CN101583694B - 由生物源混合物生产烃馏分的方法 - Google Patents
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- CN101583694B CN101583694B CN2007800453885A CN200780045388A CN101583694B CN 101583694 B CN101583694 B CN 101583694B CN 2007800453885 A CN2007800453885 A CN 2007800453885A CN 200780045388 A CN200780045388 A CN 200780045388A CN 101583694 B CN101583694 B CN 101583694B
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- 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
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- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2400/04—Diesel oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
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- C10L2200/0469—Renewables or materials of biological origin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Fats And Perfumes (AREA)
- Medicines Containing Plant Substances (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
描述了由含有脂肪酸酯并且可能含有一定量的游离脂肪酸的生物源混合物生产可以用作柴油燃料或用作柴油燃料组分的烃馏分的方法，该方法包括以下步骤：1)使所述生物源混合物加氢脱氧；2)在可能的提纯处理之后，对步骤(1)中得到的混合物进行加氢异构化，所述加氢异构化在催化体系的存在下进行，所述催化体系包含：a)包含完全无定形微孔-中孔氧化硅-氧化铝的酸性载体，其中所述氧化硅-氧化铝的SiO2/Al2O3摩尔比在30～500范围内，表面积大于500m2/g，孔体积在0.3～1.3ml/g范围内，平均孔直径小于40，b)含有一种或多种VIII族金属的金属组分，其可能与一种或多种VIB族金属混合。
Description
本发明涉及由含有脂肪酸酯并且可能含有一定量的游离脂肪酸的生物源混合物开始生产可以用作柴油燃料或用作柴油燃料组分的烃馏分的方法。所述方法包括至少一个脱氧步骤和加氢异构化步骤。植物油在柴油机中的使用追溯到Rudolf Diesel在1900年证实的用花生油运行柴油机的能力。
在第二次世界大战期间，非洲使用棕榈油和花生油作为军用车辆的燃料。战争之后，技术的发展导致几乎唯一地使用衍生自石油的燃料；此外，柴油机，尤其是关于喷油器和控制系统，进行了巨大的改进以至于对使用不同于瓦斯油的燃料有非常小的灵活性。同时，植物油燃料由于其高生产成本和产品性质上的不稳定性而逐渐被抛弃。
在七十年代的油品危机期间，注意力再次集中到植物油作为柴油燃料的使用，但是出于多种原因(内燃机中结皮的形成、喷油器的堵塞、润滑剂的稀释)这是困难的。然后研究转向从植物油开始制备甲基或乙基酯以及它们在柴油机中的应用。脂肪酸的甲基和乙基酯通过植物油与甲醇或乙醇的酯交换反应获得。八十年代提出了植物油转化的备选的方法，并且该方法在于植物油的强制加氢以产生沸点与从油获得的柴油燃料相当的烃馏分。根据操作条件改变往复比，植物油的强制加氢导致脱除氧和同时形成H2O、CO2和CO的混合物。因此，所述起始酯，普遍转化为相对于脂肪酸和丙三醇的烃。少量的游离醇可与所述烃一起形成。
脂肪油的强制加氢反应以产生液体烃燃料在例如，仍然在八十年代，由Nunes等人在题目为“Hydrocraquage sous pression d′unehuile de soja：procédéd′étude et allure générale de latransformation”(Rev.Ins t.Fr.Pet.1986年，第41卷，第421页往前)的文章中进行了研究，描述了用双功能催化剂对大豆油进行的加氢裂化。在高于673K的温度下观察到脂肪酸的脱羰基作用和脱羧基作用，由于金属催化剂的存在还有显著的氢解作用。主要的产物是直链烃。
J.Gusmao 等人(Utilization of vegetable oils as analternative source for diesel-type fuel：hydrocracking onreduced Ni/SiO2 and sulphided Ni-Mo/Al2O3，Catalysis Today 1989年第5期，第533页往前)说明了在大豆油的加氢中所获得的烃馏分是如何主要由直链烷烃(96mol％的C15～C16～C17～C18)组成的。
美国专利4992605描述了通过植物油，例如向日葵油、油菜、卡诺拉(canola)油、棕榈油、或包含在松树浆中的脂肪油(妥尔油)的加氢作用生产C15～C18范围内的烃馏分的方法。该烃馏分主要由直链烷烃(C15～C18)组成并且其特征在于高十六烷值，这使得它可以用作十六烷改进剂。
在″Hydroprocessed vegetable oils for diesel fuelimprovement″，Bioresources Technology 56(1996)，第13～18页中总结了美国专利4992605中描述的由卡诺拉开始生产加氢的产物在实验室规模上的应用。所述烃馏分几乎唯一地由直链烷烃组成并且在柴油燃料的蒸馏范围内蒸馏的馏分具有55～90范围内的十六烷值。其它加氢产物包括轻质C1～C5烃、水和CO2。将所述柴油馏分定义为“超级十六烷”。密度(0.790g/ml)与柴油燃料一致，而粘度略微更高。然而，该馏分的真实范围与差的低温性质(浊点和倾点)相关，所述低温性质与链烷烃的线性度有关，其超过20℃。由于该原因，所述“超级十六烷”馏分可以用在与常规柴油的混合物中，但是不能在冬季使用。
EP1396531描述了由植物或动物源的混合物生产烃组分的方法。描述了异构烷烃含量为73％的混合物的形成。所述方法包括预加氢步骤、加氢脱氧步骤(HDO)和使用逆流原理进行的异构化步骤。在温和的条件下进行的所述预加氢步骤对于对存在的双键进行饱和以及避免随后的方法步骤中不合意的副反应是必需的。在所述异构化步骤中，以逆流方式操作是绝对需要的，以保护催化剂防止由于原料中包含的衍生自前面的HDO步骤的水所引起的催化剂失活；当以逆流方式操作时，在所述原料与催化床的全部催化剂接触之前，除去烃原料中包含的一部分水。
现在发现了生产可以用作柴油燃料或用作瓦斯油组分的烃混合物的方法，该方法通过含有脂肪酸酯并可能含有一定量的游离脂肪酸的生物源混合物(例如植物油，如向日葵、油菜、卡诺拉、棕榈油或包含在松树浆中的脂肪油(妥尔油))的加氢脱氧作用，随后通过加氢异构化作用来实现，所述加氢异构化作用允许获得烃混合物，其中异链烷烃的含量可以超过80％，其余部分是正链烷烃。
与用已知的方法获得的那些馏分相比，加氢异构化步骤中使用的特定的催化组合物不仅允许得到更高品质的产物作为柴油燃料，而且它们还具有一些特征，这些特征允许它们在水的存在下使用而没有经历失活或者无论如何，在加氢异构化本身的过程中通过适度的升温很容易进行再生。
本发明的目的因此涉及由含有脂肪酸酯并且可能还含有游离脂肪酸的生物源混合物开始生产可以用作柴油燃料或用作柴油燃料组分的烃馏分的方法，该方法包括以下步骤：
1)使所述生物源混合物加氢脱氧；
2)在可能的提纯处理之后，对步骤(1)中得到的混合物进行加氢异构化，所述加氢异构化在催化体系的存在下进行，所述催化体系包含：
a)包含完全无定形微孔-中孔氧化硅-氧化铝(silico-alumina)的酸性载体，其中所述氧化硅-氧化铝的SiO2/Al2O3摩尔比在30～500范围内，表面积大于500m2/g，孔体积在0.3～1.3ml/g范围内，平均孔直径小于
b)含有一种或多种VIII族金属的金属组分，其可能与一种或多种VIB族金属混合。
本发明的方法中使用的生物源混合物含有脂肪酸酯，可能具有一定量的游离脂肪酸，并且它们可以是植物源或动物源混合物。脂肪酸的量可以改变，例如占全部生物源混合物的2～20wt％。所述混合物中包含的脂肪酸酯一般是脂肪酸甘油三酯，其中所述脂肪酸的烃链可以含有12～24个碳原子并且可以是单-或多-不饱和的。所述生物源混合物可以选自植物油、植物脂肪、动物脂肪、鱼油或它们的混合物，植物油或植物脂肪可以是向日葵、油菜、卡诺拉、棕榈、大豆、大麻、橄榄、亚麻籽、花生、蓖麻、芥菜、椰子油或包含在松树浆中的脂肪油(妥尔油)，或它们的混合物。动物油或脂肪可以选自熏肉脂肪、猪油、牛油、乳脂和它们的混合物。还可以使用动物源或植物源的回收的食品工业的脂肪或油。所述植物油或脂肪还可以衍生自通过基因操控所选择的植物。
本发明的方法中使用的生物源混合物还可以在进料至所述方法之前与其它组分混合，例如与一种或多种烃混合。
在第一步(HDO步骤)中，所述生物源混合物与氢气在加氢脱氧催化剂的存在下进行加氢脱氧。
在该步骤中，通过脱羧基作用和加氢作用使得所述甘油三酯的酯链中存在的双键加氢、甘油三酯结构裂化和脱氧，同时生成水。
可以使用的催化剂是本领域中已知的所有含有适当负载的一种或多种选自VIII族和VIB族的金属的加氢催化剂。为此目的的合适的载体由一种或多种金属氧化物组成，所述金属氧化物优选氧化铝、氧化硅、氧化钛、氧化锆或它们的混合物。所述一种或多种金属优选选自Pd、Pt、Ni，或选自Ni-Mo、Ni-W、Co-Mo和Co-W的金属对，Ni-Mo和Co-Mo是优选的。这些催化剂一般用适当的所述一种或多种金属的盐溶液浸渍所述氧化物载体来制备。然后，所述浸渍之后在适合于分解所述前体盐并获得所述负载的金属的气氛下进行热处理。有可能进行连续浸渍以达到合意的金属装载水平，并且在多种金属的情况下，还区分它们的负载。通过将金属前体本身从所述金属的盐溶液中沉淀到载体上，或者通过多种催化剂组分即所述金属和载体的共沉淀，而不是通过浸渍，也是已知的生产所述催化剂的方法。
还可以使用催化组合物，例如沸石上的Ni-Mo-P、Pd/沸石、Pt/MSA，其中MSA是具有EP 340868、EP659478、EP812804中描述的特定特征的氧化硅-氧化铝，并且还用作随后的加氢异构化步骤中采用的催化组合物的载体。在本发明的HDO步骤中可以很好地使用的催化剂在，例如由J.T.Richardson的″Principal of catalystdevelopment″，Plenum Press，纽约，1989年，第6章中进行了描述。
Ni-Mo、Ni-W、Co-Mo和Co-W型催化剂被预硫化。根据已知的技术实施所述预硫化步骤。
为维持所述催化剂为硫化的形式，在所述生物源装料可能的提纯步骤之后，硫化剂，例如二甲二硫，以0.02～0.5wt％的量(140～3400ppm硫)与所述生物源装料同时进料。
或者，有可能用具有高S含量(S＞1％)的“直馏”瓦斯油以这样的浓度共进料来进行，以使得它几乎对应于所述装料中总S含量相同的总S含量。
所述HDO反应在一个或多个反应器中的包含一个或多个催化床的反应区中进行。根据优选的方面，在典型的固定床加氢处理反应器中进行该反应。可以以并流(equicurrent)或逆流的方式输送氢气流和生物源原料流。所述反应器可以具有数目上多于或等于2的绝热催化床。因为它是产生热量的放热反应，因此在每个催化床中有温度的升高。通过在一个催化床和另一个催化床之间进料处于规定温度下的氢气物流和/或液体原料，有可能获得恒定的或升高的温度曲线。该操作步骤通常表示为“分开进料”。
或者对于绝热分层反应器，可以采用管束反应器。将所述催化剂适当地装填在管内部，而将传热液体(道式热载体油)输送到外罩侧以移出反应热。
为了更好地调整或者具有绝热层或者具有管束的反应器内的热曲线，根据已知循环反应器的类型，所述反应器本身可以用部分流出物的再循环来运行。循环的功能是稀释所述反应器中的新鲜原料，从而限制由于反应的放热性引起的热峰值。所述循环比，即再循环部分相对于新鲜装料的量，可以从0.5wt/wt变化至5wt/wt。
可以用于本申请的其它反应器构型是浆料反应器，所述加氢脱氧催化剂在该反应器中适当地形成微球并且分散在所述反应环境中。通过机械搅拌或通过反应流体的强制再循环可促进这种情况下的气-液-固混合。
优选在25～70巴、优选30～50巴的压力下，在240～450℃、优选270～430℃的温度下进行所述HDO步骤。优选用0.5～2h-1，甚至更优选0.5～1h-1的LHSV来进行操作。H2/生物源混合物之比优选在400～2000N1/1范围内。
在所述HDO步骤之前，可以适当地处理所述生物源原料以便除去所述装料中可能含有的碱金属(例如Na，K)和碱土金属(例如Ca)的含量。通过在适当的材料上吸附可以进行该预处理：例如可以在填充有酸性土或粘土(例如蒙脱土、膨润土、蒙皂石、酸性海泡石)的柱上使用已知的渗透技术。为此目的，可以使用市场上可以得到的产品，例如费尔特洛尔活性白土、Tonsil、Bentolites H和L、SAT-1。
或者，可以使用离子交换树脂，或者例如通过优选在室温下和大气压下与硫酸、硝酸或盐酸接触而得到的弱酸性洗涤剂。
所述HDO步骤(1)的流出物优选在被送到随后的加氢异构化之前进行提纯处理。所述提纯处理可包括分离步骤和洗涤步骤。根据该优选的方面，将步骤(1)的流出物送到高压气-液分离器中。回收基本上由氢气、水、CO和CO2和轻质链烷烃(C4-)组成的气相。还可以存在少量的NH3、PH3和H2S。分离之后，冷却所述气相并通过冷凝分离出水(可能含有痕量的醇和羧酸)和可冷凝的烃。提纯其余的气相以便允许将氢气再循环至反应步骤(1)。所述提纯采用已知的技术方法，通过碱性洗涤剂，例如NaOH或Ca(OH)2的水溶液，或者通过公知的用胺(例如MEA即单乙醇胺、或DEA即二乙醇胺)提纯的技术来进行。在所述提纯结束时，除去CO2、H2S、PH3和NH3，从而获得基本上由H2与可能的痕量CO组成的气体部分。为限制CO在循环的气体中积累，可以根据本领域技术人员已知的技术通过铜氨(cuproammonia)洗涤或者通过甲烷化作用除去CO。
在所述高压分离器中分离出的液相由烃馏分组成，该烃馏分基本上由碳原子数为14～21，普遍为15～19的直链烷烃组成。根据所述分离器的操作条件，所述液体馏分可以含有少量的H2O和含氧化合物，例如醇和羰基化合物。剩余的S可以低于10ppm。然后可以用气体烃(例如CH4)、或氮气或氢气在气提塔中洗涤所述液体馏分以便进一步降低水的含量。
将得到的烃混合物进料至随后的加氢异构化步骤(2)。所述加氢异构化步骤在氢气和催化组合物的存在下进行，其中所述催化组合物包含：
a)包含完全无定形微孔-中孔氧化硅-氧化铝的酸性载体，其中所述氧化硅-氧化铝的硅铝的SiO2/Al2O3摩尔比在30～500范围内，表面积大于500m2/g，孔体积在0.3～1.3ml/g范围内，平均孔直径小于
b)含有一种或多种VIII族金属的金属组分，其可能与一种或多种VIB族金属混合。
本发明中使用的催化组合物的酸性载体(a)包含SiO2/Al2O3摩尔比优选在50～300范围内的氧化硅-氧化铝。
根据优选的方面，所述酸性载体(a)包含孔隙度在0.3～0.6ml/g范围内的氧化硅-氧化铝。
US 5,049,536、EP 659478、EP 812804中描述了可以使用完全无定形微孔-中孔氧化硅-氧化铝作为本发明的加氢异构化步骤中的催化组合物的载体(a)，并且称为MSA。它们的粉末XRD图案没有晶体结构并且没有显示任何峰。US 5,049,536、EP 659478、EP 812804也描述了适合作为载体(a)的氧化硅-氧化铝的多种制备方法。可以用于，例如用于本发明的方法中，的氧化硅-氧化铝可以根据EP659478由氢氧化四烷基铵、可以水解为Al2O3的铝化合物和可以水解为SiO2的硅化合物开始来制备，其中所述氢氧化四烷基铵是氢氧化四(C2～C5)烷基铵，所述可水解的铝化合物是三(C2～C4)烷氧基铝以及所述可水解的硅化合物是原硅酸四(C1～C5)烷基酯；使这些试剂经过在等于或高于作为所述水解反应的副产物而产生的任何醇在大气压下的沸点的温度下操作的水解和凝胶化作用，没有从反应环境中消除或基本上消除所述醇。优选在500～700℃的温度下在氧化气氛中干燥和煅烧如此产生的凝胶6～10小时。优选通过制备氢氧化四烷基铵的水溶液并将三烷氧基铝和原硅酸四烷基酯加入到所述水溶液中进行操作，在低于水解温度的温度下进行操作，试剂的量是这样的以使得SiO2/Al2O3的摩尔比为30/1～500/1，氢氧化四烷基铵/SiO2的摩尔比为0.05/1～0.2/1和H2O/SiO2摩尔比为5/1～40/1，通过加热到高于约65℃一直到约110℃的温度引起所述水解和凝胶化作用，操作在高压釜中在体系的自生压力下或者在常压下在装配有冷凝器的反应器内进行。
根据EP 812804，可以通过包括以下步骤的方法制备可以用作所述加氢异构化步骤的催化组合物的组分(a)的氧化硅-氧化铝：
-由原硅酸四烷基酯、C3～C6烷基醇或二元醇、具有式R1(R2)3NOH(其中R1是C3～C7烷基，R2是C1或C3～C7烷基)的氢氧化四烷基铵开始，在可水解的铝化合物的存在下制备混合物，其中所述摩尔比落在以下范围内：
醇/SiO2≤20
R1(R2)3NOH/SiO2＝0.05-0.4
H2O/SiO2＝1-40
Al2O3/SiO2大于零并且小于0.02
-使所述混合物在接近所存在的所述醇或醇的混合物的沸点的温度下进行水解和随后的凝胶化作用；
-干燥并煅烧所得到的凝胶。
在本发明的方法中使用的所述催化剂的酸性载体(a)可以是含有常规粘结剂例如氧化铝、薄水铝石或拟薄水铝石的挤出产物的形式。可以根据本领域技术人员熟知的技术制备所述挤出产物。所述氧化硅-氧化铝和所述粘结剂可以以30∶70～90∶10，优选50∶50～70∶30的重量比预混合。所述混合结束时，获得的产物被固结为合意的最终形式，例如挤出的球粒或片剂。根据优选的实施方案，可以使用EP
550922和EP 665055，优选后者，中描述的方法和粘结剂，在此引入所述专利的内容作为参考。
所述挤出产物形式的酸性组分(a)的一般制备方法(EP665055)包括以下步骤：
(A)以下列摩尔比制备氢氧化四烷基铵(TAA-OH)、能够水解为Al2O3的可溶性铝化合物和能够水解为SiO2的硅化合物的水溶液：
SiO2/Al2O3：30/1～500/1
TAA-OH/SiO2：0.05/1～0.2/1
H2O/SiO2：5/1～40/1
(B)加热如此获得的溶液并且引起其水解和凝胶化作用并获得粘度在0.01～100Pa·s范围内的混合物A；
(C)首先向混合物A中加入属于薄水铝石或拟薄水铝石类的粘结剂，该粘结剂与混合物A的重量比为0.05～0.5，随后加入其量为0.5～8.0g/100g粘结剂的无机酸或有机酸；
(D)加热按照要点(C)获得的混合物到40～90℃的温度，直到获得均匀的糊剂，对该均匀的糊剂进行挤出和造粒；
(E)在氧化气氛中干燥并煅烧所述挤出产物。
还优选将塑化剂，例如甲基纤维素，加入到步骤(C)中以促进形成均匀的并且容易处理的糊剂。
以这种方式获得粒状酸性载体，优选含有其量为30～70wt％的惰性无机粘结剂，其余的量由无定形氧化硅-氧化铝组成，该无定形氧化硅-氧化铝在以上对于没有粘结剂的相同的氧化硅-氧化铝所描述的孔隙度、表面大小和结构方面基本上具有相同的特征。
关于在本发明的方法的加氢异构化步骤中使用的催化组合物的所述金属组分(b)中所含的金属，它选自VIII族金属，任选地与一种或多种VIB族金属混合。优选只含有VIII族金属的组合物。所述一种或多种VIII族金属优选选自Pt、Pd、Ni和Co。特别地，当所述金属组分只含有VIII族金属时，所述金属优选选自Pt、Pd和Ni。当所述金属组分既含有一种或多种VIII族金属又含有一种或多种VIB族金属时，所述VIII族金属优选选自Ni和Co。所述VIB族金属优选选自Mo和W。
所述VIII族金属的量优选占所述催化组合物总重量的0.1～5wt％。所述VIB族金属的量，当存在时，占所述催化组合物总重量的1～50wt％，甚至更优选5～35wt％。所述金属，或多种金属的重量百分比指的是表示为金属元素的金属含量；在煅烧之后的最终催化剂中，所述金属为氧化物的形式。
所述加氢异构化步骤(2)中使用的催化组合物中包含的所述VIII族金属和任选的VI族金属可以用本领域技术人员已知的所有技术沉积在所述载体(a)上。EP 582347、EP 1101813和WO 2005/103207中描述了可以很好地在本发明的加氢异构化步骤中使用的、含有一种或多种VIII族金属的催化组合物以及它们的制备。
特别地，EP 582347描述了可以在正链烷烃的加氢异构化反应中使用的催化组合物，其含有一种或多种VIII族金属以及根据X-射线测定为无定形的氧化硅和氧化铝凝胶载体，该凝胶载体的SiO2/Al2O3摩尔比在30～500范围内，表面积在500～1000m2/g范围内，孔体积在0.3～0.6ml/g范围内以及孔直径普遍在
范围内。EP 1101813描述了可以用于制备中间蒸馏物的催化组合物，其含有一种或多种VIII族金属以及根据X-射线测定为无定形的煅烧过的氧化硅-氧化铝凝胶载体，该载体的SiO2/Al2O3摩尔比在30～500范围内，表面积在500～1000m2/g范围内，孔体积在0.2～0.8ml/g范围内以及平均孔直径在
范围内。
WO 2005/103207描述了可以用于蒸馏物改质的催化组合物，其含有一种或多种选自Pt、Pd、Ir、Ru、Rh和Re的金属以及根据X-射线测定为无定形的氧化硅-氧化铝载体，该载体的SiO2/Al2O3摩尔比在30～500范围内，表面积大于500m2/g，孔体积在0.3～1.3ml/g范围内以及平均孔直径小于
通常，在所述加氢异构化步骤(2)中使用的只含有VIII族金属的组合物中，根据上面指出的专利中描述的制备，可以通过浸渍或离子交换引入所述金属。根据第一种技术，所述酸性组分(a)(也为挤出的形式存在，并且优选为根据EP665055中描述的方法制备的挤出的形式)用VIII族金属的化合物的水溶液润湿，在例如室温下和pH值在1～4范围内进行操作。所述水溶液优选具有以g/L表示的在0.2～2.0范围内的金属浓度。优选在空气中，在室温下干燥得到的产物，并且在氧化气氛中在200～600℃的温度下进行煅烧。
在醇浸渍的情况下，所述酸性组分(a)(也为挤出的形式并且优选为根据EP665055中描述的方法制备的挤出的形式)悬浮在含有所述金属的醇溶液中。浸渍之后，干燥并煅烧所述固体。
根据离子交换技术，所述酸性组分(a)(也为挤出的形式并且优选为根据EP665055中描述的方法制备的挤出的形式)悬浮在所述金属的络合物或盐的水溶液中，在室温下在pH值为6～10范围内进行操作。离子交换之后，分离出所述固体，用水洗涤，干燥并且在惰性和氧化气氛中进行最终热处理。为此目的，可以使用的温度是在200～600℃范围内的温度。
可以很好地在上述制备中使用的金属的化合物是：H2PtCl6、Pt(NH3)4(OH)2、Pt(NH3)4Cl2、Pd(NH3)4(OH)2、PdCl2、(CH3COO)2Ni、(CH3COO)2Co。当所述催化组合物包含多于一种VIII族金属时，按以下描述实施所述浸渍：用第一种金属的化合物的溶液润湿所述酸性组分(a)(所述酸性组分(a)也为挤出的形式并且优选为根据EP665055中描述的方法制备的挤出的形式)，干燥得到的产物，任选地煅烧该产物，以及用第二种金属的化合物的溶液浸渍。干燥并且然后在氧化气氛下在200～600℃的温度范围内煅烧所述产物。或者，可以使用含有两种或更多种不同金属的化合物的单一水溶液同时引入所述金属。
使用之前，通过已知的技术，例如通过还原处理，并且优选通过干燥以及随后的还原来活化所述催化剂。在惰性气氛下在25～100℃的温度范围内实施所述干燥，而通过在还原气氛(H2)中在300～450℃温度范围内和优选在1～50巴压力范围内的催化剂热处理获得所述还原。EP 908231和EP 1050571中描述了很好地用于本发明的加氢异构化步骤中的、含有一种或多种VIII族金属混合物和另外一种或多种VIB族金属的催化组合物以及它们的制备。特别地，EP 908231描述了催化组合物，其含有VIB族和VIII族金属的混合物以及通过X-射线测定为无定形的氧化硅和氧化铝凝胶载体，该凝胶载体的SiO2/Al2O3摩尔比在30～500范围内，表面积在500～1000m2/g之间，孔体积在0.3～0.6ml/g范围内以及平均孔直径在范围内。当所述加氢异构化催化剂在金属相(b)中还含有VIB族金属时，可以通过水或醇浸渍制备所述催化剂。更具体地，根据第一种技术，用合意的VIB族金属的化合物的水溶液润湿所述氧化硅-氧化铝(该氧化硅氧化铝也为挤出的形式并且优选为根据EP665055中描述的方法制备的挤出的形式)，在室温下或接近于室温的温度下进行操作。水溶液浸渍后，干燥所述固体并且然后用合意的VIII族金属的化合物的水溶液实施新的浸渍。水溶液浸渍后，再次干燥所述固体并在氧化气氛下进行热处理。适合于该热处理的温度在200～600℃范围内。还可以在单步中实施所述金属相的水溶液浸渍，其中用含有VIB和VIII族的金属化合物的单一水溶液润湿所述氧化硅-氧化铝基的酸性载体，随后进行与前面描述的操作步骤一样的步骤。在醇浸渍技术中，使所述氧化硅-氧化铝(也为挤出的形式并且优选为根据EP665055中描述的方法制备的挤出的形式)悬浮在VIB族金属的化合物和VIII族金属的化合物的醇溶液中，在室温下或接近于室温的值下进行操作。浸渍之后，优选在空气中在约100℃的温度下干燥所述固体并且在氧化气氛下，优选在空气中，进行热处理。
可以配制最终的加氢异构化催化剂并将其成型为具有例如EP1101813中描述的不同形状(例如圆柱状、三裂片状等)的挤出产物。
本发明的加氢异构化步骤中使用的催化组合物具有耐水性质：所述耐水效果可以从催化活性上观察到，然而催化活性可以通过升高温度而恢复，而没有发现不可逆的失活。升高几摄氏度，3～5℃，一般足以恢复由于烃装料中的1000～2000ppm的水引起的活性下降。优选在水浓度为约1000ppm，甚至更优选在低于300ppm的水平下进行操作。
用于所述加氢异构化步骤的反应器构型是固定床反应器。这种情况下，热控制并不是关键的，因为所述反应是略微放热的。由于这一原因，绝热的分层反应器是适合的。无论如何，还可以使用管束反应器。
可以将来源于加氢脱氧步骤的液体原料以相对于氢气并流或逆流的方式送到所述反应器中。当所述液体原料含有显著含量的水和/或在所述方法的第一步中没有转化的含氧化合物(＞300ppm的氧)时，优选逆流步骤。
因此以气相方式除去所述催化床的第一部分中存在的或通过加氢异构化过程中的含氧化合物生成的水，从而降低与其余催化剂的接触时间。对于该催化步骤，特别优选的安排是具有大于或等于2的层数的反应器，其中被来源于加氢脱氧步骤的液体烃物流所覆盖的第一层，因此对应于被气体氢气物流覆盖的最后一层，所述最后一层不是由所述催化剂组成，而是由结构化的惰性物料(例如陶瓷或不锈钢)，或惰性物料(例如浮石、α-氧化铝、玻璃)的颗粒或球粒的填料组成。填料的作用是促进气液接触，因为进行异构化的烃装料在流到所述催化床上之前会遇到气体氢气物流，从而进一步被脱水干燥(anhydrified)。
可以在250～450℃，优选280～380℃温度范围内和25～70巴，优选在30～50巴压力范围内进行所述加氢异构化。优选在LHSV在0.5～2h-1范围内进行操作。所述H2/HC之比优选在200～1000N1/1范围内。
对由所述加氢异构化步骤得到的混合物进行蒸馏以获得可以用作柴油燃料的提纯的烃混合物。
图1说明了可以在本发明的由含有脂肪酸酯和任选地一定量的游离脂肪酸的生物源混合物(生物混合物)开始生产可以用作柴油燃料的烃馏分的方法中使用的装置方案。图1中的方案是根据与加氢脱氧(DEOX反应器)、通过高压分离器和洗涤(SEP)进行的提纯和加氢异构化(ISOM反应器)步骤有关的上面描述的内容。该方案中，在加氢异构化反应器之后，还有随后的通过分离器和蒸馏器的分离步骤以分离出获得的瓦斯油。虚线代表了来源于第一步的流出物的可能的再循环。
出于单纯地举例说明本发明的具体方面的目的，提供了本发明的方法目的的一些实际的实施方案的实施例以便更详细地描述，绝不应当认为这些实施例限制本发明本身的整体范围。
实施例1-制备催化剂Pt/MSA
试剂和物料
在以下描述的制备中使用如下商购试剂：
氢氧化四丙基铵(TPA-OH)SACHEM
三异丙氧基铝FLUKA
硅酸四乙酯DYNAMIT NOBEL
氧化铝(VERSAL 250，拟薄水铝石)LAROCHE
甲基纤维素(METHOCEL)FLUKA
所使用的和上面没有指出的试剂和/或溶剂是广泛使用的那些并且可以很容易被专注于本领域的正常商业操作者发现。
准备性的实施例
(i)制备氧化硅-氧化铝凝胶
用去离子水中的1wt％的氢氧化四丙基铵(TPA-OH)溶液75L预先洗涤100L的反应器，维持所述液体在120℃下搅拌6小时。排放所述洗涤溶液并且加入23.5L去离子水、19.6kg 14.4wt％的TPA-OH(13.8mol)水溶液和600g(2.94mol)三异丙氧基铝。加热所述混合物到60℃并在此温度下保持搅拌1小时以获得透明的溶液。然后将所述溶液的温度升至90℃并迅速地加入31.1kg(149mol)硅酸四乙酯。关闭所述反应器并将搅拌速度调节到约1.2m/s，使所述混合物在搅拌下在80～90℃温度范围内维持3小时，用自动调温器进行调节控制以移出水解反应所产生的热量。将所述反应器中的压力升至约0.2MPa。最后，排出反应混合物并将其冷却至室温，获得均匀的并且相对而言的流体凝胶(粘度0.011Pa·s)，该凝胶具有以下摩尔比组成：
SiO2/Al2O3＝101
TPA-OH/SiO2＝0.093
H2O/SiO2＝21
(ii)制备挤出产物
将1150g预先在150℃下在空气中干燥3小时的氧化铝(VERSAL150)和190g甲基纤维素加入到维持在70～80转/分钟的搅拌速度下的10L的犁片混合器中。然后经约15分钟的时间加入按照前面描述制备并放置约20小时的5kg氧化硅-氧化铝凝胶，并使所述混合物在搅拌下放置约1小时。加入6g冰醋酸并将所述混合器的温度升高至约60℃，随后继续搅拌直到获得均匀的糊剂，该糊剂具有适合于随后的挤出的合意的稠度。
将按照上面的描述获得的均匀的糊剂加入到HUTT型挤出机中，挤出并切成具有合意尺寸(约2×4mm)的圆柱状颗粒。放置所述产物约6～8小时并且然后将其在100℃的空气流中保持5小时进行干燥。最后在马弗炉中在550℃下在氮气流中煅烧3小时并且在空气中进一步煅烧8小时。
从而获得具有酸性质的多孔固体，该固体基本上由二氧化硅/氧化铝组成(相对于各自的初始试剂而言，收率为95％)，BET为608m2/g。
(iii)用铂浸渍所述载体
将含有4.5g/L氯铂酸(H2PtCl6，0.133mol)的12.1ml盐酸(0.6M)水溶液在缓慢搅拌下滴加到含有10g按照前面的描述制备的多孔固体的玻璃容器中。将如此获得的混合物在搅拌下在室温下放置16小时。然后在60℃的空气流中经过约1小时时间蒸发所述水。然后将所得到的固体在150℃下维持2小时进行干燥，并通过经3小时时间在马弗炉中在室温～500℃的空气流中加热来进行煅烧。最后，获得在下面的实施例3中描述的加氢异构化步骤中使用的负载催化剂，该催化剂具有以下特征：
59.8wt％的无定形氧化硅-氧化铝(SiO2/Al2O3摩尔比＝102)
39.9wt％的氧化铝(拟薄水铝石)
0.3wt％的铂
孔体积：0.6ml/g
BET：600m2/g
破碎强度：10kg/cm(径向)；
90kg/cm2(轴向)
实施例2-加氢脱氧步骤(HDO)
该实验在用具有表1中表明的性质的大豆油(精炼的大豆油Sipral)进料的连续反应器中进行。
将植物油与氢气以并流方式在基于硫化物形式的NiMo/Al2O3的商业加氢催化剂UOP UF 210的存在下进料到第一步中。使用瓦斯油原位进行所述催化剂的硫化，其中所述瓦斯油含有浓度从3wt％逐渐变化到9wt％的二甲二硫(DMDS)，硫化在在230～370℃范围内逐渐改变的温度和70巴压力下进行，氢气/瓦斯油之比为1300N1/1以及LHSV为0.8h-1。将所述植物油在少量的DMDS(0.025％)的存在下进料到所述反应器中以保持所述催化剂处于硫化的形式。
所述原料和氢气以下降流模式经过反应器。
使用的操作条件如下：
·平均温度：340～350℃
·LHSV：1h-1
·压力：35巴
·H2/油：1500N1/1
表1
| 精炼的大豆油 | |
| 棕榈酸％*(C16-0) | 13.06 |
| 硬脂酸％*(C18-0) | 0.84 |
| 油酸％*(C18-1) | 27.09 |
| 亚油酸％*(C18-2) | 53.63 |
| 亚麻酸％*(C18-3) | 5.11 |
| 花生酸％(C20-0) | 0.07 |
| 酸度(mgKOH/g) | 0.11 |
| H2O(ppm) | 2200 |
| Na(ppm) | 0.3 |
| K(ppm) | 0.7 |
| Ca(ppm) | 0.3 |
| Mg(ppm) | 0.1 |
| Al(ppm) | 0.01 |
| P(ppm) | 0.65 |
| Fe(ppm) | ＜0.05 |
| Cu(ppm) | 0.02 |
*括号中的第一个数字表示碳原子，第二个数字表示不饱和度。
在气/液分离器中从气体馏分中分离出流出物产物，其中所述气体馏分由H2、CO/CO2和几乎全部由C3H8组成的轻质烃组成。
分离出水后的液体产物由正链烷烃组成，下表2和图2中表明了液体产物的性质和分布。
表2
实施例3-加氢异构化步骤
用并流的氢气在前面的实施例1中制备的Pt/MSA催化剂的存在下处理实施例2中描述的加氢脱氧步骤中获得的含有100ppm残余的水的产物。表3中表明了使用的操作条件：
表3
| 温度 | 340-360℃ |
| LHSV | 2h-1 |
| 压力 | 35巴 |
| H2/HC | 1,000N1/1 |
所述加氢异构化反应器的流出物由气相和液相组成，在气/液分离器中将两相分开，通过GC分析所述气相由C3/C4轻质链烷烃(LPG)组成，而通过GC分析分离出的含有碳原子数为5～22的链烷烃的所述液相以评价异构化水平，该异构化水平在这些操作条件下是79％并且用来评价所述蒸馏曲线。
然后将所述烃送到蒸馏塔中以便将柴油馏分(87.3％)与汽油馏分(12.7％)分开。表征了含有碳原子数为12～22的链烷烃的柴油馏分并在表4中表明了其主要性质：
表4
图3表明了涉及实施例2和3的方法的总物料平衡，在反应器DEOX中进行所述加氢脱氧步骤，SEP是气液分离器以及ISOM是进行所述加氢异构化步骤的反应器。在加氢异构化反应器之后，给出了蒸馏塔，从该蒸馏塔中回收所述柴油馏分。
Claims (56)
1.由含有脂肪酸酯并且任选含有游离脂肪酸的生物源混合物开始生产可以用作柴油燃料或用作柴油燃料组分的烃馏分的方法，所述方法包括以下步骤：
1)使所述生物源混合物加氢脱氧；
2)在任选的提纯处理之后，对由步骤(1)得到的混合物进行加氢异构化，所述加氢异构化在催化体系的存在下进行，所述催化体系包含：
a)包含完全无定形微孔-中孔氧化硅-氧化铝的酸性载体，其中所述氧化硅-氧化铝的SiO2/Al2O3摩尔比在30～500范围内，表面积大于500m2/g，孔体积在0.3～1.3ml/g范围内，平均孔直径小于
b)含有一种或多种VIII族金属的金属组分，其任选与一种或多种VIB族金属混合。
2.根据权利要求1的方法，其中所述生物源混合物是植物源或动物源混合物。
3.根据权利要求1或2的方法，其中包含在所述生物源混合物中的脂肪酸酯是脂肪酸甘油三酯，其中所述脂肪酸的烃链含有12～24个碳原子并且是单-不饱和的或多-不饱和的。
4.根据权利要求1、2或3的方法，其中所述生物源混合物选自植物油、植物脂肪、动物脂肪、动物油、鱼油或它们的混合物。
5.根据权利要求4的方法，其中所述植物油或植物脂肪，其任选衍生自通过基因操纵所选择的植物，选自向日葵油、油菜、卡诺拉、棕榈、大豆、大麻、橄榄、亚麻籽、芥菜、花生、蓖麻、椰子油或包含在松树浆中的脂肪油即妥尔油、回收的食品工业油或脂肪和它们的混合物。
6.根据权利要求4的方法，其中所述动物油或动物脂肪选自咸肉脂肪、猪油、牛脂、乳脂、回收的食品工业油或脂肪和它们的混合物。
7.根据权利要1的方法，其中在将所述生物源混合物进料至步骤(1)之前使其与一种或多种烃混合。
8.根据权利要1的方法，其中步骤(1)在氢气和加氢催化剂的存在下进行，其中所述加氢催化剂含有载体和一种或多种选自VIII族和VIB族的金属。
9.根据权利要7的方法，其中步骤(1)的催化剂的载体选自氧化铝、氧化硅、氧化锆、氧化钛或它们的混合物。
10.根据权利要7的方法，其中包含在步骤(1)的催化剂中的所述一种或多种金属选自Pd、Pt、Ni、或选自Ni-Mo、Ni-W、Co-Mo和Co-W金属对。
11.根据权利要7的方法，其中步骤(1)的催化剂选自催化组合物沸石上的Ni-Mo-P、Pd/沸石、Pt/MSA。
12.根据权利要1或7的方法，其中步骤(1)在一个或多个反应器中的包含一个或多个催化床的反应区中进行。
13.根据权利要11的方法，其中步骤(1)在固定床加氢处理反应器中进行。
14.根据权利要求7、11或12的方法，其中步骤(1)中，将氢气物流与生物源原料以并流或逆流方式输送。
15.根据权利要求7、11或12或13的方法，其中所述反应器具有数目上大于或等于2的绝热层。
16.根据权利要求11、12或14的方法，其中将某一温度下的氢气物流和/或原料液体送到一个催化床和另一个催化床之间以建立恒定的或递增的温度曲线。
17.根据权利要求7或11的方法，其中所述反应器是具有装于管内的所述催化剂和被送到外罩侧的传热液体的管束反应器。
18.根据权利要求14或16的方法，其中用一部分流出物的再循环来运行所述反应器。
19.根据权利要求17的方法，其中循环比，即再循环馏分的量与所述新鲜原料的比在0.5～5wt/wt之间改变。
20.根据权利要求7的方法，其中使用浆料反应器，其中所述加氢脱氧催化剂由微球组成并且分散到反应环境中，并且通过机械搅拌或通过所述反应流体的强制再循环来实施所述混合。
21.根据权利要求1的方法，其中步骤(1)在25～70巴压力范围内和240～450℃温度范围内进行。
22.根据权利要求20的方法，其在270～430℃的温度范围内进行。
23.根据权利要求20的方法，其中所述压力在30～50巴范围内。
24.根据权利要求20的方法，其在LHSV为0.5～2h-1范围内进行。
25.根据权利要求20的方法，其中在步骤(1)中采用400～2000N1/1范围内的H2/生物源混合物之比。
26.根据权利要求7或9的方法，其中所述基于Ni-Mo、Ni-W、Co-Mo和Co-W的催化剂在使用之前被硫化。
27.权利要求26的方法，其中为维持所述催化剂处于硫化形式，同时将硫化剂进料或者将具有高硫含量的直馏瓦斯油进料至所述生物源混合物。
28.根据权利要求1的方法，其中使所述生物源混合物在进料至步骤(1)之前经过预处理，其中通过吸收、用离子交换树脂或弱酸性洗涤剂处理来实施所述预处理。
29.根据权利要求1的方法，其中将步骤(1)得到的所述混合物在进行加氢异构化之前进行提纯处理，其中所述提纯处理包括分离步骤和洗涤步骤。
30.根据权利要求28的方法，其中在所述分离步骤中，将步骤(1)得到的所述混合物送到高压气-液分离器中以便回收气相和液相。
31.根据权利要求29的方法，其中通过冷凝来冷却含有氢气、水、CO、CO2、具有4个或更少的碳原子的轻质链烷烃和任选的少量NH3、PH3和H2S的所述气相，并且分离出所述水和可冷凝的烃，并提纯其余的气相以获得可以被再循环至所述反应步骤(1)中的氢气。
32.根据权利要求29的方法，其中在高压分离器中分离出的液相在进料至随后的加氢异构化步骤(2)中之前用氢气或氮气或气体烃在气提器中洗涤，其中所述液相由基本上由碳原子数为14～21的直链烷烃组成的烃馏分组成。
33.根据权利要求1的方法，其中步骤(2)在氢气和催化体系的存在下进行，其中所述催化体系包括：
a)包含完全无定形的微孔-中孔氧化硅-氧化铝的酸性载体，其中所述氧化硅-氧化铝的SiO2/Al2O3摩尔比在30～500范围内，表面积大于500m2/g，孔体积在0.3～1.3ml/g范围内，平均孔直径小于
b)含有一种或多种VIII族金属的金属组分，其任选与一种或多种VIB族金属混合。
34.根据权利要求1和32的方法，其中在所述步骤(2)中包含在所述酸性载体(a)中的氧化硅-氧化铝的SiO2/Al2O3摩尔比在50～300范围内。
35.根据权利要求1和32的方法，其中在所述步骤(2)中包含在所述酸性载体(a)中的氧化硅-氧化铝的孔隙度在0.3～0.6ml/g范围内。
36.根据权利要求1的方法，其中在步骤(2)中所述催化体系的酸性组分(a)的形式为含有粘结剂的挤出产物。
37.根据权利要求35的方法，其中在步骤(2)中形式为含有粘结剂的挤出产物的所述催化体系的酸性组分(a)通过包括以下步骤的方法制备：
(A)以下列摩尔比制备氢氧化四烷基铵(TAA-OH)、能够水解为Al2O3的可溶性铝化合物和能够水解为SiO2的硅化合物的水溶液：
SiO2/AI2O3：30/1～500/1
TAA-OH/SiO2：0.05/1～0.2/1
H2O/SiO2：5/1～40/1
(B)加热如此获得的溶液以引起其水解和凝胶化作用并获得粘度在0.01～100Pa·s范围内的混合物A；
(C)首先向所述混合物A中加入属于薄水铝石或拟薄水铝石类的粘结剂，该粘结剂与混合物A的重量比为0.05～0.5，随后加入其量为0.5～8.0g/100g粘结剂的无机酸或有机酸；
(D)加热并同时搅拌按照步骤(C)获得的混合物到40～90℃的温度，直到获得均匀的糊剂，对该均匀的糊剂进行挤出和造粒；
(E)在氧化气氛中干燥并煅烧所述挤出产物。
38.根据权利要求1的方法，其中在步骤(2)中所述催化体系含有一种或多种选自Pt、Pd、Ni、Co的VIII族金属作为金属组分(b)。
39.根据权利要求37的方法，其中所述催化体系只含有VIII族金属并且所述金属选自Pt、Pd和Ni。
40.根据权利要求37的方法，其中所述催化体系同时含有一种或多种VIII族金属和一种或多种VIB族金属，并且所述VIII族金属选自Ni和Co。
41.根据权利要求1、37或39的方法，其中在步骤(2)中所述催化体系同时含有一种或多种VIII族金属和一种或多种VIB族金属作为金属组分(b)，并且所述VIB族金属选自Mo和W。
42.根据权利要求1的方法，其中在步骤(2)的所述催化体系中，所述VIII族金属的量占所述催化剂总重量的0.1～5wt％。
43.根据权利要求1的方法，其中在步骤(2)的所述催化体系中，所述VIB族金属的量占所述催化剂总重量的1～50wt％。
44.根据权利要求42的方法，其中所述VIB族金属的量为5～35wt％。
45.根据权利要求1的方法，其中在步骤(2)中，所述催化体系包含一种或多种VIII族金属和根据X-射线测定为无定形的氧化硅和氧化铝凝胶载体，所述载体的SiO2/Al2O3摩尔比在30～500范围内，表面积在500～1000m2/g范围内，孔体积在0.3～0.6ml/g范围内，平均孔直径在10～
范围内。
46.根据权利要求1的方法，其中在步骤(2)中，所述催化体系包含一种或多种VIII族金属和根据X-射线测定为无定形的煅烧的氧化硅和氧化铝凝胶载体，所述载体的SiO2/Al2O3摩尔比在30～500范围内，表面积在500～1000m2/g范围内，孔体积至多0.8ml/g和平均孔直径在10～
范围内。
47.根据权利要求1的方法，其中在步骤(2)中，所述催化体系包含一种或多种选自Pt、Pd、Ir、Ru、Rh和Re的金属和根据X-射线测定为无定形的氧化硅氧化铝载体，所述载体的SiO2/Al2O3摩尔比在30～500范围内，表面积大于500m2/g，孔体积在0.3～1.3ml/g范围内和平均孔直径小于
48.根据权利要求1的方法，其中在步骤(2)中，所述催化体系含有属于VIB族和VIII族的金属的混合物和根据X-射线测定为无定形的氧化硅和氧化铝凝胶载体，所述载体的SiO2/Al2O3摩尔比在30～500范围内，表面积在500～1000m2/g范围内，孔体积在0.3～0.6ml/g范围内和孔直径在10-
范围内。
49.根据权利要求1的方法，其中在固定床反应器中进行所述加氢异构化步骤(2)。
50.根据权利要求48的方法，其中所述反应器具有多个绝热层。
51.根据权利要求1、48或49的方法，其中将经受加氢异构化的所述混合物以相对于所述氢气并流或逆流的形式进料到所述加氢异构化反应器中。
52.根据权利要求50的方法，其中以逆流方式在具有大于或等于2的层数的反应器中实施所述方法，其中由经受加氢异构化的所述混合物覆盖的第一层由结构化的惰性物料或惰性物料的颗粒或球粒的填料组成。
53.根据权利要求1或32的方法，其中在250～450℃范围的温度下和25～70巴范围的压力下进行所述加氢异构化步骤(2)。
54.根据权利要求52的方法，其在280～380℃范围的温度下进行。
55.根据权利要求52的方法，其在30～50巴范围的压力下进行。
56.根据权利要求52的方法，其在0.5～2h-1范围内的LHSV下和200～1000h-1范围内的H2/烃之比下进行。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT002193A ITMI20062193A1 (it) | 2006-11-15 | 2006-11-15 | Processo per produrre frazioni idrocarburiche da miscele di origine biologica |
| ITMI2006A002193 | 2006-11-15 | ||
| PCT/EP2007/009668 WO2008058664A1 (en) | 2006-11-15 | 2007-11-07 | Process for producing hydrocarbon fractions from mixtures of a biological origin |
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| IT1255526B (it) * | 1992-09-29 | 1995-11-09 | Eniricerche Spa | Procedimento per la preparazione di un catalizzatore efficace nella idroisomerizzazione di normal-paraffine |
| IT1312337B1 (it) * | 1999-05-07 | 2002-04-15 | Agip Petroli | Composizione catalitica per l'upgrading di idrocarburi aventi punti di ebollizione nell'intervallo della nafta |
| JP4644351B2 (ja) * | 1999-10-27 | 2011-03-02 | 出光興産株式会社 | 金属化合物担持処理耐火性無機酸化物担体及び該担体を用いた水素化処理触媒 |
| FI20021596L (fi) * | 2002-09-06 | 2004-03-07 | Fortum Oyj | Dieselmoottorin polttoainekoostumus |
| US7232935B2 (en) * | 2002-09-06 | 2007-06-19 | Fortum Oyj | Process for producing a hydrocarbon component of biological origin |
| JP2004358326A (ja) * | 2003-06-03 | 2004-12-24 | Nippon Kecchen Kk | 水素化処理用触媒とその使用方法 |
| ITMI20031360A1 (it) * | 2003-07-03 | 2005-01-04 | Enitecnologie Spa | Solido poroso amorfo cataliticamente attivo e processo per la sua preparazione. |
| US20060264684A1 (en) * | 2005-05-19 | 2006-11-23 | Petri John A | Production of diesel fuel from biorenewable feedstocks |
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2006
- 2006-11-15 IT IT002193A patent/ITMI20062193A1/it unknown
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2007
- 2007-11-07 US US12/515,086 patent/US8608812B2/en active Active
- 2007-11-07 RU RU2009119279/04A patent/RU2464297C2/ru active
- 2007-11-07 EP EP07819678.9A patent/EP2084245B1/en active Active
- 2007-11-07 ES ES07819678.9T patent/ES2672792T3/es active Active
- 2007-11-07 MY MYPI20091959A patent/MY162234A/en unknown
- 2007-11-07 JP JP2009536634A patent/JP2010509472A/ja active Pending
- 2007-11-07 BR BRPI0721487-1A2A patent/BRPI0721487A2/pt not_active Application Discontinuation
- 2007-11-07 MX MX2009005170A patent/MX2009005170A/es active IP Right Grant
- 2007-11-07 WO PCT/EP2007/009668 patent/WO2008058664A1/en active Application Filing
- 2007-11-07 CN CN2007800453885A patent/CN101583694B/zh active Active
- 2007-11-07 CA CA2669538A patent/CA2669538C/en active Active
- 2007-11-07 PT PT78196789T patent/PT2084245T/pt unknown
- 2007-11-14 AR ARP070105058A patent/AR063810A1/es active IP Right Grant
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2009
- 2009-05-12 TN TNP2009000186A patent/TN2009000186A1/fr unknown
- 2009-05-27 NO NO20092072A patent/NO345219B1/no unknown
- 2009-05-29 MA MA31934A patent/MA30930B1/fr unknown
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2014
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| EP0582347A1 (en) * | 1992-07-31 | 1994-02-09 | ENIRICERCHE S.p.A. | Catalyst for the hydroisomerization of long-chain N-paraffins and process for preparing it |
| CN1221776A (zh) * | 1997-10-09 | 1999-07-07 | 艾吉普·帕特罗里公司 | 长链正构烷烃的加氢异构化方法和适用于该目的的催化剂 |
| EP1396531A2 (en) * | 2002-09-06 | 2004-03-10 | Fortum OYJ | Process for producing a hydrocarbon component of biological origin |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2009005170A (es) | 2009-10-12 |
| BRPI0721487A2 (pt) | 2014-03-25 |
| MA30930B1 (fr) | 2009-11-02 |
| CA2669538A1 (en) | 2008-05-22 |
| NO20092072L (no) | 2009-08-05 |
| NO345219B1 (no) | 2020-11-09 |
| US20090300970A1 (en) | 2009-12-10 |
| WO2008058664A8 (en) | 2009-06-04 |
| EP2084245B1 (en) | 2018-03-21 |
| CA2669538C (en) | 2016-02-23 |
| CN101583694A (zh) | 2009-11-18 |
| JP2015004066A (ja) | 2015-01-08 |
| ITMI20062193A1 (it) | 2008-05-16 |
| PT2084245T (pt) | 2018-06-20 |
| TN2009000186A1 (en) | 2010-10-18 |
| ES2672792T3 (es) | 2018-06-18 |
| MY162234A (en) | 2017-05-31 |
| WO2008058664A1 (en) | 2008-05-22 |
| EP2084245A1 (en) | 2009-08-05 |
| JP2010509472A (ja) | 2010-03-25 |
| AR063810A1 (es) | 2009-02-18 |
| RU2009119279A (ru) | 2010-12-20 |
| RU2464297C2 (ru) | 2012-10-20 |
| CO6210703A2 (es) | 2010-10-20 |
| US8608812B2 (en) | 2013-12-17 |
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