CN106536454A - 用于对天然油和油脂进行催化脱氧的方法 - Google Patents
用于对天然油和油脂进行催化脱氧的方法 Download PDFInfo
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- CN106536454A CN106536454A CN201580039309.4A CN201580039309A CN106536454A CN 106536454 A CN106536454 A CN 106536454A CN 201580039309 A CN201580039309 A CN 201580039309A CN 106536454 A CN106536454 A CN 106536454A
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Abstract
本发明公开了一种用于对可再生油进行脱氧的方法，所述可再生油由含有甘油三酯或游离脂肪酸的天然油或油脂或它们的衍生物组成，所述方法包括以下步骤：提供催化剂，所述催化剂包含主要由氧化铝组成的载体、担载于所述载体上且以Mo和选自Ni和Co的至少一种为基础的金属化合物，和选自Cu和Cr的至少一种；以及在足以将所述可再生油脱氧的条件下，使所述可再生油与所述催化剂接触。
Description
相关申请的交叉引用
本申请要求2014年6月9日提交的美国临时专利申请No. 62/009605的提交日期权益，该申请据此以引用方式并入本文。
技术领域
本发明涉及加氢处理催化剂配方，以及这些催化剂配方在固定床连续工艺中提供极其优越的除氧性能的用途。
背景技术
可利用两步法将天然油和油脂（植物油和动物脂）制成可再生柴油，在该两步法中：步骤(1)为经由加氢处理，脱氧形成正链烷烃，其中氧作为H2O和/或CO/CO2被去除；步骤(2)为异构化/裂化步骤(1)中形成的正链烷烃，从而根据需要生产支化柴油和喷气燃料产品。
目前，商业上使用单层或多层催化床方法，并使用与石油脱硫和脱氮应用中所用的催化剂类似的标准加氢处理型催化剂，来执行上文提到的脱氧步骤(1)。这些催化剂通常以担载于主要含有Al2O3的挤出载体上的Ni、Mo和任选地P为基础。在制造过程中，先将这些催化剂制备成氧化物，随后采用原位或非原位活化方法将其转化为活性硫化状态。
可用于提供脱氧作用和氢化作用的其他活性位点的例子是硫化的贱金属，诸如硫化NiMo、硫化CoMo或硫化NiW。贱金属是在空气中加热时会氧化的金属。除了镍、钼和钨之外，可以是本文中的催化剂组分的贱金属包括铁、铅、锌、铜、锡、锗、铬、钛、钴、铼、铟、镓、铀、镝、铊以及它们的混合物。尽管参考文献使用了NiMo催化剂，但该参考文献并未明确地教导或举例说明将Cu或Cr用作助催化剂。
美国专利申请No. 20110258916教导了在氢和氢化催化剂的存在下进行的加氢处理工艺，其中氢化催化剂含有载体和选自VIII族金属和VIB族（第6族—铬族）金属的一种或多种金属。该申请的第[0043]段教导，可使用的催化剂均为本领域已知的氢化催化剂和加氢处理催化剂，其含有被适当地担载、并选自下列的一种或多种金属：VIII族金属（Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt）和VIB族金属（Cr、Mo、W）。尽管该参考文献教导NiMo是已知的，但该参考文献并未直接地教导或举例说明Cu与Cr。其中的例子使用了硫化的NiMo/Al2O3。
美国专利申请No. 20070175795要求保护基于含氧化锌的吸附剂配方和呈还原态的助催化剂氧化物（包含铬和铜）进行脱氧的催化剂。但其中的配方与本发明的不同。尽管在US ‘795描述的方法中，提出助催化剂金属选自镍、钴、铁、锰、钨、银、金、铜、铂、锌、锡、钌、钼、锑、钒、铱、铬和钯，但该参考文献暗示却并未特别教导助催化剂金属为铜或铬。
美国专利No. 8,043,600在其说明书中提及将VIB族（第6族）和VIII族用作对天然油进行加氢处理的催化剂。该参考文献也未特别教导助催化剂金属为铜或铬。
发明内容
本发明涉及催化剂配方及其在固定床连续工艺中的用途：在上述工艺的步骤1中，提供比常规的加氢处理催化剂优越的除氧性能。
这些催化剂含有Mo和选自Ni和Co的至少一种作为其主要（典型）活性组分，并以Cr、Cu的氧化物以及它们的混合物为助催化剂。这些金属氧化物助催化剂通常不存在于常规的市售加氢处理催化剂中。这些配方在与现有技术的其他金属助催化剂相同的操作条件下，提供出乎意料地优异的除氧活性。
附图说明
图1示出了本发明的催化剂与不含助催化剂的对比催化剂的除氧性能随温度的变化关系。
图2为示出将Cr添加至市售NiMo催化剂对残余氧含量的影响的曲线图。
图3示出了本发明的催化剂与对比催化剂的除氧性能随温度的变化关系。
图4示出了本发明的催化剂与对比催化剂在100%氧转化率下的烃产物选择性。
具体实施方式
参照本发明的实施方案对本发明进行了描述。对本发明的描述自始至终都参考图1至图4所示的曲线图。
可利用两步法将天然油和油脂制成可再生的柴油燃料，在该两步法中：步骤(1)为经由催化加氢处理，脱氧形成正链烷烃，其中氧作为H2O和/或CO/CO2被去除；步骤(2)为异构化/裂化步骤(1)中形成的正链烷烃，从而生产支化柴油和喷气燃料产品。
如本文所用，天然油和油脂是选自或衍生自动物脂、植物或藻类物质的那些天然油和油脂，并通常被称为可再生油。天然油不以石油或其他化石燃料源为基础。可用于本发明的可再生油包括任何那些含有含氧化合物的可再生油，所述含氧化合物诸如甘油酯、脂肪酸烷基酯和游离脂肪酸(FFA)。这些含氧组分在合适的反应条件下与催化剂接触时，可被转化为烃，如美国专利No. 4,992,605中所述。这些原料的例子包括但不限于：卡诺拉油、玉米油、豆油、油菜籽油、大豆油、菜籽油、妥尔油、向日葵油、大麻籽油、橄榄油、亚麻籽油、椰子油、蓖麻油、花生油、棕榈油、芥子油、棉籽油、牛脂、黄色和棕色油脂、猪油、鲸油、乳中的脂肪、鱼油、海藻油、污水污泥、萼距花油、亚麻荠油、麻疯果油、麻疯树油、巴巴苏仁油、棕榈仁油、海甘蓝油，等等。生物可再生是用来描述这些原料的另一术语。
可理解的是，可再生油不必是天然存在的，而是也可以是衍生物，诸如上文提到的脂肪酸烷基酯。在存在酯交换催化剂和生产脂肪酸烷基酯的条件的情况下，将甘油三酯原料与醇接触时，可生产出此类脂肪酸烷基酯。添加到反应器中的醇可以是惯常用来将含甘油三酯的原料转化为酯的一种醇或两种或更多种醇的混合物。合适的醇包括具有1至6个碳的那些，并且典型地为一元醇。甲醇通常是合适的，但所述醇可包括高级一元醇，诸如乙醇、1-丙醇、异丙醇、1-丁醇、异丁醇、1-戊醇或1-己醇。
酯交换反应中醇与甘油三酯的摩尔比通常在3:1至30:1、典型地5:1至25:1的范围内。醇与甘油三酯的摩尔比小于3:1更可能导致甘油三酯向脂肪酸烷基酯的转化率小于化学计量转化率。醇与甘油三酯的摩尔比大于30:1是不利的，因为存在的甲醇量增多会导致下游处理步骤中分离/回收甲醇的成本显著升高。因此，在上述范围内选择的醇与甘油三酯的摩尔比代表经济上合理的比率，若选择处于该范围之外的比率，则在使用本文所述的其他条件时，或在使用本文所述类型的反应中通常选用的其他条件时，所述转化率不再可预期。
酯交换反应中使用的催化剂可以是均相催化剂或非均相催化剂。合适的均相催化剂包括碱金属甲醇盐、碱金属氢氧化物以及它们的混合物，包括但不限于甲醇钠、甲醇钾、氢氧化钠和氢氧化钾。合适的非均相催化剂包括美国专利WO 2006/050925、US 2009/0069586、US 5,908,946、WO 2007/025360或US 7,420,073中所述的那些，这些美国专利的内容以引用方式并入本文。
生成的酯衍生物取决于醇中碳的数量。通常情况下，在一个或多个酯交换反应中使用甲醇时生成脂肪酸甲酯（也称FAME），而在酯交换反应中使用乙醇、丙醇、丁醇、戊醇和己醇时，分别生成乙酯、丙酯、丁酯、戊酯和己酯。
酯交换反应在常规条件下，在催化剂存在下进行。酯交换反应可在间歇式反应器中、连续式（例如，搅拌式）罐式反应器中以及固定床反应器中进行。反应器的条件应当足以利用酯交换将甘油三酯转化为酯。所述条件（也称为酯交换条件）包括在40℃至250℃范围内、更典型地在60℃至200℃范围内的温度。典型的压力将在1至100个大气压(atm)、更典型地1至50个atm的范围内，其中，最终压力取决于反应所采用的具体的醇和反应温度。
典型的植物油或动物脂的甘油酯、FFA和脂肪酸烷基酯在其结构中包含具有约8至约24个碳原子的脂肪族烃链，其中大多数油含有高浓度的具有16和18个碳原子的脂肪酸。天然油原料中的氧水平可在0.5重量%至20重量%、更典型地5重量%至15重量%的范围内。所述原料可含有痕量的杂质，诸如源自磷脂质（油中天然存在的一组化合物）的P、Na、Ca、Mg和K。这些杂质对脱氧过程的表现有不利影响，因此在该步骤之前必须被除至ppm水平。用于该目的的典型预处理工艺包括但不限于使用固体吸附剂的低温批处理工艺以及使用保护反应器的工艺，所述固体吸附剂诸如硅胶（如美国专利No. 5,231,201中所述）、离子交换树脂（如美国专利申请No. 20060264684中所述）和粘土，所述保护反应器利用加氢处理领域众所周知的在较高温度下工作的加氢处理型催化剂。所述原料还可含有衍生自动物蛋白或叶绿素的少量氮化合物。氮含量通常在0.5ppm至5000ppm范围内。额外的可选预处理步骤包括使用在加氢处理条件下工作的保护反应器，也可利用这类预处理步骤来使原料的不饱和脂肪酸组分饱和，以防出现副反应（诸如在脱氧步骤中发生聚合），如美国专利申请No.20110245551中所讨论。
可再生原料和化石燃料衍生的烃的混合物或共进料(co-feed)也可用作原料。
使用单层或多层催化床方法对天然油和油脂进行脱氧，以形成正链烷烃。在脱氧过程中，甘油三酯中的脂肪酸链被转化为正链烷烃，而甘油三酯的甘油酯部分被转化为丙烷。通常情况下，将天然油脱氧得到的烃产物分布显示出偶碳数的正链烷烃和奇碳数的正链烷烃的混合物，其中，偶碳数经由将氧作为水去除而产生，奇碳数经由将氧作为CO或CO2去除而产生。对偶数链烷烃的选择性较高表示柴油产物中的碳保留率较高，并且与氢消耗率较高密切相关。对奇数链烷烃的选择性较高，不但与氢消耗率较低密切相关，还与柴油产物中的碳保留率较低相关。
通常情况下，脱氧过程使用硫化的加氢处理型催化剂。以贵金属（诸如Pd）为基础的其他催化剂也可用来提供有助于将氧作为CO和CO2去除的更高选择性，还用来最大限度减少H2消耗，如美国专利No. 7,491,858中所述。本发明与使用硫化催化剂的脱氧工艺密切相关。
催化床通常是粒料或挤出物的固定床，其在所施加的氢气压力和升高的温度下以滴流（向下流动）模式或溢流床（向上流动）模式运行。通常情况下，天然油和油脂中也掺入了少量有机硫化合物（诸如可作为SULFRZOL从路博润公司(Lubrizol Corporation)商购获得的二丁基二硫化物），以确保催化剂上的活性位点在反应期间保持硫化状态。除了H2O、CO、CO2和丙烷之外，产物的气体部分也包含脱硫反应期间形成的H2S。在与动物脂或其他含氮原料反应的情况下，气体产物还可包含经由脱氮反应形成的NH3。
在商业工艺中，脱氧步骤之后是产物分离步骤，用于在加氢异构化或加氢裂化步骤之前将气体产物从液体柴油产物中去除。脱氧步骤通常在存在超过化学计量要求量的过量氢（可能过量最高达2至3倍）的情况下进行。该工艺还可包括产物和气体的再循环，以改善反应器中的热平衡。
适用于本发明中的脱氧工艺的催化剂为在主要由氧化铝（典型地为挤出的γ型氧化铝）构成的载体上提供催化金属的那些催化剂，其BET表面积为至少150m2/g，孔体积为至少0.5cc/g。然而，所述载体可包含具有足够大的强度和孔隙度以起到载体作用的任何合适的材料。所述催化剂可以是颗粒状形式（颗粒、小珠、球体、片状物和挤出物），例如，适合在被设计用于连续运行的固定床反应器中使用的那些。颗粒状形式的尺寸可在0.1至10mm范围内、更典型地在0.5至5mm范围内。该形式可为任何形状，例如圆柱形、三叶形或四叶形。颗粒化工艺可以是混合与挤出的组合。挤出机进料的配方除包含氧化铝外，还可任选地包含其他氧化物，诸如SiO2、TiO2和ZrO2、MgO或粘土。这些氧化物可改变最终载体的孔隙特征和/或机械强度（以压碎强度衡量）。也可使用挤出助剂（诸如甲基纤维素（例如，可作为METHOCEL从陶氏化学公司(Dow Chemical Company)商购获得）），来改善通过挤出机对进料的加工。可任选地添加酸（诸如硝酸）来使氧化铝或其他氧化物胶溶，以形成粘结剂，由此提高颗粒状材料的机械强度。可将一种或多种无机氧化物以任何形式加入混合设备，作为浆料、可胶溶固体或液体。通常将氧化铝、氢氧化铝、二氧化硅、二氧化钛和氧化锆作为固体加入或加工。硝酸铝、氢氧化铝、正硅酸四乙酯(TEOS)、异丙醇钛和硝酸氧锆是加入混合设备的典型的液体形式材料。也可使用胶体形式，诸如胶体二氧化硅。可将所述无机氧化物作为单独的成分或作为混合氧化物加入混合设备，其中，所述混合氧化物使用包括但不限于共沉淀的技术制备而成。
此外，调节水含量以优化催化剂的可挤出性。形成挤出机进料的配方首先在混合机（例如Sigma或Eirich混合机）中混合，然后通过可商购获得的单螺杆或双螺杆挤出机挤出。然后，将挤出的材料干燥，再煅烧，以形成催化剂成品。颗粒状粒子的实例通常在成形过程期间，在从500℉到2000℉、更优选地从700℉到1800℉、最优选地从900℉到1600℉的温度下煅烧。所述催化剂也可被颗粒化为具有与上述成分类似的成分的球形形式，但该颗粒化过程在Eirich或Naute混合机内完成，随后是类似的干燥/煅烧过程。
担载于载体上的催化剂金属化合物以Mo、选自Ni和Co的至少一种为基础，并包含至少一种助催化剂金属，所述助催化剂金属为选自Cu和Cr的至少一种金属。正是这种特别的助催化剂金属与MoNi、MoCo或MoNiCo相结合，才提供了本发明催化剂的优异脱氧活性。
选自Cu和Cr的助催化剂金属以足以显著增强对天然油和油脂的脱氧的量被包含在所述催化剂中。所述助催化剂按氧化物计算，在催化剂中的量优选地在0.5重量%至10重量%范围内，更优选地在1重量%至6重量%范围内，最优选地在1.5重量%至5.0重量%范围内。
可使用本领域已知的标准浸渍技术（例如，使用含有活性金属前体的溶液进行始润浸渍(incipient wetness impregnation)），将助催化剂金属连同贱金属Ni、Mo、Co结合到挤出物载体上。这些前体包括但不限于硝酸盐、碳酸盐、草酸盐等。浸渍步骤之后通常是干燥和煅烧步骤，以将助催化剂金属前体转化为氧化物形式。干燥通常在200℉至400℉的温度范围内进行。最终煅烧通常在500℉至2000℉、更优选地700℉至1800℉、最优选地900℉至1600℉的温度范围内进行。
任选地，这些助催化剂金属的一部分或全部也可在催化剂制备过程的混合步骤期间添加，并且可以以任何形式（包括但不限于金属溶液）添加。
在制造过程中，先将催化剂制备成氧化物，随后采用原位或非原位活化方法将其转化为活性硫化状态。这些金属氧化物配方的一部分或大部分可在活化步骤期间被转化为硫化状态。活化步骤通常通过将催化剂暴露于一种或多种含硫化合物和氢而进行，同时反应器的受控温度斜升为从约70℉至约650℉。
如果脱氧是通过将天然油或油脂暴露于下述催化剂温度下的催化剂而实现的，则会获得异乎寻常的脱氧结果：所述催化剂温度优选地介于约400℉和约800℉之间、更优选地介于450℉和700℉之间、最优选地介于500℉和650℉之间。工作压力优选地为约100至2500psig、更优选地为约250至2000psig、最优选地为约400至1500psig。用于催化工艺的原料的处理速率可被表示为例如液体时空速(Liquid Hourly Space Velocity, LHSV)，LHSV被定义为反应物的体积流率除以反应器中活性催化剂的体积。我们的工艺的LHSV可在0.1至10h-1、更优选0.2至5.0h-1、最优选0.5至2.0h-1的范围内。下文，将参照实例更详细地描述本发明。然而，本发明的范围不限于以下实例中示出的具体细节。
用于在实施例中进行筛选的材料：以2.0重量%至4.7重量%的Cr2O3、1.9重量%的CuO、3.4% Fe2O3和3.8% ZnO为助催化剂的NiMoP/Al2O3-SiO2催化剂。
实施例1
合成以铬为助催化剂的NiMoP催化剂（催化剂A）
按下述步骤制备NiMo的混合金属溶液。将预先称量的水、磷酸（75重量%）、三氧化钼和碱式碳酸镍（40重量%的Ni）添加到釜中，一边搅拌一边加热到200℉。200℉下蒸煮该混合物3小时或直到溶液变澄清。根据需要加水，以补偿蒸发造成的任何损失。随后将该混合物冷却至室温。向65ml的这种前体溶液中添加18.6克硝酸铬九水合物和35ml水。将该溶液混合物浸渍到99克氧化铝-二氧化硅挤出物载体（1/16英寸不对称四叶形）上，实现初始润湿。接着将经浸渍的催化剂在248℉下干燥过夜，然后置于马弗炉中1112℉下煅烧1小时。将所得的催化剂记为催化剂A，其含有23.2% MoO3、5.0% NiO、3.4% P2O5、2.2重量%的SiO2和2.0重量%的Cr2O3，BET表面积为209m2/g。
实施例2
合成以铬为助催化剂的NiMoP催化剂（催化剂B）
按下述步骤制备NiMo的混合金属溶液。将预先称量的水、磷酸（75重量%）、三氧化钼和碱式碳酸镍（40重量%的Ni）添加到釜中，一边搅拌一边加热到200℉。200℉下蒸煮该混合物3小时或直到溶液变澄清。根据需要加水，以补偿蒸发造成的任何损失。随后将该混合物冷却至室温。向65ml的这种前体溶液中添加37.2克硝酸铬九水合物和25ml水。将该溶液混合物浸渍到99克氧化铝-二氧化硅挤出物载体（1/16英寸不对称四叶形）上，实现初始润湿。接着将经浸渍的催化剂在248℉下干燥过夜，然后置于马弗炉中1112℉下煅烧1小时。将所得的催化剂记为催化剂B，其含有20.4% MoO3、5.2% NiO、3.4% P2O5、2.6重量%的SiO2和4.1重量%的Cr2O3，BET表面积为207m2/g。
实施例3
合成以铜为助催化剂的NiMoP催化剂（催化剂C）
按下述步骤制备NiMo的混合金属溶液。将预先称量的水、磷酸（75重量%）、三氧化钼和碱式碳酸镍（40重量%的Ni）添加到釜中，一边搅拌一边加热到200℉。200℉下蒸煮该混合物3小时或直到溶液变澄清。根据需要加水，以补偿蒸发造成的任何损失。随后将该混合物冷却至室温。向65ml的这种前体溶液中添加37.2克硝酸铜三水合物和25ml水。将该溶液混合物浸渍到99克氧化铝-二氧化硅挤出物载体（1/16英寸不对称四叶形）上，实现初始润湿。接着将经浸渍的催化剂在248℉下干燥过夜，然后置于马弗炉中1112℉下煅烧1小时。将所得的催化剂记为催化剂C，其含有23.8% MoO3、4.8% NiO、3.7% P2O5、2.4重量%的SiO2和1.9重量%的CuO，BET表面积为182m2/g。
对比例1
在本例中使用的参考催化剂是从美国先进炼制技术公司(Advanced RefiningTechnologies)收到的商业NiMoP加氢处理催化剂。该催化剂通过将NiMoP前体溶液浸渍到同一种载体上而制成。该参考催化剂含有27.3% MoO3、5.4% NiO、4.3% P2O5和2.1重量%的SiO2，BET表面积为170m2/g，将其记为催化剂D。
实施例4
合成以铬为助催化剂的NiMoP催化剂（催化剂E）
按下述步骤制备催化剂E。取30g硝酸铬九水合物溶解于60ml水中，制得铬溶液。将该溶液浸渍到97g催化剂D上。将经浸渍的催化剂在248℉下干燥过夜，然后置于马弗炉中1112℉下煅烧1小时。所得的催化剂含有25% MoO3、5.4% NiO、4.1% P2O5、2.2重量%的SiO2和4.7重量%的Cr2O3，BET表面积为177m2/g。
对比例2
合成以铁为助催化剂的NiMoP催化剂（催化剂F）
按下述步骤制备NiMo的混合金属溶液。将预先称量的水、磷酸（75重量%）、三氧化钼和碱式碳酸镍（40重量%的Ni）添加到釜中，一边搅拌一边加热到200℉。200℉下蒸煮该混合物3小时或直到溶液变澄清。根据需要加水，以补偿蒸发造成的任何损失。随后将该混合物冷却至室温。向65ml的这种前体溶液中添加通过将24g硝酸铁九水合物单独溶解在20ml水中而制得的溶液。将该溶液混合物浸渍到99克氧化铝-二氧化硅挤出物载体（1/16英寸不对称四叶形）上，实现初始润湿。接着将经浸渍的催化剂在248℉下干燥过夜，然后置于马弗炉中1112℉下煅烧1小时。将所得的催化剂记为催化剂F，其包含27.9% MoO3、4.5% NiO、4.1%P2O5、2.0重量%的SiO2和3.4重量%的Fe2O3，BET表面积为201m2/g。
对比例3
合成以锌为助催化剂的NiMoP催化剂（催化剂G）
按下述步骤制备NiMo的混合金属溶液。将预先称量的水、磷酸（75重量%）、三氧化钼和碱式碳酸镍（40重量%的Ni）添加到釜中，一边搅拌一边加热到200℉。200℉下蒸煮该混合物3小时或直到溶液变澄清。根据需要加水，以补偿蒸发造成的任何损失。随后将该混合物冷却至室温。向58ml的这种前体溶液中添加通过将22g硝酸锌六水合物单独溶解在42ml水中而制得的溶液。将该溶液混合物浸渍到99克氧化铝-二氧化硅挤出物载体（1/16英寸不对称四叶形）上，实现初始润湿。接着将经浸渍的催化剂在248℉下干燥过夜，然后置于马弗炉中1112℉下煅烧2小时。将所得的催化剂记为催化剂G，其包含28.7% MoO3、5.7% NiO、4.3%P2O5、2.4重量%的SiO2和3.8重量%的ZnO，BET表面积为100m2/g。催化剂G的表面积明显更低，还表明向催化剂配方中添加ZnO具有烧结效应。
评价催化剂A至G在固定床反应器中对天然油进行脱氧的性能。
在固定床反应器中以向上流动模式评价催化剂A至G在从甘油三酯除去氧方面的性能。用α-氧化铝珠（表面积极低）稀释活性催化剂床，以实现更好的热分布。通过将温度从室温多步斜升至630℉，使用煤油和H2把催化剂转化为活性硫化物。随后将料流切换成掺有100ppmw S（使用SULFRZOL —二丁基二硫化物）连同H2的精炼大豆油。使用的条件为5600SCFB（标准立方英尺/桶）的H2：油比率、750psia的压力，以及500至575℉的温度范围。催化剂A至D、F和G在1.0h-1的重时空速下评价，而催化剂D和E在1.0h-1的液体时空速（大致对应于1.3h-1的重时空速）下评价。使用气相色谱法分析来自该反应的液体产物和气体产物。
从图1中可以看出，与标准催化剂D相比，催化剂A至C随温度变化实现了高得出乎意料的除氧水平。具体地讲，在500℉的温度下，催化剂D显示出3.1重量%残余氧的基线。另一方面，催化剂B实现了低得多的2.1重量%总氧含量，与基线相比残余氧减少了33%。催化剂A显示出残余氧含量为0.97重量%，与基线催化剂D相比减少了69%。此外，催化剂C显示出残余氧含量为0.45重量%，与基线相比减少了86%。
图2示出了在将Cr添加到商业NiMo催化剂（催化剂D）之后实现了脱氧性能的显著改善。
如上所述，各种助催化剂金属此前已用作助催化剂金属，但正是专门加入Cu或Cr，才促使本发明的催化剂出现出乎意料地优异的脱氧结果。
图3示出了包含Cu和Cr的本发明催化剂与包含不同助催化剂金属的对比催化剂的除氧性能随温度的变化关系。可以观察到，尽管与基线NiMo催化剂相比，添加Cu和Cr得到了优异的除氧性能，但添加Fe和Zn对该性能有不利影响。
重要的是，在不显著改变气体或液体产物选择性的情况下改善了本发明催化剂的脱氧活性。
图4示出了本发明的催化剂与对比催化剂在100%氧转化率下的烃产物选择性。可以观察到，催化剂A、B、C和E不但脱氧活性较高，对偶数产物的选择性也较高。
采用了下述催化剂的本发明的脱氧方法在与现有技术的其他金属助催化剂相同的操作条件下提供了出乎意料地优异的除氧活性：此类催化剂含有Mo和Ni和/或Co作为主活性组分，并以通常不存在于常规加氢处理催化剂中的Cr、Cu的氧化物以及它们的混合物为助催化剂。
前述实施例和实施方案只用于进行示意性说明，无意于限制本发明的范围。此外，虽然已借助一些实施方案公开并描述了本发明，但对于本领域技术人员显而易见的是，在不脱离如所附权利要求限定的本发明范围的情况下，可对所述实施方案以及本发明的其他实施方案作出若干修改。
Claims (14)
1.一种用于对可再生油进行脱氧的方法，所述可再生油由包含甘油三酯或游离脂肪酸的天然油或油脂或它们的衍生物组成，所述方法包括以下步骤：
提供催化剂，所述催化剂包含：
主要由氧化铝组成的载体，
担载于所述载体上的金属化合物，所述金属化合物以Mo和选自Ni和Co的至少一种为基础，和
选自Cu和Cr的至少一种助催化剂；
以及
在足以促进所述可再生油脱氧的条件下，使所述可再生油与所述催化剂接触。
2.根据权利要求1所述的方法，其中所述助催化剂金属为Cu。
3.根据权利要求1所述的方法，其中所述助催化剂金属为Cr。
4.根据权利要求1所述的方法，其中所述助催化剂金属按氧化物计算，以介于约1.4重量%与约3.0重量%之间的量存在于所述催化剂配方中。
5.根据权利要求1所述的方法，其中所述助催化剂金属在所述催化剂的制造过程的挤出阶段之前引入。
6.根据权利要求1所述的方法，其中所述载体包含选自二氧化硅、二氧化钛和氧化锆的至少一种额外的氧化物。
7.根据权利要求1所述的方法，其中所述载体包含二氧化硅。
8.根据权利要求1所述的方法，其中所述催化剂包含磷。
9.根据权利要求1所述的方法，其中所述原料中的所述可再生油包含甘油三酯。
10.根据权利要求1所述的方法，其中所述原料中的所述可再生油包含游离脂肪酸。
11.根据权利要求1所述的方法，其中所述原料已经历一个或多个预处理步骤，以降低污染物的水平，所述污染物包括Na、Ca、Fe、Mg、K和P中的任何一种。
12.根据权利要求1所述的方法，其中所述使所述可再生油与所述催化剂接触的步骤在介于约500℉与650℉之间的温度下进行。
13.根据权利要求1所述的方法，其中所述使所述可再生油与所述催化剂接触的步骤在介于约450psig与1500psig之间的压力下进行。
14.根据权利要求1所述的方法，其中所述使所述可再生油与所述催化剂接触的步骤在0.5至2.0h-1的LHSV下进行。
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Also Published As
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|---|---|
| EP3152186A1 (en) | 2017-04-12 |
| EP3152186A4 (en) | 2017-12-20 |
| WO2015191416A1 (en) | 2015-12-17 |
| SG11201609969VA (en) | 2016-12-29 |
| US10184085B2 (en) | 2019-01-22 |
| EP3152186B1 (en) | 2020-11-25 |
| US20170210996A1 (en) | 2017-07-27 |
| DK3152186T3 (da) | 2021-01-25 |
| TW201602336A (zh) | 2016-01-16 |
| CA2951379C (en) | 2022-06-21 |
| CN106536454B (zh) | 2020-09-01 |
| CA2951379A1 (en) | 2015-12-17 |
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