CN104981538B - 粗妥尔油的生物精炼 - Google Patents
粗妥尔油的生物精炼 Download PDFInfo
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- CN104981538B CN104981538B CN201380065814.7A CN201380065814A CN104981538B CN 104981538 B CN104981538 B CN 104981538B CN 201380065814 A CN201380065814 A CN 201380065814A CN 104981538 B CN104981538 B CN 104981538B
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Classifications
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- C10L1/1888—Carboxylic acids; metal salts thereof tall oil
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C07—ORGANIC CHEMISTRY
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- C07C2603/00—Systems containing at least three condensed rings
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- C10G2300/1014—Biomass of vegetal origin
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Abstract
本发明提供了一种精炼粗妥尔油(CTO)的工艺。所述工艺包括在真空下将精炼CTO分馏为至少一种精炼妥尔柴油(RTD)或妥尔油脂肪酸(TOFA)的料流,所述RTD或TOFA包含2‑30体积%的树脂酸和20‑90体积%的脂肪酸,并且至少一种树脂酸(RA)的料流包含小于5体积%的脂肪酸。所述RTD或TOFA料流在随后的步骤中脱氧形成烃化合物。本发明还涉及精炼妥尔柴油。此外,本发明描述了一种制备精炼妥尔柴油(RTD)组合物的工艺,其中将粗硫酸盐松脂(CST)添加到所述精炼妥尔柴油(RTD)组合物。
Description
技术领域
本发明涉及粗妥尔油(CTO)的生物精炼。
背景技术
术语粗妥尔油,以下称为CTO,是指硫酸盐法制浆工艺中木材制浆期间获得的副产物料流。妥尔油(TO)的名称起源于瑞典语“tallolja”(“松油”)的英语化。TO由通常约75-80重量%的具有酸性(-COOH官能团)的馏分和最多至25重量%的中性馏分构成。后一种馏分通常称为不可皂化的馏分。不可皂化的馏分由一系列组分构成,例如烃、脂肪醇、植物甾醇类醇、醛等以及来自酸性和中性馏分成分之间的内反应的高分子量组分。另一方面,由具有酸性官能团的组分构成的馏分可进一步细分为两大类馏分,即(i)脂肪酸馏分和(ii)树脂酸馏分,每种馏分包含多种单独的组分。
从妥尔油组合物的此描述中可明显看出CTO代表了具有吸引力的可再生精细化学品库,该可再生精细化学品库目前因考虑到严格的环境法规和不断上涨的石油价格而获得广泛关注。
目前,CTO分馏通常通过真空蒸馏进行。目的非常明确,将CTO分为两种馏分:(i)最多至75重量%的酸性馏分以及称为(ii)妥尔油沥青(TOP)的次要馏分。酸性馏分在高温和相对高真空下工作的一系列分馏塔中进一步加工,获得富含脂肪酸和树脂酸的料流。TOP通常作为内部燃料返回制浆装置或在热电装置中用作生物燃料。最小化CTO精炼工艺中产生的TOP馏分是非常重要的,并且本发明涉及产生高产率的高附加值化学品和供汽车使用的生物燃料的CTO精炼工艺。
将CTO精炼为高附加值生物燃料的工艺在WO 2009/131510中有所公开。在WO2009/131510中,公开了将粗妥尔油转化为高质量柴油燃料的方法,其包括如下步骤:(a)移除粗妥尔油中存在的非油污染物并且回收粗妥尔油中存在的高附加值有机化合物,从而形成精炼妥尔油料流;(b)移除来自步骤a)的精炼妥尔油料流的挥发性馏分,从而形成包含在大气压下沸点为170℃或更高的有机组分的无挥发物油料流;(c)在真空分馏塔中将步骤b)的无挥发物油料流分成两种工艺料流或相,其中第一工艺料流或相基本上包含在大气压下沸点在170-400℃范围内的组分,并且第二工艺料流或相基本上包含在大气压下沸点超过400℃的组分;以及(d)通过脱羧作用和/或脱羰作用降低由来自步骤c)的沸点在170-400℃范围内的组分构成的料流中的氧含量。
本发明的一个目标是提供改进的CTO精炼方法。根据本发明的另一个具体目标是提供改进的CTO预处理工艺。本发明的又一个具体目标是提供从CTO制备树脂酸和精炼妥尔柴油(以下称为RTD)的改进工艺。本发明还有在下文提供的其他目标。
本发明第一方面的背景技术
粗妥尔油包含一系列广泛的有机化合物,包括松脂、树脂酸、甾醇(5-10%)、脂肪酸(主要是棕榈酸、油酸和亚油酸)、脂肪醇以及其他烷基烃衍生物。通过CTO妥尔油的分馏可获得树脂酸(RA)和妥尔油脂肪酸(TOFA)。RA可用作粘合剂、橡胶和油墨的组分,并且可用作乳化剂。TOFA可用作制备可再生柴油燃料,例如RTD(粗妥尔柴油)、燃料添加剂(十六烷值增强剂)的原料,或用作制备精细化学品(洗涤剂、油漆等)的基材。
CTO包含大约在约500ppm最多至数千ppm范围内的硫化合物。通常具有恶臭气味的硫化合物包括一系列广泛的有机和无机硫化合物,包括硫酸盐、亚硫酸盐、聚硫化物、元素硫、硫醇、有机硫化物和有机砜以及磺酸盐。硫化合物主要涉及低分子量组分,其存在于粗妥尔油(松脂)中,但也可存在于粗妥尔油的脂肪和二萜部分中。
制浆装置通常利用专用化学品额外提高其制浆产率。用于Kraft型工艺的典型化学品是蒽醌(AQ)。因此从利用AQ的制浆装置输入的CTO包含最多至2000ppm的某些AQ部分。
CTO包含大量脂肪酸,本文也缩写为FA。FA包含在C12至C26范围内的组分,其中C18脂肪酸异构体是主要组分。FA具有两种官能团类型:羧基和双键。FA组分在饱和至具有最多至三个双键的不同饱和度的(分离的或共轭的)组分的范围内。
粗妥尔油还包含大量高附加值C20二萜酸(本文也缩写为RA),包括松香酸、芳族脱氢松香酸以及通过芳烃取代形成的二萜酸的磺酸衍生物。二萜酸具有两种官能团类型:羧基和双键。几乎所有二萜酸都具有相同的基本骨架:具有经验式C19H29COOH的三环稠合系统。
二萜酸在松树中以若干具有分子式C19H29COOH的同分异构形式以及一些相关结构存在。最普遍的二萜酸是:
枞酸型酸
松香酸
松香-7,13-二烯-18-酸
13-异丙基-7,13-二烯-15-罗汉松酸
新松香酸
脱氢松香酸
长叶松酸
简式C20H30O2或C19H29COOH
表示大部分85-90%的典型妥尔油。
以结构式(CH3)4C15H17COOH表示
分子量302
海松酸型酸
海松酸
pimara-8(14),15-二烯-18-oic酸
左旋海松酸
异海松酸
简式C20H35O2或C19H34COOH
以结构式(CH3)3(CH2)C15H23COOH表示
分子量307
使用硫酸盐法化学制浆工艺制造木浆级化学纤维素将这些二萜酸释放至蒸煮废液。
粗Kraft松脂(通常称为CST,即粗硫酸盐松脂)是硫酸盐法制浆期间作为残余产物获得的有机液体。具有恶臭气味的粗Kraft松脂通常在封闭体系中处理,在制浆装置现场收集,并且作为燃料燃烧或输出以用于进行升级。松脂也可通过对粗妥尔油进行分馏或通过对得自树木主要是松树的树脂进行蒸馏获得。松脂馏分由通常称为萜烯的一系列广泛的有机化合物构成。萜烯根据构建各自组分所需的异戊二烯单元C5H8的数量分类,因此称为半萜(C5H8)、单萜(C10H16)、倍半萜(C15H24)、二萜(C20H32)等等。来自CTO的松脂馏分通常在大气压下在120-180℃范围内沸腾,其中单萜例如α-蒎烯和β-蒎烯是主要组分。松脂具有0.7-0.87kg/l的密度。
本发明第一方面的发明内容
本发明还涉及将任选地包含松脂、脂肪酸和树脂酸(RA)馏分的CTO(粗妥尔油)转化为可再生柴油燃料(精炼妥尔柴油(RTD))或TOFA以及纯树脂酸(RA)。根据本发明的这个方面,提供了从粗妥尔油(CTO)混合制备RTD/TOFA和RA的工艺,所述工艺涉及CTO的精炼,其中该工艺包括在真空下将精炼CTO分馏为至少一种精炼妥尔柴油(RTD)或TOFA的料流,所述RTD或TOFA包含2-40体积%的树脂酸和20-90体积%的脂肪酸,并且至少一种树脂酸(RA)的料流包含小于5体积%的脂肪酸,其中RTD或TOFA的料流任选地在随后的步骤中脱氧形成烃化合物。在该语境中,可进一步地说,RTD或TOFA还可包含如2-8体积%的中性组分,例如倍半萜和二萜和/或其部分氧化对应物,如醇、酮、醛等。此类组分还可具有接近FA和RA的沸点,这使得它们难以分离。
剩余的TOP(在回收RTD/TOFA和RA后)馏分构成被送入分馏阶段的CTO的小于30重量%。
在分馏之前,根据本文上面讨论的本发明第一方面有利地预处理CTO并将其转化为精炼CTO。在第一预处理步骤中,处理CTO以通过离心和/或过滤移除污染物,然后是移除水和挥发物的步骤,从而形成精炼CTO料流。在第二步骤中,高沸点(分子量很大)的组分在真空下作为液流(妥尔油沥青,TOP)从主要由脂肪酸和树脂酸构成的气流中分离。
将气态脂肪酸和树脂酸吸入在真空下工作的分馏塔,其中富含脂肪酸的RTD/TOFA馏分从塔的上部取出,并且富含RA的馏分从塔的底部取出。富含RTD/TOFA的气态脂肪酸料流被冷凝为液态精炼妥尔柴油“RTD”,该RTD可被输出以用于进一步升级为例如高级生物燃料组分。或者,输出进行或未进行进一步精炼以降低RA含量的RTD/TOFA料流,以用于精细化学品制造(皂、润滑剂、粘合剂和清漆)。
在本发明的另一个具体实施例中,输入来自木材加工并且在120-180℃的范围内沸腾的有机化合物(包括例如松脂),并添加至RTD。有机化合物(包括松脂)也可从挥发物馏分回收,该挥发物馏分根据本文上面的描述移除,并且有利地添加至RTD。松脂化合物(主要组分为α-蒎烯和β-蒎烯)具有相当低的密度,因此添加至RTD减少了RTD的总密度。来源于木材加工工艺并且在120-170℃的范围内沸腾的松脂和/或其他有机化学品的添加在下文进一步描述,并且涉及本发明的第二方面。
在任选的第四步中,对添加或未添加松脂化学品的RTD在工作于高于150℃的温度下的反应器中的至少一个反应区中在催化条件下进行处理,其中RTD中存在的脂肪酸脱羧和/或脱羰,从而形成可再生柴油范围燃料组分。
使用策略性布置的TFE和CTO预处理(其中移除CTO杂质)协同工作以保存所需的RTD/TOFA和RA组分,继而与现有技术相比提高了RTD/TOFA和RA产率。此外,使用在高真空水平下工作并且以最小压降特征曲线表征的分馏塔确保分馏期间的低工作温度,从而提供与现有技术相比CTO分馏的节能工艺。
本发明第一方面的具体实施例
下文描述了与根据本发明的从CTO混合制备RTD/TOFA和RA的工艺相关的具体实施例。
本发明人发现CTO可以一系列创新步骤转化为精炼妥尔柴油(RTD)或TOFA料流和高附加值树脂酸(RA)料流。RTD主要包含脂肪酸、脂肪醇和树脂酸。RTD通过RTD中有机化合物的沸点进一步表征。RTD组分在大气压下在120-420℃的范围内,更优选地在160-400℃的范围内沸腾,并且典型的RTD混合物具有0.88至0.95kg/l的密度。或者,可输出富含脂肪酸的料流,并在精细化学品的制造中用作TOFA。
如上文所公开,精炼CTO在真空下实际分馏之前,可进行一个或多个CTO预处理步骤,并且随后回收富含RTD/TOFA和RA的料流。
CTO任选地通过本文所述的工序预处理,然后是至少一个分离处理,其移除了由大气压下沸点低于约200℃,更优选地低于约170℃的组分构成的妥尔油馏分(在下文称为妥尔油挥发物)。
CTO中存在的挥发性馏分通常在十分之几重量%最多至2重量%的范围内,另外还有夹带在CTO中的0.5-3重量%的水。前一种馏分由多种不同分子量的组分,主要是C8至C16碳化合物(松脂、烃、具有不同含量的异质元素例如硫、氧、氮等的烃)构成。
挥发性有机材料在大气压下低于约200℃沸腾,但超过约120℃将从粗妥尔油料流移除。挥发物(包括松脂)可在一个或多个薄膜蒸发器或汽提塔以及它们的组合中移除,所述薄膜蒸发器或汽提塔在100-220℃范围内的温度下以及30-60kPa范围内的低压下工作。
在以下工艺步骤中,高沸点CTO组分或妥尔油沥青TOP(残余灰分、单个组分的平均沸点远大于440℃的有机馏分)从存在于CTO中的RTD/TOFA组分和树脂酸分离。除灰分之外,妥尔油沥青通常包含(i)包含不可皂化馏分(>C28)的组分;(ii)高分子量(500-600g mol-1)甾醇酯和/或蜡型酯以及(iii)Diels-Alder型分子间二聚反应的产物。CTO不可皂化物中的典型高沸点化合物是菜油甾醇(C28)、豆甾醇和谷甾醇(C29)、角鲨烯、桦木醇、羽扇豆醇(C30)、甲基桦木醇(C31)等。
在本发明的一个实施例中,使用在250-320℃和0.7-1.5kPa的低压下并联或串联工作的一个或多个薄膜蒸发器(TFE)将TOP从脂肪酸和树脂酸分离。热通过料流或热油提供给TFE。在加入到配备有一种或多种结构化填料的分馏塔之前,离开TFE的脱挥发妥尔油(脂肪酸和树脂酸)的温度应在200-330℃,优选地200-250℃的范围内。
用于分离RTD/TOFA和RA的主分馏塔在真空条件(0.1-2.5kPa,优选地0.1-1kPa)(1-25mbar,优选地1-10mbar)和150-280℃范围内的温度下工作。主分馏塔及其进料段设计根据以下目的优化:(i)使RTD/TOFA馏分的产率最大化,其中组分在170-420℃的温度范围内(在大气压条件下)沸腾;(ii)在约370-420℃(在大气压条件下)下进行显著的分馏切割;(iii)使不期望的反应最小化,以便高质量、高产率回收塔下部的树脂酸以及(iv)使分馏塔底部的压力和温度降至最低,这使得所需产物组分的降解最小化。
如上文所理解,根据一个具体实施例,真空下的分馏以至少三个步骤进行(用于从精炼CTO移除TOP的TFE,分离RTD/TOFA和RA的分馏塔以及用于精炼RA的分馏塔)。
根据上文公开的具体实施例,将CTO(通过本文所述的工序精炼)加入用于从CTO分离妥尔油沥青(TOP)的第一分馏步骤,然后是第二分馏步骤(真空分馏塔),其中在大气压下沸点在170-420℃范围内的富含RTD组分的料流从大气压下沸点高于约420℃的RA组分料流分离。在第三分馏步骤中,RA进一步精炼为具有低脂肪酸含量的RA。
通过将TFE单元用于从CTO移除妥尔沥青,可实现妥尔油沥青中剩余的树脂酸水平小于5%。将离开TFE的富含气态脂肪酸和树脂酸的料流排放到设计用于分离RTD组分和树脂酸的主分馏器中。在替代和优选的构造中,将精炼CTO加入到第一TFE中,第一TFE将挥发的TOFA和RA排放到主分馏器中,并且将富含RA和TOFA臂(arm)的CTO排放到第二TFE,第二TFE将FA和RA排放到主分馏器,并且RA料流仍富含RA,将该料流加入到第三TFE,第三TFE将RA排放进入RA纯化步骤(RA抛光塔),并且排放TOP以从制造厂输出。
从上文可看出,来自第一TFE单元的料流可与来自第二TFE单元进入分馏塔的类似料流混合,其中生成RTD和RA料流。根据本发明的另一个可能途径是从第一TFE单元单独抽取气态料流,然后将该气态料流进一步加工为TOFA,或通过脱氧作用、脱羰作用和脱羧作用中的一者或多者处理该料流以生成富含石蜡的原料,然后进入石油精炼加氢处理单元或蒸汽裂化器,以用于制备精细化学品,例如乙烯、丙烯等。
根据一个具体实施例,将从分馏塔下部回收的富含RA的料流排放进入RA纯化步骤(抛光塔),或在薄膜蒸发器中进一步加工,以用于从RA分离夹带的TOP组分,所述RA在RA纯化步骤中通过在真空下加工进一步精炼(分馏塔是RA抛光塔),以生成包含小于约4重量%脂肪酸的高质量RA。
应当理解,从分馏塔回收的富含RA的料流可在TFE单元中进一步加工,仅用于生成足够质量(RA含量、颜色、FA含量、熔点等)的RA馏分,而不是在第二RA分馏塔中加工该料流。
填充分馏塔通常由一个或多个结构化填料床、柱底部的重沸器装置以及优选地柱顶部的回流装置构成。
现代结构化填料通常由以适当方式布置的薄波纹金属板或网纱构成,其中每个特定设计的一般目的是迫使流体泵入柱,沿着这些预先设计的长路径行进,从而提供大表面积,继而确保流体和蒸气之间的接触最大化。虽然优于盘式蒸馏柱,但填充床柱还显示出某些压降。特别设计的结构化填料的利用确保实现柱顶和柱底内的压降低于1.5kPa(15mbar),优选地1kPa以及最优选地0.5kPa(10mbar以及最优选地5mbar)。
根据本发明的优选实施例,利用具有最小压降特征的结构化填料。
结构化床的高度与所需分馏度密切相关,即为实现某些分馏水平所需的理论塔板数。如上文所理解,分馏塔由一个或多个结构化床构成。因此,本发明中利用的主要结构化填料/床的高度受到调控,以实现高产率的RTD/TOFA。在床的上部回收的RTD/TOFA材料可包含20重量%树脂酸之多,甚至最多至30重量%,但优选地RTD/TOFA的树脂酸含量在1-10重量%之间,更优选地在1-5重量%RTD/TOFA化合物的范围内。在用作精细化学品制造的原料,用作燃料,用作催化床中部分或完全脱羧作用以生成缺氧可再生柴油燃料组分的进料,或输出用于进一步处理为石油精炼中柴油范围可再生燃料组分之前,RTD/TOFA可通过蒸馏、过滤、冷却等进一步精炼。此处提及的名称“可再生柴油范围燃料组分”理解为在170-400℃的范围内沸腾的烃。然而,该填料的主要功能是将批量RTD/TOFA分离为顶部料流,并生成富含RA的底部料流。
根据本发明的一个优选实施例,从离开TFE的气态料流分离RTD/TOFA和二萜酸(树脂酸)在连接至TFE的填充床真空分馏塔中实现。
在TFE单元内将进料作为薄膜涂上,在本发明的所有实施例中该单元连接至分馏塔。因此TFE中的保留时间非常短,使得所需的RTD/TOFA和RA组分得以保存,从而提高了RTD/TOFA和RA产率。
进一步限定RTD/TOFA分馏切割的典型方法是在柱顶部安装回流装置,其在150-220℃的温度范围内工作。在回流方法中,通常大部分产物返回到柱中柱顶端附近的位置。一般来讲,更高的回流比得到更明显的蒸馏切割馏分。有利地,将另一个结构化填料安装在进入的回流料流之下。因此,填料(i)均匀地重新分配相对较冷的回流料流,并且(ii)确保存在较大的表面积,继而使回流效果最大化。
因此,根据本发明的一个具体实施例,分馏塔配备有柱顶端附近的回流构造。根据本发明的另一个具体实施例,通过选择合适的回流比而使由沸点为370-420℃的组分构成的料流的高端更明显。此外,根据本发明的又一个具体实施例,返回柱的回流料流的均一性通过柱中的辅助结构化填料实现。
然而,为了实现有效分离,还应确保贯穿柱的流体流动为均一的。当实现均一流体流动时,在当前条件下为液体的组分优选地为填料表面上的细滴,而沸腾的组分作为蒸气移动。柱中的均一流动通过适当的分配器和/或结构化填料实现。
通常,热和对应的蒸气通过安装在塔底部的重沸器装置提供给填充床分馏塔。如可从上文理解,分馏塔优化的一个目的是使大规模加热导致的不期望反应最小化。因此,必要的热和蒸气优选地仅通过直接连接至分馏塔的TFE提供。塔的液体体积保持最小。例如,支持TFE的换热器也可布置于系统中。
在利用填充床分馏塔的主塔中分馏后获得的主料流为RTD和富含RA的料流,其进一步精炼为本发明所公开工艺的高纯度RA主题产物。
RA的进一步加工在根据本发明的第二分馏塔(RA抛光塔)中进行。在第二分馏塔中,获得一个具有在170-420℃范围内沸点的富含脂肪酸组分的RTD/TOFA料流,以及一个高质量RA料流和任选地一个包含有色体和其他不期望高沸点组分的TOP料流。第二分馏塔的设计根据以下目的进行优化:(i)使RA馏分的产率最大化;(ii)具有最少含量FFA的RA馏分以及(iii)高(亮)色级的RA馏分。
根据本发明,RA抛光塔是由一个或多个结构化床构成的填充床分馏塔。塔在提供0.01-0.1kPa(0.1-1.0mbar)压力的单独真空管路上工作。通过批量RTD/TOFA馏分的缺失使低真空水平容易实现。此外,低真空水平允许利用基本上相同的工作温度(150-280℃)用于RA分馏,因此当暴露于高温时显著减少了RA典型的降解反应的风险。
RA抛光塔中的RA分馏在安装于塔中部的分馏塔主要填料(相对于其他填料床安装在塔的中间)中实现。填料设计提供剩余的FFA与RA馏分的有效分离。分离也可受到选择通过与结构化填料一起安装在塔顶部的回流装置的合适回流比的影响,确保返回回流料流的均一性。
由RTD/TOFA组分构成的回收料流从安装在顶部填料下方的“抽出塔盘”排放,而RA料流从安装在中间填料下方的“抽出塔盘”排放。
必要的热和蒸气通过富含RA的材料料流递送,所述富含RA的材料料流从主塔和RA抛光塔之前的一个或多个TFE单元排放。来自TFE的蒸气排放到抛光塔中低填充床下,所述低填充床经优化为分离所有较重和/或有色组分,所述组分继而以TOP料流从塔的底部排放到TFE。该TFE单元可以例如用降膜蒸发器(FFE)补充。
因此,本发明公开了其中无挥发物和纯化的CTO料流分离为三个单独的料流或相的工艺,其中一个料流或相RTD/TOFA由沸点为约170-400℃的组分构成,一个料流或相妥尔油沥青(TOP)由沸点超过440℃的组分构成,并且第三料流包含在约390-440℃沸腾的二萜酸或树脂酸,所有温度均在大气压下。
脱臭和至少部分脱硫松脂(包括α-蒎烯)的第四料流可任选地在从第一分馏塔回收RTD之后添加到RTD料流,所述松脂在大气压下120-200℃范围内沸腾。将松脂和其他低沸点材料添加到产物RTD,以降低RTD的密度,并且增加RTD中在低于约200℃下沸腾的组分的份数。因此,可添加松脂和其他低沸点有机组分以增加RTD中C8-C12碳分子的份数15重量%之多。优选地,RTD包含约2-15重量%的C8-C12松脂组分,更优选地2-8重量%的此类组分。
根据本发明的一个具体实施例,基于精炼CTO进料的RTD/TOFA的总产率大于50%,例如大于55重量%,并且RA的总产率大于15重量%。根据一个具体实施例,基于CTO进料的RTD/TOFA的总产率在55-70重量%的范围内,例如大约60重量%,并且RA的总产率在10-25重量%的范围内,例如大约15重量%。从分馏塔首先获得的RTD/TOFA相可表示大约60重量%的精炼CTO进料,并且从RA抛光塔获得的第二RTD相表示大约3重量%的送入第一分馏塔的精炼CTO进料。可控制和调整第一分馏塔以实现通常在2-30%范围内的RTD/TOFA的所需RA含量。如本文所述,RTD的总产率可通过添加松脂进一步增加。
在本文所述的从CTO回收RTD/TOFA和RA的所有实施例中,生成最终高沸点残余产物TOP,其表示在10重量%和30重量%之间,或可能最多至35重量%的送入CTO分馏的CTO。此外,本发明工艺的特征在于与传统和现有技术CTO分馏工艺相比的低比能耗。CTO分馏为RTD/TOFA和RA的总能耗(热油和/或料流)低于约600千瓦时/吨精炼CTO进料,优选地低于约500千瓦时/吨精炼CTO进料。当前CTO分馏工艺使用远高于1000千瓦时/吨的CTO分馏比能量。
根据本发明第一方面的一个实施例,提供了从CTO混合制备RTD和RA的工艺,其中精炼CTO由已在涉及CTO洗涤和杂质分离的预处理步骤中进行加工的CTO获得,从该预处理步骤获得第一精炼CTO料流,然后所述第一精炼CTO料流通过闪蒸、汽提和/或在薄膜蒸发器中处理来进一步加工,以从CTO移除挥发性组分,形成第二精炼和基本上无挥发物的CTO料流,该料流在薄膜蒸发器中进一步加工,以从富含脂肪酸和树脂酸的第三料流分离和移除TOP,该料流加入到第一分馏塔,用于以高产率回收RTD/TOFA和RA。
RTD馏分可与低沸点有机材料(在大气压下沸点120-200℃)混合,所述低沸点有机材料包括在妥尔油分馏装置中移除的松脂或从制浆装置输入的松脂。该低密度有机材料(密度0.7-0.87kg/l)优选地脱硫,并且脱臭松脂和/或妥尔油头馏分(C8-C16碳化合物)在粗妥尔油分馏装置或输入的粗松脂中回收。
根据本发明制备的RTD可同样地用作氧化精炼柴油燃料;然而,RTD有利地通过脱羧和/或熟知的石化脱氧/氢化工艺升级至高级柴油燃料。从分馏柱回收的RTD(添加或不添加松脂)可有利地直接或间接加入到位于粗妥尔油分馏装置附近或远处位置的额外加工塔板,其中RTD的至少一部分氧含量在存在催化剂的情况下通过脱羧和/或脱羰反应途径减少。脱羧和/或脱羰反应在150-350℃范围内的温度下在具有一个或多个催化床的混合床反应器中进行。通过合适的催化剂促进脱羧和脱羰反应。典型的脱羧/脱羰催化剂包括活性炭、碳负载贵金属和/或过渡金属、活性(酸性)氧化铝、氧化锆等、漂白土、碳酸盐基催化剂和过渡金属催化剂。在过渡金属催化剂中,可使用标准耐硫催化剂例如NiMo/Al2O3。
脱羧反应是吸热的,并且氢可任选地在脱羧期间注入,以从放热氢化反应提供热。
因此,本发明的第一方面描述了从粗妥尔油回收树脂酸和粗妥尔柴油RTD或TOFA的工艺。粗妥尔柴油RTD在催化条件下进一步处理,移除氧从而形成含烃可再生柴油化合物。
本发明第二方面的发明内容及其具体实施例
本发明还涉及优化RTD组合物以及用于制备此类组合物的工艺。根据本发明的优化RTD组合物包含1-30重量%树脂酸(RA)和70-95重量%脂肪酸(FA),并且还包含1-10重量%粗硫酸盐松脂(CST)和0-1重量%蒽醌。如上文所述,RTD组合物还可包含如2-8体积%中性组分。
采用根据本发明的RTD组合物获得的优点特别是,所制备的粗硫酸盐松脂(CST)并且任选地蒽醌的含量用作高价值组分,即增加工艺中RTD的总产率。此外,CST减少了RTD混合物的密度,并且增加了来自森林类原材料的RTD的产率。本文所述的CTO生物精炼产生的CST以及输入的CST可添加到根据本发明制备的RTD组合物中。
根据本发明的一个实施例,提供了用于制备优化RTD组合物的工艺。该工艺涉及低密度精炼妥尔柴油(RTD)组合物的制备,其中将粗硫酸盐松脂(CST)添加到精炼妥尔柴油(RTD)组合物。
可纯化待混合到RTD组合物中的CST。该纯化涉及硅的移除,所述硅来自制浆装置和造纸装置所用的消泡剂,并且该纯化可以例如通过吸附于介质例如矾土、活性炭来实现。因此,根据一个具体实施例,所添加的粗硫酸盐松脂(CST)的纯化涉及至少硅的移除。根据又一个实施例,粗硫酸盐松脂(CST)的纯化通过吸附进行。
根据一个具体实施例,CST在从CTO或精炼CTO分离挥发性组分(沸点在120-250℃的范围内)期间制备。如上所述,CST还可从硫酸盐法制浆装置输入,并且添加到根据本发明的RTD组合物中。
根据本发明该工艺方面的一个具体实施例,挥发性组分的沸点低于200℃。挥发性组分的移除可以例如在由汽提塔和/或薄膜蒸发器构成的工艺系统中进行。
另外,该工艺有利地整合到本发明的其他方面,即所述工艺用第一预处理步骤补充以用于制备精炼CTO,所述第一预处理步骤包括CTO洗涤和杂质的分离,然后是在精炼CTO中分离沸点在120-200℃范围内的挥发性组分以用于制备无挥发物妥尔油料流。无挥发物妥尔油料流随后在薄膜蒸发器(TFE)中处理,以移除妥尔油沥青(TOP)。
TFE中的加工在真空、约300℃的温度下进行(该温度下的停留时间为约2min)。在TFE中从精炼妥尔油料流移除TOP产生在10-30重量%范围内的TOP,并且气态脂肪酸和树脂酸的料流对应于加入到TFE的约70-80重量%精炼妥尔油料流。应当指出的是,相对于本发明的方面,表达“TFE”可自然地指单个TFE,也可以是若干TFE,以及例如本发明的第一方面中论述的若干TFE。
根据本发明的又一个具体实施例,将另外的基本上不含TOP的精炼妥尔油料流送入分馏塔,在该处分馏成一个富含沸点在170-410℃范围内的组分的精炼妥尔柴油(RTD)料流,以及一个沸点在410-440℃范围内的树脂酸料流。CST有利地在RTD从分馏塔排放后添加到RTD,以用于进一步提高RTD的产率,并且降低RTD的密度。
根据又一个实施例,基于送入分馏装置的CTO计,RTD的总产率高于55重量%,例如甚至高于65重量%,并且RA的总产率高于15重量%。例如,从分馏塔获得的第一RTD相为大约60重量%。
在最终RA抛光分馏塔中,RTD在上部分回收,并且高质量RA在下部分回收。在抛光塔中回收的RTD包含基本上占总RTD产率的约1-5%的脂肪酸。将从RA抛光塔的下部回收的酸值为160-180mg KOH/克样品的高质量RA从装置输出。根据RA和/或RTD的市场,从分馏塔回收的RTD料流的RA含量可控制在2-40%之间,例如在2-30%的范围内。正如所理解的,组合第一和第二RTD料流并且从装置输出,添加或不添加装置中生成或输入到装置的CST。
根据本发明的另一个实施例,如上所述,从分馏塔回收的富含RA的料流在RA抛光塔中进一步精炼,其中RA精炼到所需的纯度(RA含量90重量%或更高,FFA小于4重量%,软化点高于70℃,并且颜色的加德纳色值在6-7之间)。
本发明涉及预处理的另一方面的背景
通过CTO的真空蒸馏制备的妥尔油松香(或树脂酸)可用作粘合剂、橡胶、油墨和乳化剂的基本组分,而妥尔油脂肪酸(TOFA)可用于制备皂和润滑剂。
然而,粗妥尔油是来自硫酸盐法制浆操作的残余料流,包含多种杂质。典型的CTO污染物包括残余矿物酸、碱金属盐和/或皂、碱土金属盐和/或皂、过渡金属、纤维素纤维以及分子量远高于1000个单位的大有机木质素化合物。杂质的存在通常是在硫酸盐法制浆装置处制备CTO期间从盐水分离妥尔油无效导致的。跟随CTO的少量盐水包含大多数上述杂质。
杂质导致CTO加工期间出现问题,并且对所需馏分,即RTD、TOFA和妥尔油树脂酸(RA)的产率造成有害影响。因此,不同类型的盐和/或皂、纤维素纤维和木质素沉积在各种加热表面,导致出现流动问题和/或限制了热传递。另外,盐可导致薄膜蒸发器单元(TFE)内的喷溅,提供了非挥发性组分被夹带入气相的可能。残余矿物酸(通常为硫酸)、各种盐和过渡金属在CTO储存和加工期间充当催化剂。H2SO4是游离脂肪酸(FFA)和来自具有(-OH)官能团的中性馏分的各种组分之间的酯化反应的高效催化剂。通常所获得的酯的特征在于高分子量,从而导致最后所需的TOP馏分减少。这些高分子量酯通常在CTO储存期间形成。在CTO加工期间,硫酸攻击FFA内的双键,导致高分子量聚合产物最终也进入TOP。硫酸也是树脂酸脱羧生成对应的烃的活性催化剂,因此基本上减少了妥尔油树脂酸的产率。取决于工艺布局/设备,所获得的烃最终进入RTD/TOFA或树脂酸馏分,在两种情况下各自馏分的质量均下降。各种类型尤其是过渡金属的盐也是非常具有活性的催化剂,用于活化双键官能团和树脂酸脱羧。
这几年来,一直致力于在分馏之前移除CTO中的杂质。目前最成功的方法似乎是所谓的CTO消除沥青,其中进入的油料流通过TFE单元,在其中经受快速加热,并且大多数FFA和树脂酸挥发和进一步加工,获得单独的TOFA和妥尔油树脂酸馏分。在该方法中,大多数杂质跟随TOP料流收集在TFE底部。尽管进行了短暂热处理,但大部分CTO组分经历了杂质导致的不期望反应,如上所述。此外,一些杂质夹带于所生成的蒸气中。
根据本发明的CTO预处理有助于移除典型的CTO杂质。本发明的精炼步骤期间不存在CTO杂质可使所需的CTO组分得以保存,因此提高了RTD/TOFA和RA产物的产率,甚至提高了TOP的质量。此外,就颜色和/或异构体分布而言RA馏分具有更高的等级,因为有色体与杂质导致的有害效果相关,而RA异构化通过CTO杂质与分馏所需的升温组合来促进。
本发明第二方面中描述的技术解决方案有助于制备高质量RTD馏分和RA馏分的有益协同作用。该解决方案允许与现有技术相比更节能的工艺。当根据本发明制备RTD时忽略了用于精炼TOFA的大量能耗。此外,与通常用于CTO分馏工艺的耗能和能量密集蒸馏步骤相比,创新性分馏序列允许生物燃料(RTD)和精细化学品(RA)的有效分离。
本申请的另一个方面涉及使用粗硫酸盐松脂(CST),其寻求RTD产率的进一步最大化,并且通过(i)减少所得组合物的密度以及(ii)改善沸点(BP)分布的平衡来改善RTD组合物。因此,无CST的RTD具有相当窄的BP分布340-400℃(约90重量%的RTD具有该范围内的沸点),而具有CST的RTD组合物具有更均匀的BP分布140-400℃(CST本身包含一系列与TO头馏分(倍半萜和二萜以及轻质FA C12-C16)结合的组分,覆盖了最终RTD产物的整个BP范围)。
在下文中,我们描述了用于改进的将妥尔油精炼和分馏为高价值馏分的工艺,与现有技术相比,该高价值馏分以更高的产率和更好的质量获得。
与根据本发明的预处理相关的该第三方面的发明内容
如上所述,根据本发明的一个目的,提供了作为预处理工艺从CTO移除杂质的改进工艺。
该目标通过用于预处理粗妥尔油(CTO)的工艺获得,所述工艺包括涉及CTO洗涤和第一油相分离的第一预处理步骤,所述第一油相包括精炼CTO和保持杂质的水相,以及涉及从水相分离第二油相的第二步骤。应当指出的是,涉及从水相分离第二油相的第二步骤可在与第一步骤相同的设施(装置)中,或在直接连接至其中正进行第一分离步骤的装置的单元或装置中进行,但第二步骤也可作为整个分离步骤,或在涉及其中分离是该目的的一部分的后处理的后续步骤中,在另一个装置中进行。
如上所述,本发明的此方面涉及有效移除典型的粗妥尔油杂质,例如残余矿物酸、碱、碱土金属盐/皂、过渡金属、纤维/外来物和木质素化合物,以生成精炼妥尔油。因此,根据本发明的预处理CTO的工艺的一个实施例,纤维、盐、残余无机酸和/或木质素构成了杂质。残余无机酸是用于制浆装置将妥尔油皂转化为妥尔油的酸,通常是硫酸。
应进一步说,本发明的其他重要方面为例如从精炼妥尔油分离挥发性馏分,以及将无挥发物妥尔油分馏到料流,该料流由以下组分构成:a)在柴油范围沸腾的组分(RTD);b)高质量树脂酸(RA)和c)高质量大分子量馏分(妥尔油沥青,TOP),尤其适合在宽范围的工业应用中用作能量来源。
根据本发明该方面的预处理工艺的具体实施例
根据本发明,CTO料流可在分馏之前进行预处理,以移除污染物。在CTO预处理工艺的一个实施例中,使CTO在CTO洗涤步骤中接触水,其中所用的水量小于约5重量%(基于进入的CTO)。洗涤水可包含添加剂。根据本发明,CTO和洗涤液体之间的接触可通过动态搅拌器进行。然而,应当说能够提供CTO和水相之间的紧密接触的任何一件设备均为根据本发明合适的。由于少量洗涤水,提供有效混合的装置是必要的。洗涤水的目的是移除一些CTO杂质(无机盐和残余酸(H2SO4)),而水添加剂的目的是移除其他杂质,例如过渡金属和各种皂。另外,添加剂修饰金属离子,以增强其对水相的偏好。因此,根据本发明的预处理工艺,适度混合例如静态搅拌器不会提供必要的接触。因此,根据一个具体实施例,CTO洗涤通过给予CTO和水相之间紧密接触的混合工序进行。
促进洗涤液体和CTO之间紧密接触的参数是温度。因此,根据本发明的一个具体实施例,接触在高于90℃,优选地在约95℃的温度下受到影响。
根据本发明,在洗涤步骤内可添加各种添加剂,从而帮助移除CTO杂质。此类添加剂的一个功能可以是结合CTO内的所有金属离子。该结合通常通过目标金属离子和添加剂(在络合物形成术语内通常是指配体)之间的络合物形成进行。配体范围可从离子型到分子型,从而络合物形成途径可变。根据本发明,这样形成的络合物是水溶性的。根据本发明,存在多个可用作添加剂的配体。根据一个具体实施例,将至少一种螯合剂添加到第一预处理步骤。此处术语“螯合剂”具体指络合物形成的方式。草酸是一种优选的可用螯合剂。柠檬酸和乙二胺四乙酸(EDTA)是其他优选的螯合剂,因为这些螯合剂也常用于其他应用,并且因为它们还覆盖一系列广泛的金属离子,即不特定于某种离子。
该预处理工艺中如何使用添加剂的一个可能例子如下所述。将预热的CTO与添加剂溶液混合。添加剂溶液应为相对浓缩的,例如30%添加剂,因为较少的水分提供了增加添加剂分布在整个CTO的效率的可能性,从而更好地接触金属杂质。添加剂剂量通常相对于总金属杂质过量约十倍。CTO和添加剂在例如动态搅拌器的帮助下紧密混合,从而将所得的混合物运送到反应器(无混合的简易槽),其中反应器大小允许最小15min的停留时间。停留时间对于确保完成添加剂和金属杂质之间的反应是必须的。在反应完成后,混合物与通过搅拌器(不一定为动态类型)的剩余量的水(总共最多至5%)混合并且离心。一旦添加剂和金属杂质接触并反应,即可通过额外的水提取水溶性金属杂质。
如可从上文理解,旨在进一步加工根据预处理工艺获得的油相。根据本发明的一个具体实施例,将回收的第二油相送入包含精炼CTO的第一油相。从而提高进一步加工的总产率。另一个选择是将第二油相循环回到(未精炼的)CTO储存装置。将第二油相回收和/或循环至第一精炼油相的目的是实现高于预处理步骤的高CTO产率。该预处理步骤的CTO产率(以输入/精炼CTO输出测量)高于96%,优选地高于98重量%。
第一和第二预处理步骤中相的分离可通过根据本发明的不同加工机械进行。根据一个具体实施例,第一预处理步骤中相的分离在分离器单元中进行,其中分离由离心力驱动。也可单独或组合使用其他类型的分离设备,例如过滤和滗析的组合。在后一种情况中,过滤有利地在滗析前面,因为木质素、纤维和其他非油杂质可妨碍水相分离。另一方面,其中分离被离心力驱动的加工单元是优选的加工机械,因为其在非常短的时间内在紧凑的单个设备中从妥尔油(TO)有效地分离水相和固体杂质。根据本发明的又一个具体实施例,在第二步骤中相的分离通过滗析进行。对于该步骤中的预期料流,油-水比例更均匀,并且该料流的流速低得多,其打开了有效使用滗析的可能性。保存第一洗涤步骤期间所用的高温是有利的,因为该温度有助于第二分离步骤的分离。如上所述,不同类型的分离器可用于根据本发明的预处理,例如离心或滗析。
在根据本文上面所述的原理移除污染物后,通过从精炼CTO料流移除挥发物进一步处理精炼CTO。根据本发明的一个具体实施例,将得自预处理的精炼CTO送入加工系统,该系统提供沸点低于170℃的挥发性组分的分离,从而得到“无挥发物妥尔油料流”。用于从精炼CTO料流移除挥发物的加工系统可包括单元组合,例如闪蒸容器-TFE(薄膜蒸发器)或汽提塔(配备有高表面积填料的填充柱)。TFE是根据本发明从精炼CTO料流移除挥发物的最优选的加工系统。
值得注意的是,存在一系列不同的在该步骤移除的挥发性化合物。挥发性化合物包括水、溶于水的各种气体(如果存在水)、萜烯和各种亚硫化合物,例如甲基硫醚和甲基硫醇。
在从精炼CTO料流移除挥发物之后,基本上不含挥发物的精炼CTO通过包括一个或多个真空分馏装置的真空蒸馏加工系统分馏成RTD/TOFA和RA。将精炼CTO进一步加工为各高价值馏分在下面进一步详细描述。
附图的具体实施方式
图1示出了根据本发明的一个实施例的可能预处理的CTO加工期间的不同步骤。
在以“CTO洗涤”表示的第一步骤中,粗妥尔油在一系列混合、反应和分离步骤中处理,其中所得料流(以“精炼CTO”表示)中杂质的水平基本上减少或下降至用于定量的分析方法的限值。为了实现杂质移除,使CTO通过在高温(仅低于水的沸点)下充分混合而接触相对少量的包含至少一种添加剂组分的水(基于CTO计最多至5重量%)。其后将由此所得的混合物引入能够将料流分离成油(精炼CTO)和水相的分离单元。水的用量根据水中CTO杂质如残余矿物酸和不同的无机盐和皂(如果存在)的优良溶解度指示。应当强调,所用的水应满足某些质量要求(pH6.5-7.2;硬度<5°dH;Ca+Mg+Na<1mg/kg),其中典型的例子是蒸气冷凝液。添加剂组分通常是与金属阳离子尤其是过渡金属阳离子具有高亲和力的螯合剂。此类添加剂与这些金属阳离子形成非常稳定的水溶性络合物。与广泛的金属阳离子具有亲和力的添加剂是优选的,以保持工艺的简单性,其中典型的例子为但不限于草酸、柠檬酸、乙二胺四乙酸(EDTA)等。分离单元有利于相分离。特别有利的单元是使用离心力进行相分离的那些。通常此类分离单元与液体相分离,最终固体(例如纤维、非油组分和木质素)的分离和排放组合。鉴于所添加的水量有限,澄清器型分离器在本发明中受到特别关注。因此混合、反应和分离的组合使用涵盖了全部不同的CTO杂质,并且确保它们显著减少或实际移除。
水相优选地经受第二分离步骤,其中第二油相从水相和其他固体杂质分离。因此回收的第二油相可与精炼CTO料流组合(图1中虚线箭头示出的选择)。另一个选择是评估这样回收的第二油相的质量,如果不能满足要求则将其送回CTO,再次通过预处理序列(图1中虚线箭头示出的选择)。
图2示出了根据本发明第一方面的CTO加工期间的不同步骤。实线表示主流程的基本设计,而虚线表示可选流程。
根据本发明的第一方面,将CTO或优选地精炼/洗涤CTO送入加工系统,提供对CTO中存在的挥发性组分进行分离的单元。所谓挥发性组分是指在大气压下沸点低于约170℃的组分。典型的例子是包含松脂馏分以及一些羧酸如C12-C14的组分。其他挥发物包括水、亚硫和其他气体等。考虑到以下真空分馏步骤,挥发物移除是必然要求。挥发物移除在相对低真空(约5kPa)(约50mbar)下工作的TFE单元中最有利地进行,其结合了由精炼CTO在高温下的短扩散途径和短停留时间所决定的轻质组分的有效蒸发。然而,适当的挥发物移除也可通过在低度真空和高温下精炼CTO逆流接触填充床柱中的汽提介质来实现。
借助一个或多个TFE单元(消除沥青TFE),将无挥发物妥尔油料流分馏成液态底部重馏分(TOFA臂,但仍富含RA)和由TOFA和树脂酸构成的气相馏分。将蒸气料流引入主分馏塔。仔细选择工作条件允许定制主要由FFA和一定量树脂酸构成的最轻馏分(以RTD产物表示)的沸点范围。在大气压下,该馏分的所需沸点范围在170最多至约400℃之间。这样获得的RTD馏分进一步用于制备高质量柴油范围燃料组合物,或进一步精炼成TOFA,以用于精细化学品制造。相当高质量的富含树脂酸的馏分可以作为主分馏塔的底部产物获得。树脂酸馏分的质量在以“RA抛光”表示的在非常高真空下工作的单独分馏塔中进一步改善,该分馏塔允许使用相对温和的温度,从而基本上保存了树脂酸。将从主分馏器的下部排放的富含树脂酸的料流和连接至RA抛光塔的TFE单元中制备的气态馏分送入RA抛光塔。将从连接至主分馏柱的一个或多个TFE排放的富含树脂酸的料流送入该TFE。TOP从该TFE单元下部的装置排放。少量高沸点组分作为底部馏分从RA分馏塔排放,并且排放到连接至抛光柱的TFE。将从RA抛光塔的上部回收的由FFA和一定量RA构成的轻质馏分与从主分馏塔回收的RTD馏分混合。任选地,作为引证,将从RA抛光塔回收的RA料流排放到RTD储存装置或再循环回RA抛光塔之前的TFE单元。
图3示出了根据本发明第二方面的CTO加工期间的不同步骤。
在本发明的第二方面中,CTO以针对本发明第二方面所述的类似方式处理。此处附加步骤涉及(i)通过添加在挥发物移除步骤期间从CTO回收的松脂馏分制备RTD组合物和/或(ii)输入CST馏分。将松脂(从CTO回收)和输入的CST(图3的虚线箭头)二者添加到混合的RTD馏分,从而形成改善的RTD组合物。
Claims (3)
1.一种精炼粗妥尔油(CTO)的工艺,其中所述工艺包括在真空下将精炼CTO分馏为至少一种精炼妥尔柴油(RTD)的料流,所述RTD包含2-30体积%的树脂酸和20-90体积%的脂肪酸,
其特征在于所述工艺包括预处理步骤,所述预处理步骤涉及CTO洗涤和杂质分离,第一精炼CTO料流从所述预处理步骤获得,然后所述第一精炼CTO料流在汽提塔或薄膜蒸发器中进一步加工,以移除形成的挥发性组分并且生成第二精炼和基本上无挥发物的CTO料流,所述第二精炼和基本上无挥发物的CTO料流在真空下的分馏中被进一步加工,其中所述真空下的分馏在至少三个单元中以至少三个步骤进行:
(1)将第二精炼和基本上无挥发物的CTO加入第一分馏步骤,用于将妥尔油沥青(TOP)从存在于精炼CTO中的RTD组分和树脂酸分离,其中所述第一分馏步骤在250℃-320℃和0.7kPa-1.5kPa的低压下在以并联或串联布置的一个或多个薄膜蒸发器(TFE)中进行,并且在加入到配备有一种或多种结构化填料的分馏塔之前,离开所述TFE的含有RTD组分和树脂酸的脱挥发妥尔油的温度在200℃-330℃的范围内,其中热通过料流或热油提供给所述TFE;
(2)然后是在主真空分馏塔中,对在所述第一分馏步骤中获得的含有所述RTD组分和所述树脂酸的料流进行第二分馏步骤,所述主真空分馏塔在1mbar-25mbar的真空条件下且在150℃-280℃范围内的温度工作,其中将在大气压下沸点在170-420℃范围内的富含RTD组分的料流从大气压下沸点高于420℃的RA组分料流分离;
(3)在第三分馏步骤中,来自所述第二分馏步骤中的所述RA组分料流被进一步精炼成具有低脂肪酸含量的RA,其中在所述第二分馏步骤中从所述主真空分馏塔的下部回收的所述RA组分料流被排放进入第二分馏塔中进行的RA纯化步骤中,或者在薄膜蒸发器中被进一步加工以用于从RA分离夹带的TOP组分,所述RA通过在第二分馏塔中进行的所述RA纯化步骤中在真空下加工而被进一步精炼,以生成包含小于4重量%脂肪酸的高质量RA;
使得所述分馏还产生至少一种包含小于5体积%的脂肪酸的树脂酸(RA)料流,其中RTD料流在随后的步骤中脱氧形成烃化合物。
2.根据权利要求1所述的工艺,其中脱氧在存在氢的情况下进行。
3.根据权利要求1或2所述的工艺,其中所述第三分馏步骤在作为RA抛光塔的分馏塔中进行,其中获得一个富含沸点在170-420℃范围内的脂肪酸组分的料流和一个富含RA的料流。
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