CN103597028B - 水性倾点下降剂分散体组合物 - Google Patents
水性倾点下降剂分散体组合物 Download PDFInfo
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- CN103597028B CN103597028B CN201280028533.XA CN201280028533A CN103597028B CN 103597028 B CN103597028 B CN 103597028B CN 201280028533 A CN201280028533 A CN 201280028533A CN 103597028 B CN103597028 B CN 103597028B
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Abstract
本发明涉及水性倾点下降剂分散体组合物,其包含:热塑性聚合物,优选乙烯乙酸乙烯酯(EVA);分散剂;水;任选的水性凝固点下降剂;和任选的稳定剂,其中所述分散的热塑性聚合物的体积平均粒度等于或小于1微米,以及涉及制造和使用所述组合物的方法。
Description
技术领域
本发明涉及在水性介质中包含热塑性聚合物的倾点下降剂组合物,其提供原油倾点降低、在宽温度范围内作为液体存在、并表现出对乳液分层(creaming)的长期稳定性,以及涉及制备所述倾点下降剂组合物的方法。
背景技术
各种类型的原油需要使用倾点下降添加剂以便改善低温下的流动。许多倾点物质在环境生产场所温度下是蜡质的固体。为了能够向井下泵送这些蜡质物质,它们需要转变成液态,例如通过将它们溶解或将它们分散在液体介质中。煤油已经用作这类介质。然而,出于种种原因,包括易燃性、环境影响和经济考虑,煤油不是理想的。
当在寒冷气候使用时,这些倾点下降剂的溶液或分散体还必须在低温、例如-10℃或更低下保持为液体。一种解决方案是将所述蜡质倾点下降剂分散在水和二醇例如乙二醇或丙二醇的混合物中。使用水是经济的,并且它也增加了安全性,因为不需要使用易燃液体介质。
除了其它类别的聚合物之外,乙烯和C1至C4脂肪酸的乙烯基酯的共聚物,通常包含15重量%至40重量%的乙烯基酯含量,已经显示出是原油和中间馏分的有效流动改进剂(这些是所谓的乙烯乙酸乙烯酯共聚物(EVA共聚物)),例如,参见USP3,048,479、3,567,639和3,669,189。对于寒冷气候条件,期望水性EVA分散体具有高固体含量(例如大于25%EVA),同时仍然能够在低温下(-10℃或更低)流动。
然而,将EVA分散到含有乙二醇的水性分散体中是有问题的。对于一些EVA聚合物、尤其是含有少部分乙酸乙烯酯的那些,所述聚合物具有高熔点并且在不使用溶剂下,所述EVA不能通过常规分散技术充分分散。此外,EVA分散体通常不表现出抗乳液分层(向载体介质顶部迁移)的长期稳定性。
需要一种包含合适添加剂的分散在不含易燃溶剂的介质中的倾点下降剂,它提供原油倾点降低、在宽温度范围内(环境至40℃)作为液体存在、和表现出对乳液分层的长期稳定性。
发明内容
本发明是这样一种水性倾点下降剂分散体组合物,其包含:i)乙烯乙酸乙烯酯共聚物(EVA),量为12至50重量%;ii)分散剂,优选油酸、硬脂酸、山萮酸或芥酸(euric acid)的钠盐,或油酸、硬脂酸、山萮酸或芥酸的钾盐、或其混合物,其量为1至10重量%;iii)水;任选的iv)水性凝固点下降剂,优选氯化钠、氯化钾、氯化钙、甲醇、乙醇、丙醇、丙二醇、甘油、乙二醇的乙醚、乙二醇的丙醚、乙二醇的丁醚、乙二醇的己醚、二乙二醇、或丙二醇,并更优选乙二醇;任选的v)稳定剂,优选聚乙烯醇;或乙烯丙烯酸共聚物、乙烯甲基丙烯酸共聚物、聚丙烯酸聚合物、聚丙烯酸共聚物或丙烯酸与氨基甲酸酯共聚物的离聚物;并更优选聚乙氧基化非离子型表面活性剂,其量为0.5重量%至5重量%;和任选的vi)其他的添加剂,其选自杀生物剂、着色剂、消泡剂或其混合物,其中重量百分比是基于水性倾点下降剂分散体组合物的总重量并优选分散的EVA的体积平均粒度等于或小于1微米,所述水:水性凝固点下降剂混合物以40至75重量%的量存在,所述水:水性凝固点下降剂比率是40:60至70:30。
优选在本文中上面公开的水性倾点下降剂分散体组合物中,所述分散剂ii)包含下列一种或多种:a)具有式R1COOR2的脂肪酸/盐,其中R1是8至25个碳原子的直链饱和或不饱和烃基并且R2是H或碱形成基团;b)烷基、芳烃和/或烷基芳烃磺酸盐;c)烷基丙烯酸酯和/或烷基甲基丙烯酸酯和丙烯酸和/或甲基丙烯酸的聚合物的盐,或马来酸酐-苯乙烯共聚物的偏酯的盐;d)阳离子型表面活性剂;e)两性离子表面活性剂;或f)非离子型表面活性剂。
在另一种实施方式中,本发明是抑制石蜡沉积和/或改善油流动性质的方法,所述方法包括向油添加有效量的上文所述的倾点下降剂组合物。
附图说明
图1是用于制备本发明的水性倾点下降剂分散体组合物的典型的熔融挤压设备示意图。
具体实施方式
可用作本发明的倾点下降剂的组分i,是一种热塑性聚合物。本发明的合适的热塑性聚合物是乙烯与至少一种饱和脂族C1至C24-羧酸的乙烯基酯的共聚物,例如,参见USP3,382,055。在这样的聚合物中,可以同时使用不同的乙烯基酯。所述聚合物原则上可通过本体、乳液或溶液聚合来制备。作为共聚单体,可以使用例如乙酸、丙酸、丁酸、2-乙基己烷羧酸、壬酸和硬脂酸、特别是C2至C4-羧酸的乙烯基酯,尤其乙酸乙烯酯。优选的热塑性聚合物是乙烯乙酸乙烯酯共聚物。通常,所述乙烯基酯含量在10至80重量%、优选20至45重量%、更优选25至32重量%、更优选28至32重量%的范围内。
乙烯基酯含量小于30%的共聚物可以适合地通过本体高压方法制备。
德国专利公布No.1,914,756描述了通过自由基溶液聚合制备的每摩尔份乙酸乙烯酯具有3至20摩尔份乙烯的共聚物,所述共聚物具有1,000至2,900的分子量,具有轻度的乙烯链支化。根据ASTM试验方法D1238-6T测定的熔融粘度指数在1和800克/10分钟(g/10min)之间,优选5至400g/10min,更优选5至150g/10min。包含2至45重量%的乙酸乙烯酯并且具有6至150g/10min的熔融粘度指数的可商购乙烯乙酸乙烯酯共聚物,例如DuPont以名称ELVAXTM销售的,可用于本发明。除非另外指出,熔融粘度指数根据ASTM D1238在190℃以及2.16千克(kg)的负荷下测定。
本发明的乙烯与至少一种饱和脂族羧酸的乙烯基酯的所述共聚物在室温下不溶于所述载体介质中。
优选地,本发明的水性倾点下降剂分散体组合物中所用的热塑性聚合物的使用量,基于所述水性倾点下降剂分散体组合物的总重量,等于或大于20重量%,更优选量等于或大于25重量%,更优选量等于或大于30重量%。优选地,本发明的水性倾点下降剂分散体组合物中所用的热塑性聚合物的使用量,基于所述水性倾点下降剂分散体组合物的总重量,等于或小于65重量%,更优选量等于或小于60重量%,更优选量等于或小于55重量%。
除了热塑性树脂之外,本文中描述的分散体包含分散剂。在本文中使用时,术语“分散剂”是指帮助形成和/或稳定分散体的试剂。一些分散剂还可以用来形成乳液并由Paul Becher详细说明(Emulsions:Theory and Practice,第三版,Oxford University,New York,2001),所述文献以其全部内容通过引用并入本文。作为组分ii用于本发明的合适的分散剂(有时称为表面活性剂)可以分类为阴离子、阳离子、两性离子或非离子型的。阴离子型表面活性剂包括含有与水溶性(亲水)基团结合的长亲脂性尾部的物质,其中所述亲水基团含有阴离子部分例如羧酸、磺酸或酚基,它们被阳离子例如碱金属或铵中和。所述亲脂性尾部优选是烷基,通常具有约8至约25个碳原子。
典型的阴离子型表面活性剂包括羧酸或其盐,例如具有式R1COOR2的脂肪酸/盐,其中R1是约8至约25个碳原子的直链饱和或不饱和烃基和R2是H或碱形成基团例如Li、Na、K、或NR4(R独立地是氢、烷基、芳基或芳基烷基)。或者R2可以是二价或多价金属,在这种情况下,通常存在合适的酸基团数量,以提供中性盐。多价金属离子包括Mg、Ca、Sr、Ba、Cr、Mn、Fe、Co、Ni、Cu、Zn、Sn、Pb和其它。典型的脂肪酸盐包括硬脂酸钠、棕榈酸钠、油酸铵和三乙醇胺棕榈酸盐。可用作阴离子型表面活性剂的其他羧酸/盐包括椰子油脂肪酸和妥尔油酸的酸/盐,尤其是钠和钾盐,以及其它羧酸盐化合物,包括胺盐例如三乙醇胺盐、酰化多肽、和N-月桂基肌氨酸的盐例如N-十二酰基-N-甲基甘氨酸钠盐。本发明中优选的分散剂是山萮酸(R1=C21H43);芥酸(R1=C21H41);油酸、硬脂酸、山萮酸或芥酸的钠或钾盐,和/或其混合物。芥酸可以是例如菜籽油的形式,这是一种含有大约40至50重量%芥酸并且其余主要由具有18个碳原子的链构成的天然油。
其它阴离子型表面活性剂包括烷基、芳烃和烷基芳烃磺酸盐,例如烷基苯磺酸盐、直链烷基苯磺酸盐、四丙烯苯磺酸钠、十二烷基苯磺酸钠、苯-、甲苯-、二甲苯-和异丙苯磺酸盐、木质素磺酸盐、石油磺酸盐、石蜡磺酸盐、仲n-烷基磺酸盐、α-烯烃磺酸盐、烷基萘磺酸盐;n-酰基-n-烷基牛磺酸盐;磺基琥珀酸酯;羟乙基磺酸盐;具有式R1OSO3R2的烷基硫酸盐,其中R1和R2如上定义,例如十二烷基硫酸锂、十二烷基硫酸钠、十二烷基硫酸钾和十四烷基硫酸钠;具有式R1SO3R2的烷基磺酸盐,其中R1和R2如上定义,例如月桂基磺酸钠;硫酸化和磺化酰胺和胺;硫酸化和磺化酯,例如月桂酸甘油单酯硫酸钠、磺乙基油酸钠和月桂基磺基乙酸钠;硫酸酯盐,例如硫酸化线性伯醇、硫酸化聚乙氧基化直链醇和硫酸化甘油三酯油;磷酸酯和多磷酸酯;全氟化羧酸;和聚合阴离子型表面活性剂,例如藻酸。
还包括聚合阴离子型表面活性剂,例如烷基丙烯酸酯和/或烷基甲基丙烯酸酯与丙烯酸和/或甲基丙烯酸的聚合物的盐、和马来酸酐-苯乙烯共聚物的偏酯的盐。阴离子型表面活性剂可以是酸前体的盐,所述酸前体与碱性物质反应形成所述盐。优选地,所述酸前体当场中和形成盐。
可以分类为阴离子型表面活性剂的另一组物质是被称为高碱性或超碱性物质的那些物质。这些是酸性有机化合物(羧酸,磺酸,膦酸,酚等等)的碱性金属盐,优选碱金属盐或碱土金属盐。高碱性物质通常是单相、均质的牛顿(Newtonian)体系,其特征在于金属含量超过根据金属以及与所述金属反应的具体酸性有机化合物的化学计算量进行中和所应该存在的量。所述高碱性物质通过酸性物质(通常是无机酸或低级羧酸,优选二氧化碳)与包含酸性有机化合物、反应介质、化学计量过量的金属碱和助催化剂例如酚或醇的混合物反应而制备,所述反应介质包含对所述酸性有机物质而言的至少一种惰性有机溶剂(矿物油,石脑油,甲苯,二甲苯等等)。所述酸性有机物质通常将具有足够数量的碳原子,以提供在油中的溶解度并提供对产物的表面活性剂活性的量度。过量金属的量通常根据金属比率表示。术语“金属比率”是金属总当量与酸性有机化合物当量的比率:中性金属盐的金属比率为1;具有正盐中存在的金属的4.5倍的盐将具有3.5当量的金属过量,或比率为4.5。
高碱性物质通常用作润滑添加剂并且是本领域技术人员公知的。虽然它们可用于一些应用,但它们的实用范围可能不同于其它表面活性剂。也就是说,已经偶尔观察到它们在暴露于电场之后沉积出被认为是碳酸钙的物质。然而,在这不是问题的情况下,使用它们可能是合适的并因此认为它们在本发明的范围之内。描述制造磺酸、羧酸、和这些中任何两种或更多种的混合物的碱式盐的技术的专利包括USP2,501,731、2,616,905、2,616,911、2,616,925、2,777,874、3,256,186、3,384,585、3,365,396、3,320,162、3,318,809、3,488,284和3,629,109,它们全部以其全文通过引用并入本文中。
阳离子型表面活性剂与阴离子型表面活性剂类似,只是所述分子的极性部分具有正电荷。阳离子型表面活性剂的例子包括长链胺和它们的盐,例如来源于动物和植物脂肪酸和妥尔油的伯胺以及合成的C12至C18伯、仲或叔胺;二胺和它们的盐,季铵盐包括来源于例如牛油或氢化牛油的四烷基铵盐和咪唑鎓盐,或N-苄基-N-烷基-二甲基卤化铵;聚乙氧基化长链胺;季铵化的聚乙氧基化长链胺;和氧化胺例如N-烷基二甲基氧化胺(有时称为两性离子型),如鲸蜡基二甲基氧化胺或硬脂基二甲基氧化胺。
两性离子型表面活性剂包括氨基酸例如β-N-烷基氨基-丙酸、N-烷基-β-亚氨基二丙酸、咪唑啉羧酸盐、N-烷基甜菜碱、磺基甜菜碱(sulfobetaine)和磺基甜菜碱(sultaine)。
非离子型表面活性剂是其中极性官能度不是由阴离子或阳离子基团提供、而是由中性极性基团例如通常醇、胺、醚、酯、酮或酰胺官能团提供的物质。典型的非离子型表面活性剂包括聚乙氧基化烷基酚例如聚乙氧基化对壬基酚、对辛基酚、或对十二烷基酚;来源于椰子油、牛油或合成材料包括油烯基衍生物的聚乙氧基化直链醇;聚乙氧基化聚氧化丙烯二醇(环氧乙烷和环氧丙烷的嵌段共聚物),通常具有1000至30,000的分子量;聚乙二醇;聚乙氧基化硫醇;长链羧酸酯,包括天然脂肪酸的甘油和聚甘油酯、丙二醇酯、山梨糖醇酯、聚乙氧基化山梨糖醇酯、聚氧乙烯二醇酯和聚乙氧基化脂肪酸;烷醇胺“缩合物”,例如通过脂肪酸的甲酯或甘油三酯与等摩尔或两倍等摩尔量的烷醇胺反应制造的缩合物;叔炔二醇;聚乙氧基化硅氧烷,通过反应性硅氧烷中间体与封端烯丙基聚环氧烷例如环氧丙烷或混合环氧乙烷/环氧丙烷共聚物的反应而制备;N-烷基吡咯烷酮,和烷基聚葡萄糖甙(多糖的长链缩醛)。许多这些以及其它离子和非离子型表面活性剂在Rosen,"Surfactants andInterfacial Phenomena,"John Wiley&Sons,7-31页,1989中论述。
其它非离子型表面活性剂更具体地包括乙氧基化椰油基酰胺;油酸;叔十二烷基硫醇;改性的聚酯分散剂;基于聚异丁烯基琥珀酸酐的酯、酰胺或混合酯-酰胺分散剂;基于聚异丁基酚的分散剂;ABA型嵌段共聚物非离子型分散剂;丙烯酸接枝共聚物;辛基苯氧基聚乙氧基乙醇;壬基苯氧基聚乙氧基乙醇;烷基芳基醚;烷基芳基聚醚;胺聚二醇缩合物;改性的聚乙氧基加合物;改性的封端烷基芳基醚;改性的聚乙氧基化直链醇;线性伯醇的端乙氧基化物;高分子量叔胺例如1-羟乙基-2-烷基咪唑啉;噁唑啉;全氟烷基磺酸酯;失水山梨糖醇脂肪酸酯;聚乙二醇酯;脂族和芳族磷酸酯。还包括烃基取代的琥珀酸酰化剂与胺的反应产物。这些反应产物和制备它们的方法描述在USP4,234,435、4,952,328、4,938,881和4,957,649中,它们全部以其全文通过引用并入本文。
其它非离子型表面活性剂包括官能化的聚硅氧烷。这些物质含有例如以下的官能团:氨基、酰胺基、亚氨基、磺酰基、磺酰氧基(sulfoxyl)、氰基、羟基、烃氧基、巯基、羰基(包括醛和酮)、羧基、环氧基、乙酰氧基、磷酸酯、膦酰基和卤代烷基。这些聚硅氧烷可以是线性或支化的,并通常具有超过800、即最多10,000或20,000的分子量。所述官能团可以随机分布在聚合物链上或存在于嵌段中。所述官能团可以作为烷基或烷基芳基以及例如--(C2H4O)a--(C3H6O)b--R的基团存在,其中a和b独立地是0至约100的数字,条件是a或b的至少一个是至少1,并且R是H、乙酰氧基或烃基。其它合适的取代基可以包括C3H6X,其中X是OH、SH或NH2。这类物质的例子包括来自Union Carbide的SILWETTM表面活性剂和来自GoldschmidtChemical Corp.,Hopewell,Va的TEGOPRENTM硅氧烷表面活性剂。
非离子型表面活性剂包括聚氧化烯烷基醇或酚,例如乙氧基化壬基酚;多元醇的链烷酸酯(优选链烷酸偏酯),例如甘油单油酸酯、甘油单月桂酸酯、失水山梨糖醇单油酸酯、失水山梨糖醇倍半油酸酯、失水山梨糖醇单月桂酸酯和失水山梨糖醇倍半月桂酸酯,以及4,4-二羟甲基-2-十七碳烯基-2-噁唑啉。优选的物质包括用二乙醇胺中和的妥尔油脂肪酸;TRITONTM表面活性剂(出自The Dow Chemical Company),包括具有1至70个环氧乙烷单元的辛基酚系列和具有4至40个环氧乙烷单元的壬基酚系列;IGEPALTM表面活性剂(出自Rhone-Poulenc),含有7至50个环氧乙烷单元;TERGTITOLTM表面活性剂(出自TheDowChemical Company),含有4至41个环氧乙烷单元;和NEODOLTM(出自Shell ChemicalCompany),含有3至13个环氧乙烷单元。上述商业物质通常是线性伯醇乙氧基化物、仲醇乙氧基化物、或(在TRITON材料的情况下)支链烷基酚乙氧基化物。
优选地,本发明的水性倾点下降剂分散体组合物中所用的分散剂,基于所述水性倾点下降剂分散体组合物的总重量,使用量等于或大于1重量%,更优选量等于或大于2重量%,更优选量等于或大于3重量%。优选地,本发明的水性倾点下降剂分散体组合物中所用的分散剂,基于所述水性倾点下降剂分散体组合物的总重量,使用量等于或小于10重量%,更优选量等于或小于9重量%,更优选量等于或小于8重量%。
本发明的水性倾点下降剂分散体组合物任选含有稳定剂,其功能是保持产品在宽范围条件下的稳定性,例如储存和运输温度下的相和粒子稳定性。优选地,所述分散体在40℃和-40℃之间是稳定的。所述稳定剂还可以提供剪切稳定性保护,以允许所述产品通过许多不同的泵送系统传递。合适的稳定剂可以是单体表面活性剂、聚合稳定剂、和/或其混合物。合适的单体表面活性剂是上文公开的。
优选的单体稳定剂是聚乙氧基化非离子型表面活性剂。最优选的是亲水亲脂平衡(HLB)值等于或小于16的那些,更优选HLB值等于或小于12,最优选HLB值等于或小于10的那些。不受理论约束,预期HLB较低的非离子型表面活性剂在所述水性凝固点下降剂存在下对所述分散体的粒子的吸附更好。
HLB值是经验数字,表明非离子型表面活性剂的乳化性质。HLB值表达了所述表面活性剂的亲水(亲水)部分(例如环氧乙烷链)比起非极性亲脂性(亲油)部分的相对效果。HLB值通常基于试验乳化数据。然而,它们可以通过各种方式计算,例如,参见“Surfactantsand Interfacial Phenomena”;M.J.Rosen;第二版;John Wiley and Sons;1989。对于只具有环氧乙烷链作为亲水部分的非离子型表面活性剂而言,HLB值通过将环氧乙烷的重量百分比除以五来简单估算。
在本发明中用作稳定剂的优选的非离子型表面活性剂是包含两个部分的分子:包含烃基的疏水部分或疏水物和含有乙氧基(CH2CH2O)的亲水部分或亲水物。本发明优选的表面活性剂具有不含酚基并且含有6至12(更优选8至11)个碳原子的疏水物,或者所述疏水物含有与8或9个碳原子连接的酚基(也分别称为辛基酚或壬基酚),并且所述优选的表面活性剂具有含有1至6个乙氧基(更优选2至4个)的亲水物。这些分子的例子包括具有2至13个环氧乙烷单元的NEODOLTM表面活性剂乙氧基化物(出自Shell Chemical Co.),例如具有含9至11个碳原子的疏水物以及含有平均2.5个乙氧基的亲水物的乙氧基化醇(由Shell作为NEODOL91-2.5销售)、具有含有2-乙基己基的疏水物和含有平均3个乙氧基的亲水物的乙氧基化醇(由The Dow Chemical Company作为ECOSURFTMEH-3销售)、和具有4个乙氧基的乙氧基化壬基酚(由The Dow Chemical Company作为TERGITOLTMNP-4销售)。优选地,如果本发明中使用乙氧基化非离子型表面活性剂的话,它与一种或多种上面公开的分散剂组合使用。
其它聚合稳定剂包括聚乙烯醇,或者乙烯丙烯酸共聚物、乙烯甲基丙烯酸共聚物、聚丙烯酸聚合物和共聚物、和相关类型丙烯酸和氨基甲酸酯共聚物的离聚物和/或盐。优选的聚合稳定剂是聚丙烯酸聚合物(以商品名CARBOPOLTM销售,出自B.F.Goodrich),和乙烯丙烯酸共聚物(以商品名PRIMACORTM销售,出自The Dow Chemical Company)。
稳定剂的量随着聚合物组成和固体水平而变,但基于所述水性倾点下降剂分散体组合物的总重量,优选的稳定剂范围是0.5重量%至10重量%。基于所述水性倾点下降剂分散体组合物的总重量,更优选从约0.5重量%至7重量%,并且甚至更优选从0.5重量%至5重量%。
如果本发明中使用聚乙氧基化非离子型表面活性剂(即含乙氧基的非离子型表面活性剂),它可以单独作为分散剂(量在上文中公开)或者作为稳定剂结合一种或多种分散剂使用。如果它与一种或多种分散剂组合使用,它的使用量基于所述水性倾点下降剂分散体组合物的总重量,优选等于或大于0.1重量%,更优选量等于或大于0.25重量%,更优选量等于或大于0.5重量%,更优选量等于或大于1重量%,和更优选量等于或大于2重量%。如果在本发明中含乙氧基的非离子型表面活性剂与一种或多种分散剂组合使用,它的使用量基于所述水性倾点下降剂分散体组合物的总重量,优选等于或小于10重量%,更优选量等于或小于7重量%,并更优选量等于或小于5重量%。
本发明的倾点下降剂分散体组合物可以含有通常存在于这类组合物中的一种或多种其他添加剂或添加剂混合物,例如,杀生物剂、着色剂、消泡剂等等。基于所述组合物的总重量,这样的添加剂的添加量通常小于1重量%。
本发明的倾点下降剂以在液体介质中的分散体供应,所述液体介质优选包含水,所述倾点下降剂在所述液体介质中通常在10℃不可溶,并优选在环境温度、即约20℃、或甚至30℃或40℃下也不可溶。也就是说,所述介质首先在环境温度(约20℃)下是液体并优选凝固点为10℃或更低。一些优选的介质、特别是混合物,具有低到0℃、-20℃、-30℃、-40℃或更低的凝固点。此外,所述介质在这样的温度、优选环境温度下不溶解显著量的所述倾点下降剂。更具体地说,所述介质优选在环境温度或适度升高的温度下溶解小于4重量%、更优选小于2或甚至1重量%的所述倾点下降剂。(在有些情况下,这种小的可溶部分可以包含杂质和未反应的物质,使得实际溶解的倾点下降剂的量甚至比例更低,例如小于0.5重量%。)优选地,所述介质保持直至30℃、或更优选至40℃或50℃或更高都是非溶剂。
为了所述液体介质是所述倾点下降剂的非溶剂,所述介质通常应该具有合适的极性度。极性可以通过多种方式测量或表达。因此,在一种实施方式中,所述溶剂的分子将优选具有10至80重量%的杂原子,例如氧或氮,更优选20至70%,并甚至更优选25至60重量%。或者,所述介质可以具有至少3、优选至少10的介电常数。前述参数通常是所述介质作为整体的参数,如果所述介质是混合物的话,包括所混合的所有组分。
合适的液体介质包括乙酸酯(例如乙酸2-乙氧基乙酯)、酮(例如丙酮,丁酮,戊酮,己酮),或优选水性二醇混合物(例如乙二醇和水的混合物)。可以单独或与水组合使用的物质包括乙二醇及其衍生物,例如单甲醚、单乙醚、单丙醚、单丁醚和单己醚;二乙二醇及其衍生物,例如单甲醚、单乙醚、单丙醚、单丁醚和单己醚;丙二醇及其衍生物,包括单甲醚、单丙醚和单丁醚;和二丙二醇及其衍生物,例如单甲醚、单丙醚和单丁醚。
可用作本发明液体介质的其它合适类型的物质包括内酯例如丁内酯,和醇例如丁醇、二丙酮醇(4-羟基-4-甲基-2-戊酮)、2,6-二甲基-4-庚醇、己醇、异丙醇、2-乙基己醇和1-戊醇。
最优选的液体介质是水。如本文中定义,水性是指含有水、溶解在水中、或分散在水中。
优选地,本发明的水性倾点下降剂分散体组合物不含任何非环、环状、饱和、不饱和的烷烃、芳烃、或烷基芳烃类烃溶剂。例如,戊烷、戊烯、己烷、己烯、石油醚、环己烷、苯、甲苯、二甲苯、汽油、煤油、柴油、重质芳族石脑油等等不适合作为本发明的液体介质。
优选地,本发明的水性倾点下降剂分散体组合物不含任何这样的烃溶剂,换句话说,本发明的水性倾点下降剂分散体组合物是没有烃溶剂的。
在本发明的倾点分散体组合物中,与其中EVA溶解在液体介质中的溶液(例如在使用烃溶剂的情况)相比,EVA是分散而不是溶解在所述液体介质中。
对于许多应用和/或环境条件而言,让水性倾点下降剂分散体的凝固点等于或低于0℃、优选等于或低于-10℃、更优选等于或低于-20℃、更优选等于或低于-30℃、更优选等于或低于-40℃、并且甚至更优选等于或低于-50℃,是有利的。众所周知,溶液或混合物的凝固点比纯溶剂的凝固点低,而凝固点降低的程度与溶质的重量摩尔浓度成正比。对本发明而言,所述溶液优选是水性的,换句话说,所述溶剂或主要分散液体介质是水,并且所述溶质称为凝固点下降剂。可用作水的凝固点下降剂的不同类型溶质是本领域公知的,并且由电解质组成,例如氯化钠、氯化钾、氯化钙等;一元醇例如甲醇、乙醇、丙醇等;多元醇例如乙二醇、丙二醇和甘油等;二醇醚例如乙二醇的乙醚、丙醚、丁醚和己醚;二乙二醇;丙二醇等。最优选的是甲醇、乙醇、乙二醇和丙二醇,因为这些的分子量最低,并且相对便宜和容易获得。这些当中,乙二醇最优选,原因包括它的不易燃性、低蒸气压和相对低的环境影响。
如果存在的话,掺入本发明的水性分散体组合物中的凝固点下降剂的量由所述水性倾点下降剂分散体组合物期望的凝固点所决定。一般而言,基于所述水性倾点下降剂分散体组合物的最终重量,一种或多种这样的凝固点下降剂的使用量可以等于或大于5重量%,优选等于或大于10重量%,并更优选等于或大于15重量%。一般而言,基于所述水性倾点下降剂分散体组合物的最终重量,一种或多种这样的凝固点下降剂的使用量可以等于或小于40重量%,优选等于或小于35重量%,并更优选等于或小于30重量%。
所述液体介质还可以是任何上述物质的混合物,包括与水的混合物,只要所述倾点下降剂基本上不溶于这样的混合物中即可。如果所述液体介质是二醇和水的混合物,则所述物质的相对量要使得水组分即使在低温例如0℃至-40℃下也不会凝固。这样的水:二醇混合物的优选重量比是:40:60、50:50、60:40至70:30。然而,要理解使用的比率不遵守上文列出的那些,而是由要达到的最终凝固点决定,并且可以由本领域技术人员在无需过度试验下容易地确定。
基于所述水性倾点下降剂分散体组合物的总重量,优选所述液体介质在本发明中的使用量等于或大于35重量%,更优选量等于或大于40重量%,并更优选量等于或大于45重量%。基于所述水性倾点下降剂分散体组合物的总重量,优选所述液体介质在本发明中的使用量等于或小于75重量%,更优选量等于或小于70重量%,并更优选量等于或小于65重量%。
虽然可以使用任何方法,但制备本文中描述的水性倾点分散体组合物的一种便利的方式是通过熔融捏和。可以使用本领域已知的任何熔融捏和设备。在一些实施方式中,使用捏和机、Banbury混合器、单螺杆挤压机、或多螺杆挤压机。所述熔融捏和可以在通常用于熔融捏和热塑性树脂(i)的条件下进行。生产本发明分散体的方法没有特别的限制。例如,一种优选的方法是根据USP5,756,659、7,763,676和7,935,755(所有文献以其全文通过引用并入本文)的方法,包括将热塑性聚合物(i)、分散剂(ii)和任何其它添加剂熔融捏和。优选的熔融捏和机是,例如,具有两个或更多个螺杆的多螺杆挤压机,所述熔融捏和机可以在螺杆的任何位置添加捏和盘。如果需要,可允许所述挤压机沿着待捏和的材料的流动方向从上游到下游,依次设有第一材料供应入口和第二材料供应入口、以及进一步的第三和第四材料供应入口。此外,如果需要,可以在所述挤压机的任意位置添加真空排气口。在一些实施方式中,包含热塑性聚合物、分散剂和任何其它添加剂的倾点分散体首先被稀释到含有约1至约3重量%的水,然后随后进一步稀释到包含大于25重量%的水。在一些实施方式中,所述进一步稀释提供具有至少约30重量%水的分散体。通过熔融捏和得到的水性分散体可以进一步补充二醇,优选乙二醇。在上文描述的水性倾点下降剂分散体可以按所制备的使用或用补加的水和/或二醇进一步稀释。
图1示意性地示出了可用于本发明方法的挤压设备。挤压机20,优选双螺杆挤压机,与背压调节器、熔体泵或齿轮泵30连接。优选地,所述设备还包含碱储器40和初始水储器50,每个都包括泵(未显示)。需要量的碱和初始水分别从所述碱储器40和所述初始水储器50提供。可以使用任何合适的泵,但在一些实施方式中,可以使用在240巴的压力下提供约150cc/min流量的泵以向挤压机20提供碱和初始水。在其它实施方式中,液体注射泵在200巴下提供300cc/min的流量或在133巴下提供600cc/min的流量。在一些实施方式中,所述碱和初始水在预热器中预热。
丸粒、粉末或薄片形式的热塑性EVA聚合物从进料机80进给到挤压机20的入口90,所述树脂在挤压机20中被熔融或调合。在一些实施方式中,将分散剂和/或稳定剂通过开口与树脂一起添加到所述树脂中,而在其它实施方式中,所述分散剂和/或稳定剂单独提供到双螺杆挤压机20。所述树脂熔体然后从挤压机的混合和输送区递送到乳化区,在此通过入口55添加来自储器40和50的初始量的水和碱。在一些实施方式中,分散剂可以补充或只添加到所述水流中。在所述分散剂是脂肪酸的盐的一种实施方式中,所述分散剂可以作为所述脂肪酸的盐添加,或者它可以作为脂肪酸添加到挤压机中,其在所述挤压机中转化为所述脂肪酸的盐形式。在一些实施方式中,在挤压机20的稀释和冷却区,用来自储器60的补加水和/或二醇和/或稳定剂通过入口95进一步稀释所述乳化混合物。通常,所述分散体在冷却区中被稀释到至少30重量%水。另外,所述稀释混合物可以稀释任意次数,直到达到想要的稀释水平为止。
在制造本发明的水性倾点下降剂分散体的一种方法中,在生产EVA的水性分散体的挤压机中相继进行:步骤a,将乙烯乙酸乙烯酯(EVA)、分散剂和水合并以形成EVA的水性分散体;和步骤b,将所述EVA的水性分散体与iv水性凝固点下降剂混合,以形成所述水性倾点下降剂分散体组合物。
在制造本发明的水性倾点下降剂分散体的优选方法中,一部分或全部的水和/或二醇和/或稳定剂不添加到双螺杆挤压机20中,而是添加到已经离开所述挤压机之后的含有分散聚合物的流中。换句话说,步骤b不发生在生产EVA的水性分散体的挤压机中。以这种方式,挤压机20中的蒸汽压力积聚被最小化。
在一些实施方式中,在所述方法的任何点向所述分散体添加碱性物质或其水溶液、分散体或浆液,优选添加到挤压机。通常,所述碱性物质作为水溶液添加。但在一些实施方式中,它以其它方便的形式、例如丸粒或颗粒添加。在一些实施方式中,所述碱性物质和水通过所述挤压机的单独的入口添加。在所述熔融捏和方法中可用于中和或皂化的碱性物质的例子包括,碱金属和碱土金属例如钠、钾、钙、锶、钡;无机胺例如羟胺或肼;有机胺例如甲胺、乙胺、乙醇胺、环己胺、四甲基氢氧化铵;碱金属和碱土金属的氧化物、氢氧化物和氢化物例如氧化钠、过氧化钠、氧化钾、过氧化钾、氧化钙、氧化锶、氧化钡、氢氧化钠、氢氧化钾、氢氧化钙、氢氧化锶、氢氧化钡、氢化钠、氢化钾、氢化钙;以及碱金属和碱土金属的弱酸盐例如碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、碳酸氢钙、乙酸钠、乙酸钾、乙酸钙;或氢氧化铵。在具体的实施方式中,所述碱性物质是碱金属的氢氧化物或碱性金属的氢氧化物。在一些实施方式中,所述碱性物质选自氢氧化钾、氢氧化钠及其组合。
本发明的水性倾点下降剂分散体组合物的热塑性聚合物具有有利的粒度分布。在具体的实施方式中,分散的热塑性聚合物的粒度分布定义为体积平均粒径(Dv)除以数均粒径(Dn),其等于或小于2.5,优选等于或小于2.0。在其它实施方式中,所述分散体具有小于或等于1.9、1.7或1.5的粒度分布。
优选的体积平均粒度等于或小于2微米(μm),优选等于或小于1.5μm,优选等于或小于1.2μm,更优选等于或小于1μm。在其它实施方式中,所述平均粒度范围从0.05μm到1μm。在再其它实施方式中,所述分散体的平均粒度范围从0.5μm到1.2μm,优选0.5μm到1μm。对于非球形的粒子而言,粒子的直径是所述粒子的长轴和短轴的平均值。粒度可以在CoulterLS230光散射粒度分析仪或其它合适的装置上测量。
本发明的分散体具有约5到约13.5,优选从约8到约13,更优选从约10到约12的pH。
在优选实施方式中,本发明是抑制石蜡(也称为蜡)的沉积和/或改善油的流动性质的方法,所述方法包括向所述油添加有效量的本发明的倾点下降剂分散体组合物。有效的EVA聚合物剂量通常为从百万分之1(ppm)到5,000ppm,优选10ppm至300ppm。
本发明的倾点下降剂分散体组合物可以在可能产生蜡沉积、胶凝、增稠、成渣等的任何潜在冷区位置的上游或下游,通过分批或连续注入或挤压添加到输油管线中。同样,所述聚合物组合物可以在所述冷区(储器,罐,容器等)添加,以降低油的倾点。所述油可以是原油、凝析油、中间馏分、燃料油、柴油等等。
本发明的倾点下降剂分散体组合物可以单独或与其它添加剂组合使用,所述添加剂包括脱蜡辅助剂、腐蚀抑制剂、沥青质抑制剂、结垢抑制剂、抗氧化剂、润滑添加剂、去雾剂(dehazer)、传导性改进剂、十六烷值增进剂、淤渣生成抑制剂等等。
通过以下实施例可以更好理解前述内容,提供所述实施例是为了说明而不是想要限制本发明的范围。
实施例
实施例1
一百(100)重量份的包含约28重量%乙酸乙烯酯的乙烯乙酸乙烯酯共聚物,密度约0.95g/cc(根据ASTM D-792确定),熔融指数约43g/10min(ASTM D1238,在190℃和2.16kg下),和DSC熔点约74℃(ASTM3418),可从DuPont作为ELVAXTM240W商购,以及3.0重量份分馏脂肪酸,可得自Croda Inc.,商品名为PRIFRACTM2989(包含约88%山萮酸),将它们在双螺杆挤压机中在190℃下以6.2kg/小时的速率熔融捏和。
在熔融捏和树脂/稳定剂后,将7.5重量%的氢氧化钾水溶液以0.37kg/hr的速率连续进给到下游注入端口中。这种水性分散体随后在离开所述挤压机之前用补加的水以5.6kg/hr的速率稀释。
得到固体含量为51.2重量%和pH11.2的水性分散体。通过Coulter LS13320粒子分析仪测量的所述分散的聚合物相由0.41微米的平均体积直径和1.13的粒度分布(Dv/Dn)构成。
实施例2至5
向实施例1的分散体添加包含任选的表面活性剂的水/乙二醇混合物,以得到本发明的水性倾点下降剂分散体。所述组分添加在一起的次序不是本发明的关键。每种组合物具有30重量%的固体。在实施例2至5中,使用以下添加次序。向所述乙二醇添加(任选的)表面活性剂,(任选的)表面活性剂/乙二醇混合物然后添加到实施例1的分散体中,以产生水与乙二醇按重量计50:50的最终比率。这提供了直至约-40℃的防冻。混合利用磁性搅拌器实现,但可以使用任何通用的技术,包括(但不限于)磁力搅拌、机械混合例如掺合器、顶置式混合设备等等。表1描述了实施例2至5的组成,量基于所述水性倾点下降剂分散体组合物的总重量,以重量%列出。将约10克所述组合物放入20ml螺纹小瓶(Fisher Scientific#03-339-5A)中,并放入-40℃的干冰/丙酮浴进行平衡。平衡之后,从所述浴中取出小瓶并略倾斜。如果所述组合物在小瓶倾斜时移动,它被分类为在-40℃下流动。砂砾(Grit)这个术语用于描述向所述分散体添加乙二醇时、或当向乙二醇添加所述分散体时形成较大的粒子。据认为这些大粒子可以由小粒子的不稳定而形成,小粒子团聚并形成不需要任何放大就可以容易地看出的大粒子。
表1
实施例6
九十七(97)重量份的包含约32重量%乙酸乙烯酯的乙烯乙酸乙烯酯共聚物,密度约0.96g/cc(根据ASTM D-792确定),熔融指数约43g/10min(ASTM D1238,在190℃和2.16kg下),和DSC熔点约63℃(ASTM3418),可从DuPont作为ELVAXTM150商购,以及3.0重量份分馏脂肪酸,可得自Croda Inc.,商品名为PRIFRACTM2989(包含约88%山萮酸),将它们在双螺杆挤压机中在150℃下以6.0kg/小时的速率熔融捏和。
在熔融捏和树脂/稳定剂后,将10.7重量%的氢氧化钾水溶液以0.31kg/hr的速率连续进给到下游注入端口中。该水性分散体随后在离开所述挤压机之前用补加的水以5.8kg/hr的速率稀释。
得到固体含量为50.9重量%和pH11.6的水性分散体。通过CoulterLS13320粒子分析仪测量的所述分散的聚合物相由0.42微米的平均体积直径和1.15的粒度分布(Dv/Dn)构成。
实施例7至10
实施例7至10如上文对实施例2至5所述进行制备,除了实施例6的分散体添加到包含任选的表面活性剂的水/二醇混合物中以得到本发明的水性倾点下降剂分散体。实施例7至10的组成和性能描述在表2中,量基于所述水性倾点下降剂分散体组合物的总重量,按重量%列出。
表2
通过测量含蜡原油(比较例A)的倾点降低,来证明实施例2至5和7至10的倾点下降。在所述试验中,API比重为30(密度0.877g/ml)和倾点(未处理的)为39℃的含蜡原油用本发明的倾点下降剂以百万分之750(ppm)或1500ppm的处理速率处理。
所述原油首先通过将它在紧密密封的容器中在约60oC下保持至少3小时进行预处理,以消除热史和匀化所述原油混合物。利用具有一次性吸头的重复吸管,将热油根据期望的处理速率分配到含有适量倾点下降剂的样品小瓶中。所述小瓶然后盖紧盖子并在大约60℃下在间歇式振荡下保持至少两个小时,以允许所述倾点下降剂与所述原油相互作用。利用可得自Instrumentation Scientifique de Laboratoire的自动MPP5Gs仪器测量混合物的倾点。用这种仪器得到的倾点测量结果与ASTMD-97“石油产品倾点的标准试验方法(Standard Test Method for pour point of Petroleum Products)”相关联。进行重复测量。
结果显示在表3中。比较例A是没有添加剂的原油,比较例B是用10%的EVA的甲苯溶液(用于实施例1的相同EVA)处理的比较例A的原油,和比较例C是用10%的EVA的甲苯溶液(用于实施例6的相同EVA)处理的比较例A的原油。报告的值精确度在约±3℃内。从表3报告的值可以看出,本发明的倾点下降剂组合物可以将倾点降低9℃或更多。此外能够看出,所述结果与利用相同聚合物的甲苯溶液得到的结果相等或很相当。
表3
*未添加倾点下降剂。
Claims (12)
1.水性倾点下降剂分散体组合物,其包含:
i.乙烯乙酸乙烯酯共聚物(EVA),其量为从12至50重量%;
ii.分散剂,其量为从1至10重量%;所述分散剂包含阴离子型表面活性剂和非离子型表面活性剂二者;
iii.水;
和
iv.任选的水性凝固点下降剂;
其中重量百分比是基于所述水性倾点下降剂分散体组合物的总重量。
2.权利要求1的水性倾点下降剂分散体组合物,其中所述分散的EVA的平均粒度等于或小于1微米,最终组合物中分散剂的量是1至10重量%,并且所述最终组合物中的水:水性凝固点下降剂混合物以40至75重量%的量存在,所述水:水性凝固点下降剂的重量比是40:60至70:30。
3.权利要求1的水性倾点下降剂分散体组合物,其还包含:
v.稳定剂,其量为从0.5重量%至5重量%。
4.权利要求1的水性倾点下降剂分散体组合物,其中所述聚合物i是具有28至32重量%乙酸乙烯酯的乙烯乙酸乙烯酯共聚物,并且其熔融指数根据ASTM D1238在190℃和2.16kg下测定为43g/10min。
5.权利要求1的水性倾点下降剂分散体组合物,其中所述聚合物i是具有40重量%乙酸乙烯酯的乙烯乙酸乙烯酯共聚物,并且其熔融指数根据ASTM D1238在190℃和2.16kg下测定为52g/10min。
6.权利要求1的水性倾点下降剂分散体组合物,其中所述分散剂ii包含以下一种或多种:
a.具有式R1COOR2的脂肪酸/盐,其中R1是8至25个碳原子的直链饱和或不饱和烃基并且R2是H或碱形成基团;
b.烷基、芳烃和/或烷基芳烃磺酸盐;
c.烷基丙烯酸酯和/或烷基甲基丙烯酸酯和丙烯酸和/或甲基丙烯酸的聚合物的盐,或马来酸酐-苯乙烯共聚物的偏酯的盐;
并且所述分散剂ii任选地包含以下一种或多种:
d.阳离子型表面活性剂;或
e.两性离子表面活性剂。
7.权利要求1的水性倾点下降剂分散体组合物,其中所述分散剂ii中包含的所述阴离子型表面活性剂是油酸、硬脂酸、山萮酸或芥酸的钠盐,或油酸、硬脂酸、山萮酸或芥酸的钾盐,或其混合物。
8.权利要求1的水性倾点下降剂分散体组合物,所述组合物以0.5重量%至5重量%的量含有稳定剂v,其中所述稳定剂选自聚乙氧基化非离子型表面活性剂;聚乙烯醇;或乙烯甲基丙烯酸共聚物、聚丙烯酸聚合物、聚丙烯酸共聚物、或丙烯酸和氨基甲酸酯共聚物的离聚物。
9.权利要求1的水性倾点下降剂分散体组合物,所述组合物以0.5重量%至5重量%的量含有稳定剂v,其中所述稳定剂选自聚乙氧基化非离子型表面活性剂;聚乙烯醇;或乙烯丙烯酸共聚物、乙烯甲基丙烯酸共聚物、聚丙烯酸聚合物、或丙烯酸和氨基甲酸酯共聚物的离聚物。
10.权利要求1的水性倾点下降剂分散体组合物,所述组合物含有水性凝固点下降剂iv,其中所述水性凝固点下降剂选自氯化钠、氯化钾、氯化钙、甲醇、乙醇、丙醇、乙二醇、甘油、乙二醇的乙醚、乙二醇的丙醚、乙二醇的丁醚、乙二醇的己醚、二乙二醇、或丙二醇。
11.权利要求1的水性倾点下降剂分散体组合物,其还包含选自杀生物剂、着色剂、消泡剂或其混合物的其他添加剂vi。
12.抑制石蜡沉积和/或改善油流动性质的方法,所述方法包括向所述油添加有效量的权利要求1的倾点下降剂组合物的步骤。
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BR112017010805B1 (pt) | 2014-12-05 | 2022-08-09 | Dow Global Technologies Llc | Propante revestido para o tratamento de petróleo e método de tratamento de uma formação subterrânea |
AU2016222955A1 (en) * | 2015-02-27 | 2017-09-28 | Dow Global Technologies Llc | Hydrocarbon solvent stable aqueous pour point depressant dispersion composition |
WO2016171741A1 (en) * | 2015-04-23 | 2016-10-27 | Bridwell Randolph Earl | Methods and compositions for lowering ice temperature and freezing point of water |
JP6901469B2 (ja) | 2015-10-07 | 2021-07-14 | ダウ グローバル テクノロジーズ エルエルシー | 水性ヒートシールコーティング組成物を調製するためのプロセス |
EP3426702B1 (en) * | 2016-03-10 | 2019-10-30 | Basf Se | Aqueous polymer dispersions, a method for their preparation and the use thereof as pour-point depressants for crude oil, petroleum, and petroleum products |
WO2018177619A1 (en) | 2017-03-30 | 2018-10-04 | Clariant International Ltd | Fluids for fracking of paraffinic oil bearing formations |
EP4253333A1 (en) * | 2017-06-02 | 2023-10-04 | Carbonet Nanotechnologies Inc. | Sequestering agents, kits therefor, and methods of using sequestering agents and kits therefor |
RU2020115424A (ru) | 2017-10-31 | 2021-11-08 | Дау Глоубл Текнолоджиз Ллк | Способы получения водных композиций термоплавких покрытий |
EP3704206A1 (en) | 2017-11-03 | 2020-09-09 | Baker Hughes Holdings Llc | Treatment methods using aqueous fluids containing oil-soluble treatment agents |
CN111233142A (zh) * | 2020-03-03 | 2020-06-05 | 深圳市长隆科技有限公司 | 一种适用于北方冬季低温条件的高效复合碳源及其制备方法 |
CN113402724B (zh) * | 2021-06-11 | 2022-10-28 | 东北石油大学 | 一种纳米复合降凝剂的制备方法 |
US20230348806A1 (en) * | 2022-04-28 | 2023-11-02 | Baker Hughes Oilfield Operations Llc | Phase change materials to address reversion problems in heavy oils |
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