03-09 | Chevron U.S.A. Inc. | Hydraulic fluid compositions and preparation thereof |
US7655605B2 (en) * | 2005-03-11 | 2010-02-02 | Chevron U.S.A. Inc. | Processes for producing extra light hydrocarbon liquids |
US20070142242A1 (en) * | 2005-12-15 | 2007-06-21 | Gleeson James W | Lubricant oil compositions containing GTL base stock(s) and/or base oil(s) and having improved resistance to the loss of viscosity and weight and a method for improving the resistance to loss of viscosity and weight of GTL base stock(s) and/or base oil(s) lubricant oil formulations |
US20080096779A1 (en) * | 2005-12-21 | 2008-04-24 | Chevron U.S.A. Inc. | Turbine oil composition method for making thereof |
US7846880B2 (en) * | 2006-12-20 | 2010-12-07 | Chevron U.S.A. Inc. | Light base oil fraction and lubricant having low wt% noack volatility |
US20090036546A1 (en) * | 2007-07-31 | 2009-02-05 | Chevron U.S.A. Inc. | Medicinal Oil Compositions, Preparations, and Applications Thereof |
US20090088353A1 (en) * | 2007-09-27 | 2009-04-02 | Chevron U.S.A. Inc. | Lubricating grease composition and preparation |
-
2009
- 2009-10-23 US US12/605,153 patent/US8663454B2/en not_active Expired - Fee Related
-
2010
- 2010-10-18 BR BR112012008973A patent/BR112012008973A2/pt not_active IP Right Cessation
- 2010-10-18 CA CA2777981A patent/CA2777981A1/en not_active Abandoned
- 2010-10-18 MX MX2012004178A patent/MX2012004178A/es not_active Application Discontinuation
- 2010-10-18 DE DE112010004112T patent/DE112010004112T5/de not_active Withdrawn
- 2010-10-18 CN CN201080047637.6A patent/CN102575143B/zh not_active Expired - Fee Related
- 2010-10-18 WO PCT/US2010/053002 patent/WO2011049847A2/en active Application Filing
-
2012
- 2012-08-21 US US13/590,265 patent/US20130125785A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
BR112012008973A2 (pt) | 2019-09-24 |
MX2012004178A (es) | 2012-05-29 |
US20130125785A1 (en) | 2013-05-23 |
US8663454B2 (en) | 2014-03-04 |
CA2777981A1 (en) | 2011-04-28 |
DE112010004112T5 (de) | 2012-09-13 |
US20110094414A1 (en) | 2011-04-28 |
WO2011049847A2 (en) | 2011-04-28 |
WO2011049847A3 (en) | 2011-08-18 |
CN102575143A (zh) | 2012-07-11 |
WO2011049847A8 (en) | 2012-01-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2005322299B2 (en) | Hydraulic oil with excellent air release and low foaming tendency | |
AU2007337109B2 (en) | Lubricant base oil blend having low wt% Noack volatility | |
AU2006242580B2 (en) | Medium-speed diesel engine oil | |
KR100592138B1 (ko) | 저 점도 윤활 기유 | |
AU2007337107B2 (en) | A light base oil fraction and lubricant having low wt% Noack volatility | |
CN101715480B (zh) | 功能流体组合物 | |
CN101437928B (zh) | 具有低牵引系数的基油的齿轮润滑剂 | |
KR20080108348A (ko) | 낮은 브룩필드 비를 갖는 기어 윤활유 | |
BRPI0620165A2 (pt) | óleo lubrificante sem cinzas, fluido hidráulico sem cinzas ou um óleo de máquina de papel sem cinzas, processo para fabricar um fluido hidráulico sem cinzas ou um óleo de máquina de papel sem cinzas com estabilidade de oxidação alta, e, método para melhorar a estabilidade de oxidação de um fluido hidráulico sem cinzas ou um óleo de máquina de papel sem cinzas | |
BRPI0620160A2 (pt) | óleo lubrificante, processo para fabricar um óleo lubrificante com estabilidade de oxidação alta, e, método para melhorar a estabilidade de oxidação de um óleo lubrificante | |
JP2009500489A (ja) | 工業潤滑油及びグリース組成物中のhvi−pao | |
CN102575143B (zh) | 使用气变液基础油料配制密封液 | |
CN102046763A (zh) | 齿轮油组合物,其制备方法和应用 | |
US8480879B2 (en) | Process for improving lubricating qualities of lower quality base oil | |
CN104245905B (zh) | 润滑油组合物 | |
CN101889070A (zh) | 基础油配制剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150318 Termination date: 20151018 |
|
EXPY | Termination of patent right or utility model |