CN102822320A - 汽油升级方法 - Google Patents
汽油升级方法 Download PDFInfo
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- CN102822320A CN102822320A CN2011800167771A CN201180016777A CN102822320A CN 102822320 A CN102822320 A CN 102822320A CN 2011800167771 A CN2011800167771 A CN 2011800167771A CN 201180016777 A CN201180016777 A CN 201180016777A CN 102822320 A CN102822320 A CN 102822320A
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract
本发明涉及允许通过利用具有降低的扩散限制的结晶催化剂转化包含4至20个碳原子的烯烃的原料来调节汽油/柴油平衡的方法。所述方法包括:-在存在或不存在包含芳香族化合物的料流的条件下处理包含4至20个碳原子的烯烃的原料流,-使所述料流与催化剂在有效地使至少一部分所述烯烃低聚并且最终使至少一部分所述芳香族化合物烷基化的条件下接触,其中所述催化剂为选自结晶铝硅酸盐、结晶铝磷酸盐、结晶硅-铝磷酸盐、结晶沸石的具有微/中孔结构的结晶化合物,或者所述催化剂为包含至少20重量%的至少一种上述结晶化合物的复合材料,并且其中所述结晶化合物的中孔体积为至少0.22ml/g。
Description
本发明涉及允许通过利用具有降低的扩散限制(diffusionallimitation)的结晶催化剂,优选基于沸石的催化剂,转化添加有或未添加芳香族化合物并包含4至20个碳原子、更特别地4至15个碳原子、优选4至9个碳原子的烯烃的原料来协调汽油/柴油平衡的方法。
当今的精炼厂必须适应不断发展和波动的市场,总是需要更强的适应性。尤其是在这些年显著发展的汽油/中间馏分市场:在当前和将来的欧洲市场的需求中,观察到产品焦点正从汽油向中间馏分转移。
为了应对上述失衡,根据市场需求重新调整汽油/柴油平衡的好的方法在于将至少一部分汽油升级为中间馏分(航空煤油(jet)、柴油)。
在当今的典型精炼厂中,大部分C4-C8分子最终在汽油调和组分总和(gasoline-pool)中。重要的是需要指出,这些分子仅有约5%一开始就存在于输送的原油中,而其余的在提炼厂加工过程中的裂化中产生。流化催化裂化(Fluidized Catalytic Cracking,FCC)中产生的约50%的C4和40%的C5实质上为烯烃。当前C4烯烃被用作烷基化和醚化单元的原料,以产生具有高辛烷值的汽油组分,更高级的烯烃通常直接混合到汽油调和组分总和中。
在这个背景下,允许在汽油与馏分油之间重建平衡的便利方案将通过使包含在汽油原料中的不饱和分子(烯烃和/或芳香族化合物)选择性低聚和/或烷基化使这些不饱和分子转化成存在于中间馏分范围内(即柴油和煤油)的较重分子。
本发明涉及利用具有降低的扩散限制的催化剂,优选基于沸石的催化剂,从具有较低分子量的分子料流中制造具有较高分子量的有机分子的方法。
当今,已经可以商业获得不同的技术来通过低聚转化烯烃。
通常已知的低聚方法包括使包含4至10个碳原子的原料与固体酸催化剂如固体磷酸(Solid Phosphoric Acid,SPA)催化剂、结晶分子筛或无定形氧化硅-氧化铝(silica-alumina)接触。
利用SPA催化剂时,催化床上的压降由于催化剂的焦化、膨胀而逐步增加,因此是持续运行的限制因素,一旦达到最大可允许压降,就要结束单元。
无定形氧化硅-氧化铝催化剂提供在相当低的温度(140-160℃)下运行的优点,因此在受到二次反应(裂化,等)限制前,允许较大范围的操作温度。但是,这些催化剂系统无形状选择性,所产生的柴油馏分油表现出差的十六烷值。
在MOGD方法(莫比尔烯烃制汽油和馏分油工艺(Mobil Olefins toGasoline and Distillate))中会发现结晶分子筛的应用,由莫比尔(Mobil)提出(US-4,150,062;US-4,227,992;US-4482772;US-4506106;US-4543435),并且在七十和八十年代之间利用ZSM-5沸石作为催化剂得到了发展。
以类似方式,德国的Lurgi AG(WO2006/076942)开发了甲醇到合成燃料(Methanol to Synfuels,MTS)的方法,其大体上类似于MOGD方法。Lurgi路线是简化的Lurgi MTP技术与Süd Chemie的COD技术(US5063187)的组合。该方法产生比率约1∶4的汽油(RON 80)和柴油(十六烷值~55)。
与无定形氧化硅-氧化铝催化剂相反,沸石催化剂具有由沸石结构的微孔性产生的形状选择性,因此使得柴油馏分油具有好的十六烷值。
但是,微孔也可能具有在催化反应过程中对反应物和/或产物的不期望的吸附效果的负面影响,其经常显示为降低分子进入沸石结晶的速率。
推测在催化作用中,这些空间约束造成沸石微孔体积的可达性(accessibility)的降低,并且可以阐述为沸石结晶一直不能有效利用。
在宏观规模,这显示为需要较高的操作温度(一般至少200℃)以限制孔的阻塞并且提高低聚物的分散,因此相当限制操作窗,这是因为高的操作温度有利于二次反应(在温度高于300℃时二次反应如裂化/异构化/焦化变得突出)。
一个有关低聚/烷基化的限制在于一方面的低聚/烷基化与裂化之间的竞争。为了避免这些不期望的反应并且增强催化剂向较重形成(heaviesformation)的选择性,需要设计最佳可达的催化剂。形状选择性沸石似乎是最有希望的催化剂,因为通过选择合适的材料可以限制异构反应。对于轻烯烃的转化,通常10元环沸石在微孔尺寸范围非常合适。
为了最大化沸石结晶的有效性,一个降低扩散限制的方案在于利用小结晶尺寸的沸石。尽管该观念已经被开发利用于若干沸石中(A.Corma,Nature,396(1998),353),但是在工业实践中使用小的脱铝沸石结晶可能并不总是可行的。
获得具有降低的扩散限制的原料的一个更加一般地应用的策略在于在微孔沸石结晶中产生由中孔(2-50nm)组成的次级孔(secondary pore)系统。
近几年,开发了若干允许获得邻近沸石微孔性的结构化的中孔性的可替代技术,例如:
-将中孔材料的壁重结晶成沸石材料;
-中尺度阳离子聚合物模板;
-通过使用两亲性有机硅沸石来构建中孔材料;
-利用模板为中孔定形来引发沸石晶粒的组装。
对于这些方法中的一些,已经表明可以得到在多种反应中具有改善性能的催化剂。例如,WO 2009/153421公开了具有分级和有组织的孔性质的结晶材料的合成及其在轻烯烃低聚中的应用。
尽管最近几年在这些结构化中孔材料的合成、其形成机制的表征和理解领域具有相当的发展,但是由于其成本(特别涉及高成本的有机模板),它们在工业中的有效应用依然高度受限。
因此,从成本来看,经典的水热和酸浸方法依然是最有吸引力的技术,现在广泛用在工业中。但是,通过这些方法引入的中孔通常不易控制,材料经常表现随机和非最佳的中孔性。在Janssen等的论文(A.H.Janssen,Angew.Chem.Int.Ed.,40(2001),1102)中,利用三维电子显微镜证明,市售蒸气处理和酸浸沸石Y中的大部分中孔为未最佳连接到沸石结晶的外表面的空穴。显然,对于催化剂,预期相互连接的圆柱形中孔系统比结晶中的中孔空穴更能增强对于反应物的可达性和反应产物的扩散性。
最近,已经出现了另一些方法,作为上述方法的替选。其在于通过碱性介质的处理小心对如此合成的沸石进行脱硅(Ogura M.,Chem.Lett.(2000),82;Ogura M.,Appl.Catal.A Gen.219(2001),33)。硅原子的去除导致沸石结晶中显著量的余孔(extra-porosity)。证实在ZSM-5的情况下,该方法的最佳Si/Al比为25-50(Groen J.C.,J.Phys.Chem.B,108(2004)13062,Groen J.C.,JACS 127(2005),10792)。另一些出版物进行了BEA、FER、MOR的碱处理(Groen JC等,Microporous Mesoporous Materials,69(2004),29)。
当使用这些组合了微孔性和中孔性的分级沸石时,证明对于利用乙烯的苯的烷基化具有提高的催化性能,所述组合了微孔性和中孔性的沸石通过利用有机碱的水溶液对ZSM-5进行脱硅来制备:在微孔的催化剂粉的单个材料中的组合和由于补充中孔网络而改善的运输允许降低至少一部分扩散限制(Perez-Ramirez J等,Appl. Catal.A,364(2009),191-198)。Christensen C.H.等报道了相同的结论JACS,(2003),125,13370-13371。
本申请人发现利用该方法获得并且因此活性部位表现出最佳可达性的催化剂导致由汽油向馏分油转化的增强的催化性能,因此有利于工艺设计:更宽范围的操作条件(较低温度和/或较高LHSV),同时保持更高或至少类似的产率和对中间馏分的选择性。
本发明的第一个目的涉及在存在或不存在芳香族化合物的条件下,通过利用催化剂转化包含4至20个碳原子的烯烃的汽油,以将汽油升级成中间馏分的方法,所述催化剂包含具有允许显著降低扩散限制的组合的微/中孔结构的结晶化合物。
因此本发明涉及由汽油料流制造中间馏分的方法,所述方法包括:
-在存在或不存在包含芳香族化合物的料流的条件下,处理包含4至20个碳原子的烯烃Cn的原料流,
-使所述料流与催化剂在有效地使至少一部分所述烯烃低聚并且最终使至少一部分所述芳香族化合物烷基化的条件下接触,
其中所述催化剂为选自结晶铝硅酸盐、结晶铝磷酸盐、结晶硅-铝磷酸盐(silico-aluminophosphate)、结晶沸石的具有微/中孔结构的结晶化合物,或者所述催化剂为包含至少20重量%的至少一种上述结晶化合物的复合材料,并且其中所述结晶化合物的中孔体积为至少0.22ml/g,优选至少0.25ml/g,最优选至少0.30ml/g。
因为活性位点的更高的可达性,在烯烃转化中使用这些催化剂表现出增强的活性和效率。
优选地,结晶化合物的中孔体积为至少0.2ml/g,更优选为至少0.3ml/g。
优选地,结晶化合物的微孔体积小于或等于0.20ml/g,更优选小于或等于0.17ml/g,最优选小于或等于0.15ml/g。
结晶化合物的中孔体积微孔体积可以大于或等于1,更优选大于或等于2,最优选大于或等于2.5。
关于催化剂
在用到本发明方法中之前,可以将催化剂,特别是沸石结构的微孔-中孔结晶硅酸盐进行以下处理中的一种或若干种:
-任选地,脱铝处理(通过水热方法和/或酸浸),以使得(i)降低材料的酸度(ii)增加(尽管很轻微)原材料的中孔率。这些处理描述在美国专利US5601798中。
-通过包含至少强无机碱(NaOH、KOH)和/或有机碱(例如TMAOH、TPAOH,等)的碱性介质的处理,小心对材料进行脱硅,所述碱性介质的浓度为0.1至2M,优选0.15至1M。碱处理在搅拌下进行,温度为环境温度至100℃,优选至多85℃。
应当将环境温度理解为18℃至25℃的温度,更优选20℃。
碱处理的持续时间可以包括5至120分钟,优选10至60分钟,有利地为15至30分钟。之后将得到的材料过滤,随后可以用大量极性溶剂(例如,纯的软化水)洗涤。
任选地,在过滤步骤之前将所述碱性溶液中和,以停止脱硅反应。实际上,如果脱硅太严重,可能导致沸石结构的结晶的显著损失,这可能导致材料固有活性的降低。
-如果在催化剂制备期间使用了碱或碱性稀土金属,则可以对材料进行离子交换步骤,通常使用铵盐或无机酸。
-之后将催化剂一般地焙烧,例如在大气压力下于400至800℃进行1至10小时。
-任选地,最后使材料进行温和地水热处理,目标是恢复由碱处理引起的结晶缺陷。
如已经提到的,用在本发明方法中的催化剂可以是复合材料,其包含至少20重量%的至少一种选自结晶铝硅酸盐、结晶铝磷酸盐、结晶硅-铝磷酸盐、结晶沸石或其混合物的具有微/中孔结构的结晶化合物。
可以将结晶化合物(如前述最终改进的)与粘合剂、优选无机粘合剂混合,并且定形为期望的形状如小球。选择粘合剂以使得在本发明的反应中对所使用的温度和其他条件具有耐受性。粘合剂优选为无机材料,其选自粘土、二氧化硅、金属硅酸盐、金属氧化物如ZrO2和/或金属、包含二氧化硅和金属氧化物的混合物的凝胶。如果与结晶化合物联合使用的粘合剂其自身为催化活性的,那么这可能改变转化和/或催化剂的选择性。对于粘合剂,非活性物质可以适于作为稀释剂以控制转化的量,从而可以经济并且有目的地获得产物,而不用使用其他控制反应速率的方法。理想的是提供具有好的压碎强度(crush strength)的催化剂。这是因为在商业用途中,期望防止催化剂破碎成粉末状物质。这些粘土或氧化物粘合剂通常仅用于提高催化剂的压碎强度的目的。
用在本发明方法中的结晶化合物优选呈现沸石类型的结构。
在碱处理之前,沸石结构的Si/Al原子比优选为至少15,更优选为至少25,最优选为至少30。
在碱处理之前,沸石结构的Si/Al原子比优选低于60,优选低于50。
优选地,用在本发明中的结晶化合物的中孔体积为至少0.2m/g,最优选为至少0.3ml/g。
优选地,结晶化合物的微孔体积低于或等于0.20ml/g,更优选低于或等于0.17ml/g,最优选低于或等于0.15ml/g。
结晶化合物的微孔体积/中空体积的比率可以大于或等于1,更优选大于或等于2,最优选大于或等于2.5。
结晶化合物可以选自MFI(ZSM-5、硅沸石1、硼硅沸石C、TS-1)、MEL(ZSM-11、硅沸石2,硼硅沸石D、TS-2、SSZ-46)、FER(镁碱沸石、FU-9、ZSM-35)、MTT(ZSM-23)、MWW(MCM-22、PSH-3、ITQ-1、MCM-49)、TON(ZSM-22、Theta-1、NU-10)、EUO(ZSM-50、EU-1)、MTW(ZSM-12)MAZ、SAPO-11、SAPO-5、FAU、LTL、BETAMOR、SAPO-40、SAPO-37、SAPO-41。
优选地,催化剂表现ZSM-5型结构。
关于操作条件
反应优选在以下条件下进行:
-温度125至300℃,优选130至280℃,最优选150℃。
-重量时空速度(WHSV)0.5h-1至5h-1,更优选0.5h-1至3h-1,最优选0.5h-1至2h-1。
-压力为从大气压至200barg,优选15至100barg,最优选15至60barg。
关于原料
本发明的原料通常获自石油精炼或石油化学产品的运作。特别地,其可以获自热裂化或催化裂化的蒸气。
含有烯烃的原料还可以替选地获自烃料流的脱氢作用,所述烃料流获自原油、天然气或油田凝析油(field condensate)的处理。
原料的组成成分(烯烃和芳香族化合物的量、烯烃和芳香族化合物的类型)取决于处理的原料和所使用的条件。处理可以利用获自催化裂化或热裂化的全部汽油级分或可替选的其一部分进行。
还可以考虑料流的混合物,例如还可以考虑重整油和LCN汽油级分。
优选地,原料选自沸点为30至100℃的包含烯烃的汽油如LCCS、或者沸点为30至170℃的烯烃和芳香族化合物的混合物如LCN。
LCCS(Light Catalytic Cracked Spirit,轻催化裂化汽油)的通常的原料组成成分可见于表1,LCN(Light Cracked naphta,轻裂化石脑油)的通常的原料组成成分可见于表2。
表1:LCSS的通常组成成分
表2:LCN的通常组成成分
关于反应器
在反应器内冷却的情况下可以使用多个反应器的系统,这样可以小心控制反应放热,以防止高于正常中等范围的过高温度。
可以是等温或隔热型的固定床,或者一系列这样的反应器,或者活动床反应器。可以在利用一些列平行“摇动”反应器构造的固定床反应器中连续进行低聚/烷基化作用。发现本发明的各种优选催化剂表现出了足够高的稳定性。这使得低聚和烷基化过程能够连续在两个平行“摇动”反应器中进行,其中当一个或两个反应器运行时,其他反应器进行催化剂的再生。本发明的催化剂还可以再生若干次。
本发明的一个目的是利用连续的多阶段催化技术将包含烯烃的料流转化成重烃而成为馏分油。可以在冷却反应器内部的情况下使用多个反应器的系统,这样可以小心控制反应放热,以防止高于正常中等范围的过高温度。有利地,一个反应器内的最大温差不超过75℃.
任选地,可以在中间的闪蒸分离步骤中利用两个阶段之间的压力差异。
利用以下实施例和附图对本发明进行描述而不限制其范围。
图1:脱硅ZSM-5和亲本(parent)样品的吸附-解吸附等温曲线(TPN:标准条件:0℃和760mmHg)。
实施例
微孔-中孔ZSM5的制备
将Zeolyst供应的NH4-形式的、晶粒大小0.1μm的ZSM-5沸石(催化剂A)(Si/Al=40)(CBV 8014)的样品在碱性介质中如下处理:在606ml NaOH(0.2M)中于338K(65℃)剧烈搅拌30分钟。将所得悬浮液在冰水浴中冷却,并且通过加入H2S04(1M)来中和反应介质,直到pH为中性。观察由于溶解的硅原子的沉淀导致的凝胶的形成,并且通过大量软化水的洗涤来去除。之后将重新得到的固体在383K(110℃)干燥过夜。最后,通过在回流中用200ml NH4Cl(0.1M)进行离子交换18小时将经碱处理的样品转化成H-形式。之后将产物在110℃(60℃/h)干燥过夜,之后在空气中于823K(550℃)焙烧6小时。得到催化剂B。
制备的微孔-中孔ZSM-5的性质
催化剂A和B的主要性质归纳如下(表3和图1),并且通过下述方法进行表征。
利用ICP-AES(电感耦合等离子体原子发射光谱)(Perkin-Elmer3000DV)来确定样品的化学组成成分(Si/Al摩尔比率以及Na含量)。
在自动孔隙率仪(Micromeritics Tristar 3000)上测量在77K的N2吸附-解吸附等温线。在测量之前,先将样品在真空中于573K脱气12小时。利用适于等温线的吸附分支的BJH模型(Barett E.P.,Joyner L.G.,Halenda P.P,J.Am.Chem.Soc.1951,73,373-380.Rouquerol F.,RouquerolJ.,Sing K.,Adsorption by Powders and Porous Solids,Academic Press,SanDiego,1991)得到中孔尺寸的分布。利用t-plot法区别微孔和中孔。
图1示出了催化剂A(亲本样品)和B(脱硅的ZSM-5)的氮气吸附/解吸附等温曲线。两种N2等温曲线的比较突显了在中间压力下吸收的增强,表明组合了微孔和中孔的分级孔系统的形成。
如表3所示,中孔体积由0.097ml/g增加至0.327ml/g,而微孔体积由0.161ml/g下降至0.119ml/g。
因此,Si/Al比从46降低至34。
表3亲本和碱处理的沸石的结构特征
a:P/Po=0.99时的体积吸附
b:V中=V总-V微
c:t-plot法
催化剂性能
在由n-庚烷(nC7)和1-己烯(1C6 =)的混合物组成的模型原料的低聚中评价两种催化剂(催化剂A和B)的性能。
使用以下操作条件:55barg(巴(表压)),WHSV(重量时空速度)为1或2h-1,温度为从150到至多200℃。
亲本沸石(催化剂A)和碱处理的样品(催化剂B)的性能呈现在表4中。
表4-在模型原料(nC7/1C6 =)中于55barg,1h-1或2h-1WHSV和不同温度下的产物的不同组的产率
Cx代表具有x个碳原子的烷烃
Cx =代表具有x个碳原子的烯烃
这些结果表明通过使用本发明所定义的呈现特定微/中孔结构的催化剂,成功实现了输入温度的显著降低,而不影响总C6烯烃转化。
这强调了与亲本沸石相比,碱处理的沸石的酸性位点的可达性提高。
相比于亲本沸石,在150℃的温度下,利用碱处理的具有2倍高的WHSV(2h-1相对于1h-1)的ZSM-5实现了更好的烯烃转化。
Claims (7)
1.一种用于从汽油料流中制造中间馏分的方法,所述方法包括:
-在存在或不存在包含芳香族化合物的料流的条件下处理包含4至20个碳原子的烯烃Cn的原料流,
-使所述料流与催化剂在有效地使至少一部分所述烯烃低聚并且最终使至少一部分所述芳香族化合物烷基化的条件下接触,
其中所述催化剂为选自结晶铝硅酸盐、结晶铝磷酸盐、结晶硅-铝磷酸盐、结晶沸石的具有微/中孔结构的结晶化合物,或者所述催化剂为包含至少20重量%的至少一种上述结晶化合物的复合材料,并且其中所述结晶化合物的中孔体积为至少0.22ml/g,优选至少0.25ml/g,和最优选至少0.30ml/g,并且其中将所述催化剂在使用前用碱性介质处理。
2.根据权利要求1所述的方法,其特征在于所述结晶化合物呈现沸石型结构,优选ZSM-5型结构。
3.根据权利要求1或2所述的方法,其特征在于所述碱性介质为浓度0.1至2M,优选0.15至1M的NaOH溶液。
4.根据前述权利要求中任一项所述的方法,其特征在于在125至300℃,优选在130至280℃的温度下进行所述烯烃转化。
5.根据前述权利要求中任一项所述的方法,其特征在于所述烯烃转化的重量时空速度(WHSV)为0.5h-1至5h-1,更优选为1h-1至3h-1,最优选为2h-1。
6.根据前述权利要求中任一项所述的方法,其特征在于在大气压力至200barg,更优选为15至100barg,最优选为15至60barg的压力下进行所述烯烃转化。
7.根据前述权利要求中任一项所述的方法,其特征在于所述原料选自沸点为30至100℃的包含烯烃的汽油如LCCS、或者沸点为30至170℃的烯烃和芳香族化合物的混合物如LCN。
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KR102068312B1 (ko) * | 2013-10-18 | 2020-01-20 | 에스케이이노베이션 주식회사 | 활성화된 eu-2 제올라이트 및 이의 용도 |
US9732285B2 (en) | 2013-12-17 | 2017-08-15 | Uop Llc | Process for oligomerization of gasoline to make diesel |
US9670425B2 (en) | 2013-12-17 | 2017-06-06 | Uop Llc | Process for oligomerizing and cracking to make propylene and aromatics |
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US11149214B2 (en) | 2018-12-17 | 2021-10-19 | Saudi Arabian Oil Company | Method and process to maximize diesel yield |
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FR2931708A1 (fr) * | 2008-05-28 | 2009-12-04 | Inst Francais Du Petrole | Catalyseur a base d'un materiau cristallise a porosite hierarchisee et organisee et son utilisation en oligomerisation des olefines legeres |
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US4150062A (en) | 1976-12-20 | 1979-04-17 | Mobil Oil Corporation | Light olefin processing |
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US4482772A (en) | 1983-11-03 | 1984-11-13 | Mobil Oil Corporation | Multistage process for converting oxygenates to hydrocarbons |
US4506106A (en) | 1984-01-04 | 1985-03-19 | Mobil Oil Corporation | Multistage process for converting oxygenates to distillate hydrocarbons with interstage ethene recovery |
US4543435A (en) | 1985-01-17 | 1985-09-24 | Mobil Oil Corporation | Multistage process for converting oxygenates to liquid hydrocarbons with ethene recycle |
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US5601798A (en) | 1993-09-07 | 1997-02-11 | Pq Corporation | Process for preparing zeolite Y with increased mesopore volume |
US8299312B2 (en) * | 2005-10-28 | 2012-10-30 | Neste Oil Oyj | Process for dimerizing olefins |
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FR2931818A1 (fr) * | 2008-05-28 | 2009-12-04 | Inst Francais Du Petrole | Procede d'oligomerisation des olefines legeres utilisant un catalyseur a base d'un materiau amorphe a porosite hierarchisee et organisee |
FR2931708A1 (fr) * | 2008-05-28 | 2009-12-04 | Inst Francais Du Petrole | Catalyseur a base d'un materiau cristallise a porosite hierarchisee et organisee et son utilisation en oligomerisation des olefines legeres |
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