CN104854220B - 使用itq‑39沸石低聚烯烃的方法 - Google Patents
使用itq‑39沸石低聚烯烃的方法 Download PDFInfo
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- CN104854220B CN104854220B CN201380048760.3A CN201380048760A CN104854220B CN 104854220 B CN104854220 B CN 104854220B CN 201380048760 A CN201380048760 A CN 201380048760A CN 104854220 B CN104854220 B CN 104854220B
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- catalyst
- itq
- oxide
- zeolitic material
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- 239000003054 catalyst Substances 0.000 claims abstract description 53
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- 230000008569 process Effects 0.000 claims description 16
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- -1 ethylene, propylene, Butylene Chemical group 0.000 claims description 12
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- 239000002184 metal Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 10
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- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及在基于ITQ‑39沸石的催化剂存在下使烯烃低聚从而制备柴油馏分内的烃的多相方法。本发明中所述的低聚方法包括至少:a.将包含至少ITQ‑39沸石材料的催化剂进料至反应器中;b.为该反应器供应包含至少一种烯属化合物的料流;和c.使包含至少ITQ‑39材料的催化剂和有机化合物能够在进行该反应所需的时间内保持接触。
Description
说明书。
发明领域
烯烃低聚的多相方法。
背景
轻烯烃,例如丙烯和丁烯的低聚代表不含硫和芳烃的液体合成燃料的主要工业生产和生产的可持续路径。这些方法能够根据催化剂的选择性和操作条件制备汽油或柴油范围内的烯属化合物的混合物。
如本领域现状所述,在高温(> 300℃)和低压(≤30 bar)下,汽油产率提高,而高压和低温有利于形成柴油馏分中的较重低聚物。
采用酸催化剂实现低分子量烯烃低聚成柴油范围内的产品,以这样一种方式使反应机制涉及形成碳正离子。为了获得高品质柴油产品,应该限制支化度,并且这个问题通过两个可能的策略解决:通过改性酸中心(它们的强度或它们环境的强度)或通过应用“形状选择性”的概念,使用具有足够尺寸通道的催化剂以能够控制低聚物生长和其支化度(Catal.Today 77 (2003), 467)。
在文献中,存在很多用于轻烯烃低聚成所报道的中级馏出物的固体酸催化剂。
所述固体磷酸(SPA)被在Ind.Eng. Chem.28 (1936) 1461, Energy Fuels 20 (2006) 439 and 1799, 和Appl.Catal.308 (2006) 204中描述为源自Fischer-Tropsch的用于制备“聚合汽油”和中级馏出物的烯烃低聚的催化剂。中孔材料Si/Al MCM-41也被描述成作为不含烯烃的料流的低聚方法中的催化剂(Catal.Today 75 (2002) 125)。测试含有和不含少量金属(Ni, Rh或Pt)的这些材料。
研究用于烯烃的低聚反应成柴油的其他催化剂为粘土,如Catal.Commun.6 (8) (2005) 25 568和Clay Minerals (3) (1990) 355中所述,杂多酸和其金属盐(Preprints ACS Div. Petrol.Chem.36 (4) 1991) 605)和Appl.Catal.16 (2) (1985) 193中所述的阳离子交换树脂。
证明中孔沸石是最适合在烯烃低聚方法中的高品质中级馏出物的沸石。在文献中报道的最多的研究(例如在AIChE J. 32 (9) (1986) 1526中)基于MFI沸石。此外,在不同的专利中,要求保护了用于该方法的具有10-元环的不同结构。
US4227992和US4211640要求保护作为烯烃低聚方法的催化剂的ZSM-11和提及其他沸石例如ZSM-12、ZSM-21和丝光沸石TEA。GB2106131和GB2106533要求保护质子形式的ZSM-5和ZSM-11用于具有25重量%选择性的轻烯烃低聚成具有75的十六烷值的柴油产品的用途。
在90年代,专利保护了几种中孔沸石和其作为轻烯烃低聚成高品质低聚物和基本上线性低聚物(其可以成为高粘度指数(VI)的润滑油)的催化剂的用途,所述高品质低聚物还可成为具有高十六烷值的柴油和/或具有高添加值的化学中间体。大部分这些沸石被处理成提高其选择性,消除表面酸度,以这样一种方式提高产品的品质,其也被称为选择活化(selectivation)方法。在US5234875中,描述了通过焦化选择活化ZSM-23沸石,当与未改性催化剂比较时大幅提高其得到低支化产品的性能,相比于所述的未改性催化剂大幅提高低支化产品。在US5284989中,描述了采用二元羧酸处理以去活其表面酸度的三种中孔沸石ZSM-22、ZSM-23和ZSM-35,用于在丙烯低聚方法中制备具有低支化度的烃。这些产物可以用作烷基化剂用于制备可生物降解的烷基苯和烷基苯基磺酸酯。
几篇专利(WO95/19945; WO95/22516; US6143942)要求保护不同的中孔沸石例如ZSM-22、ZSM-57、ZSM-5(单独或组合)在轻烯烃低聚方法中的用途。因此,它们能够控制烯烃的低聚度,例如低聚成丙烯三聚物。
在WO93 / 082780中,采用不同含量的可力丁选择活化沸石ZSM-23,并在管状固定床反应器中在丁烯料流的低聚方法中测试。清楚显示了由于选择活化导致的支化度降低,另外观察到通过酸中心去活25至30%实现支化度降低和生成单支化异构体的选择性提高。
US2006/0194999公开了用于低聚方法的催化剂,其包含MWW型酸性沸石作为固体磷酸的取代物,产生对应于具有高辛烷值的汽油馏分产物的产物和其他发动机燃料例如柴油。
提议含有Al和Ti的硅质岩作为轻烯烃低聚成高品质喷射燃料柴油馏分的催化剂(31 Gas Oil (2005) 70; EP0293950; EP1249486)。
FR2887538A1描述了不同的沸石MEL, ITH, MFI, NES, EUO, ERI, FER, CHA,MFS, MWW, MTT, TON和MOR的用途,它们在第一步中预先去铝酸盐化,然后另外添加硅,它们最终转化成其质子或酸形式。
FR2894850A1描述了MEL, ITH, MFI, NES, EUO, ERI, FER, CHA, MFS, MWW,MTT, TON和MOR沸石在用于获得柴油和喷射燃料的低聚方法中的用途。采用系列VIB 和VIII的金属浸渍沸石,然后气相沉积孔径大于沸石孔径的非晶SiO2。使用其酸或质子形式的催化剂。
FR2837199和FR2837213公开了沸石MEL, MFI, NES, EUO, FER, CHA, MFS, MWW,NU-85, NU-86, NU-88 和IM-5在烃转化的多步方法中作为低聚步骤的催化剂的用途。
WO2002/36491公开了UZM-4沸石作为低聚方法中的催化剂的用途,但该专利不包括催化应用的实例。
WO2007/079038描述了SSZ-74沸石催化剂在低聚方法中的用途,但该文献不包括催化应用的实例。
本发明涉及在WO2008/092984中描述的基于使用含有ITQ-39的催化剂的烯烃低聚方法,其中该催化剂不仅非常活泼,而且其提高柴油馏分的选择性,并且与迄今为止报道的其他催化剂相比对具有反应时间(TOS: 接触时间)的去活高度稳定。
发明描述
在一般方式中,本发明描述制备沸点在柴油的通常范围内的烃馏分的方法,其在于使进料与一种或多种烯烃与催化剂在某种条件下接触。
本发明涉及制备烃的烯烃低聚方法,该方法包括:
a. 将包含至少所述沸石材料ITQ-39的催化剂引入反应器中;
b. 向所属反应器进料包含至少一种烯属化合物的料流;
c. 使包含至少所述ITQ-39材料的催化剂和有机化合物能够保持接触进行该反应所需的时间。
优选地,所获得的烃可以用作燃料,最优选地,他们是柴油馏分中的烃。
在优选的实施方案中,所述烯属化合物优选选自乙烯、丙烯、丁烯类、戊烯类、己烯类或它们的混合物。此外,此类烯属化合物可以10至100重量%的优选浓度存在于所述料流中。
在优选的实施方案中,将所述烯烃料流进料至反应器,其可以至少部分来自精制方法。
根据另一优选实施方案,所获得的产品可以为柴油范围内的液体燃料。
所述沸石材料ITQ-39 (P200700334)以其煅烧状态anhidrous具有以下组成,其通过以下实验式给出:
其中M选自H+、具有电荷+ n的无机阳离子和其混合物,X为至少一种+3氧化态的化学元素,Y为+4氧化态的非Si的至少第二化学元素,x为0至0.3的值,y为0至0.1的值,其中合成材料具有X射线衍射图,其至少具有如表I中所述的角2θ(度)和相对强度(I/I0)的值:
其中“vs”是指60-100的相对强度,“s”是指40-60的相对强度,“m”是指20-40的相对强度,“w”是指0-20的相对强度,以百分比形式测定,取决于最大强度峰,h是指作为肩出现的衍射峰。
所述沸石材料ITQ-39,在煅烧除去在内部堵塞的有机物质之后,具有X射线衍射图,其至少具有如表II所示的角2θ (度)和相对强度(I / I0)的值:
其中,vs, s, m, w和h具有与表1所述的相同含义。
所述沸石材料ITQ-39可以从包含至少SiO2源、一种或多种选自Ge, Ti, Sn, V和其混合物的四价元素Y的源、一种或多种选自Al, B, Ga, Fe, Cr和其混合物的三价元素X的源、带有电荷n+的无机阳离子M的源、具有方案1中所述结构的有机双阳离子SDA-1的源的反应混合物起始合成:
。
方案1
氟离子和水源,在80至200℃的温度下加热所述反应混合物直到获得结晶,形成多微孔结晶沸石材料ITQ-39,其中所述材料具有以下组成范围:
SDA-1(OH)2/SiO2=0.01-1.0,
M1/nOH/SiO2=0-0-1,
X2O3/SiO2=0-0.15,
YO2/SiO2=0-0.1,
F/SiO2=0.1-3.0, y
H2O/SiO2=0.5-50。
为了除去堵塞在结晶多微晶结构内的有机材料并由此获得酸形式的沸石,如上所述的合成沸石可以加热至高于250℃的温度,持续2分钟至25小时的时间或经历提取过程或这两种处理的组合。
在本发明的具体实施方案中,所述沸石材料ITQ-39可以其酸形式使用,其中全部阳离子交换中心实际上都被质子占据。
在另一具体实施方案中,所述沸石材料ITQ-39的酸度可以部分被中和。根据其中ITQ-39可以其部分酸形式使用的该实施方案,所述沸石的一些阳离子交换中心被碱性阳离子而非质子占据,所述碱性阳离子优选选自第IA族和第IIA族质子的金属阳离子(参见EP2386354)。离子交换中心中的阳离子的量可以为1至99%(摩尔),优选2至95%,更优选3至90%,甚至更优选为10至85%其中优化的中和水平取决于起始沸石的二氧化硅/氧化铝比和所选择的碱性阳离子。碱性阳离子可以在沸石合成期间添加或可以在本领域现状所熟知的合成后处理中添加。优选地,所使用的阳离子选自锂、钠、钾、铷、铯和其混合物,优选钠、钾、铯和其混合物。
根据本发明的具体实施方案,所述沸石材料ITQ-39也可以包含另外的阳离子,其可以为任何稳定金属或有机阳离子,但优选选自V, Cr, Mn, Fe, Co, Ni, Cu , Zn, Mo,W, Y, Ti, Ga, 稀土元素(例如Ce和La), 铵离子和其组合。
在其他实施方案中,如果需要的话,所述沸石材料ITQ-39,为酸形式或其部分中和的形式,可以采用表面改性剂(在本发明中的称为选择活化方法),例如二元羧酸例如草酸、大体积有机分子(参见例如US4520221和US4568786)、可力丁或大体积螯合剂/多价螯合剂例如氨基羧酸盐(例如乙二胺四乙酸(EDTA)、二亚乙基三胺五乙酸、羟基乙基亚乙基二胺三乙酸盐)和氨基磷酸盐或氨基膦酸盐(例如氨基三亚甲基磷酸盐、四亚甲基亚乙基二氨基膦酸盐)或六卤代硅酸盐处理。通过使用所述表面改性剂的该选择活化方法的目的是降低沸石晶体外的铝的含量或消除其含量,从而去活所述沸石材料的外表面。所考虑的其他选择活化方法为通过采用本领域现状下熟知的硅酸化剂例如SiCl4或任何六氟硅酸盐处理的选择性焦化方法或选择活化方法。
根据另一具体实施方案,所述ITQ-39沸石材料可以通过在25℃或更高的温度下采用pH大于8的水溶液处理所述材料进行足够长时间改性以生成次级中孔隙(WO2011/002630)。
根据具体实施方案,所述沸石材料itq-39改性生成另外的中孔隙。
在其他实施方案中,如果需要的话,所述沸石材料ITQ-39,其中次级中孔隙通过在pH>8,在25℃或更高的温度下在水溶液中处理生成,可以通过表面改性剂例如二元羧酸、大体积有机分子例如可力丁、或大体积络合剂例如EDTA选择活化。具有次级中孔隙的ITQ-39沸石催化剂的外表面也可以通过选择性焦化处理或采用本领域现状下已知的硅酸化剂例如SiCl4或任何六氟硅酸盐进行选择性去活。
根据优选的实施方案,所述沸石材料ITQ-39通过上述选择活化方法去活。优选地,选择活化可以通过采用草酸处理或采用乙二胺四乙酸(EDTA)处理完成。
根据优选的实施方案,基于ITQ-39沸石使用的催化剂可以通过至少一种基质形成,所述基质包含至少一种金属氧化物,该金属氧化物可以选自非晶氧化物、低结晶率氧化物、或其组合。优选地,所述氧化物可以选自氧化铝、二氧化硅-氧化铝、二氧化硅、粘土、氧化镁、氧化钛、氧化硼、氧化锆、氧化钒、氧化铬、氧化钼、氧化锰、氧化锌、氧化铁、氧化镍、氧化钴、氧化钨、氧化锑、氧化铈、氧化镧和其他可以使用的稀土氧化物,优选选自氧化铝、二氧化硅-氧化铝、二氧化硅、粘土、氧化镁、氧化钛、氧化硼、氧化锆和其组合,更优选γ-氧化铝。
此外,所述基质也可以包含至少磷酸铝、磷酸锆、煤、铝酸盐和其组合。
优选地,基于沸石ITQ-39的催化剂的基质包含至少一类二氧化硅、氧化铝、二氧化硅-氧化铝或其组合,优选γ-氧化铝。也可以使用本领域现状下所熟知的粘合剂。
根据本发明的具体实施方案,基于所述ITQ-39沸石的催化剂可以另外包含过渡金属,例如V, Cr, Mn氢化金属(hydrogenating metal)或本领域现状下所述的任何物质,例如第VIII族金属或它们几种的组合。这些第VIII族金属的引入可以通过一个或多个离子交换步骤或通过浸渍技术或通过溶液中过量前体进行,它们全部是本领域现状下所熟知的技术。此外,第VIII族金属的源可以为相应的硝酸盐、磷酸盐、碳酸盐、卤化物或它们的组合。
根据本发明的具体实施方案,基于ITQ-39的沸石催化剂可以进一步包含至少一种第VIII族金属或它们的多于一种的组合。优选地,所述金属选自铱、钌、铑、铼、钯、铂、铁、钴、镍和其组合。
根据本发明的另一具体实施方案,所述催化剂可以进一步包含至少一种促进剂,该促进剂选自磷、硼和其组合,优选地所述促进剂为磷。这些促进剂可以使用本领域现状下已知的任何技术引入所述催化剂中。根据该具体方案,一种可以用作源H3PO4, (NH4)H2PO4,(NH4)2HPO4或其组合。
根据另一优选的实施方案,所述催化剂可以包含至少一种第VIIA族元素,优选氟。
此外,基于沸石ITQ-39的催化剂可以可用于工业规模应用的任何形态形成,例如挤出物、丸、球和尤其通过“喷射干燥”方法获得的微球。
通常,基于ITQ-39的本发明的沸石催化剂可以具有相对于总催化剂重量的以下组成:
- 0.1至99 wt%的沸石材料ITQ-39;
- 0.1至99 wt%的基质;
- 0至20%的本领域现状下通常定义的氢化金属,例如第VIII族金属。
在优选的实施方案中,组成百分比为:
- 0.5至90 wt%的沸石材料ITQ-39;
- 0.1至75 wt%的基质;
- 0至10%的氢化金属。
根据另一更优选的实施方案,组成百分比为:
- 1-85 wt%的沸石材料ITQ-39;
- 0.1至60 wt%的基质;
- 0至5%的氢化金属。
本发明的基于沸石ITQ-39的催化剂可以进一步包含最多30%,优选最多20%的其他促进剂、或尤其是粘合剂。
根据具体实施方案,本发明中所使用的进料由至少一种2至10个碳,更优选3至7个碳的烯烃构成。这些烯属化合物可以选自乙烯、丙烯、丁烯类、戊烯类或其混合物。这些烯烃可以选自乙烯、丙烯、丁烯类、戊烯类或其混合物。这些烯烃可以纯形式使用或与其他组分例如烷烃(正丙烷、正丁烷或戊烷)或惰性气体例如氮气混合。根据具体实施方案,烯烃应该为混合物料流的10至100重量%,优选25至100重量%的比例。
所述进料料流的化合物可以来自不同的源,例如油、天然气、来自生物量的进料和转化方法如Fischer-Tropsch和其他技术例如气-液(气-液)。此外,所述料流可以含有氢气,优选0.1至80%摩尔百分比的料流,更优选0.5至50%。
根据具体实施方案,所述烯属料流可以从精制方法例如LPG料流、催化裂解产品、或Fischer-Tropsch单元的产品,从生物燃料加工单元、尤其是甲烷至液体烃的加工工厂至少部分地除去。
本发明所述的低聚方法可以连续模式通过使所述料流与所述催化剂在固定床反应器中或在流化床反应器中接触进行。在固定床反应器的情况下,可以使用任何已知的构造,例如并联操作的多个床,以这样一种方式使得在它们中的一些中进行反应,而在其他床中再生催化剂。在流化床的情况下,也可以进行所述反应从而能够从反应区除去催化剂以使其进入再生循环。
根据优选实施方案,所述低聚方法可以在100至500℃,优选在120 至400℃,更优选在150至350℃的温度下,在0.1至200 bar,优选在2至150 bar,更优选在5至80 bar的压力下,在0.1至100 h-1,优选0.25至50 h-1的催化剂上料流的空间速度(WHSV)下进行。
根据本发明的方法获得的烃馏分可以包含多于10重量%,优选多于35重量%,最优选多于50重量%的化合物,其在大气条件下具有在柴油燃料通常范围内沸点(127至427℃),它们优选为C10至C24 (174至391℃)的化合物。此外,根据本发明的方法获得的烃馏分可以经历后处理,例如馏分蒸馏以回收纯柴油和所获得的馏分的氢化。
在优选的实施方案中,本发明的方法在氢气存在下进行。
本发明还涉及包含至少沸石材料ITQ-39的催化剂在用于制备柴油馏分内的烃的烯烃低聚方法中的用途。
后文的实施例意在为本发明示例和提供更好的理解,但在任何情况下都不受限制。
附图简要描述
图1:在200℃, 40 bar下和0.08h的接触时间τ下,在存在于60:40 (摩尔比)的混合物丙烯:丙烷中的丙烯低聚中,烯烃转化率与反应时间的函数(接触时间, TOS),采用商业来源的沸石ITQ-39和ZSM-5获得。
图2:在200℃, 40 bar下和0.08h的接触时间τ下,在存在于60:40 (摩尔比)的混合物丙烯:丙烷中的丙烯低聚中,累积的C5+液体馏分中的选择性(TOS = 0-3 h和TOS = 3-6 h),采用 ITQ-39沸石和采用商业来源的ZSM-5沸石获得。
实施例
实施例1 二氢氧化物形式的双阳离子的制备
按照以下方案中描述的通常方法合成有机双阳离子SDA:
在通常方法中,进行1-丙基-4-哌啶酮(化合物A)与吡咯烷(化合物B)的还原胺化反应,导致形成相应的二胺(化合物C)。通过转化为SDA双阳离子(化合物D)的乙基卤化物季化二胺。
更具体地,所述有机双阳离子制备如下:
将21.600g的吡咯烷溶解于250ml的甲醇中,该溶液采用HCl (5 M 在甲醇中)酸化至pH = 7.2,在0℃下在外部浴中连续冷却所述混合物。然后,加入14.30 g的1-丙基-吡咯烷酮,然后加入5.14 g的NaBH3CN。将所得混合物保持在室温下搅拌72小时。
将HCl (5 M在甲烷中)缓慢加入该混合物中,直到通过氮气的连续料流移动HCN实现低于2的pH。通过旋转蒸发浓缩所得溶液,添加KOH (25 wt%)的溶液,直到实现大于12的pH。在这个阶段,出现白色沉淀。所得混合物被NaCl饱和并添加至水中。最后,采用乙醚萃取二胺1-丙基-4-吡咯啉-1-基-哌啶,并经无水MgSO4干燥同时搅拌。
如下进行二胺的季化:将65.68 g的碘乙烷添加至19.11 g二胺在150 ml乙醇中的溶液。48小时之后,加入另外的30.80 g的碘乙烷。将所述混合物保持在回流下搅拌并通过外部浴加热至85℃。通过旋转蒸发仪浓缩所述溶液。
几小时之后形成半固体相。添加20 ml甲醇以将其溶解,并将乙醚用于固体沉淀,其在真空下过滤。
根据以下方法使用离子交换树脂采用氢氧化物交换阳离子碘:将61.13 mmol的阳离子碘溶解于水中。将165 g的Amberlite IRN-78树脂添加至所得溶液中并在搅拌下保持所述混合物直到下一天。然后过滤该样品,用超纯水洗涤并获得二氢氧化物溶液。使用酚酞作为指示剂采用HCl水溶液滴定二氢氧化物,获得大于60%的交换效率。最终溶液含有0.47当量氢氧化物/1000 g溶液。
实施例2:沸石材料ITQ-39的合成
将1883 g异丙醇铝添加至28,753 g正硅酸四乙酯(TEOS)。然后,添加在之前实施例中获得146.910 g溶液。在搅拌的同时使所述混合物蒸发直到完全除去从TEOS水解形成的乙醇。在该点添加2.92 g的HF (48 wt%)。通过在外部浴中搅拌和加热除去水以获得凝胶的最终组成,其为:
其中,所述SDA为实施例1中所述的双阳离子。
将所述凝胶引入具有内部聚四氟乙烯夹套的不锈钢高压釜中并在135℃下静态加热35天。采用蒸馏的水和丙酮洗涤通过过滤分离之后获得的固体。
在表III中示出合成材料的XRD图。
实施例3:通过煅烧沸石材料ITQ-39进行的活化
在空气流动中在580℃下将如实施例2中所述获得的沸石材料ITQ-39煅烧3小时。在表IV中示出煅烧材料的XRD图。
实施例4:沸石ITQ-39作为用于丙烯低聚的催化剂的用途
将如实施例3中所述煅烧的沸石材料ITQ-39转化成丸,研磨并筛分成0.2-0.4 mm的粒度。将丸形式的0.5 g该样品采用SiC (0.4-0.6 mm)稀释以获得4.0 cm3的床体积。将所述混合物装载到不锈钢固定床反应器中,通过Gilson活塞泵以液相将进料料流C3 =: C3(60:40摩尔比)进料至反应器中。在反应期间,通过气动阀电子Badger控制压力。通过具有其位于催化床内部的相应热电偶的两个独立加热区控制在催化床中的温度。
在开始低聚实验之前,通过在20 ml/min的N2的流体中升高温度至520℃煅烧,并在200 ml / min的空气流体中在520℃下煅烧5小时将催化剂原位活化。
在T = 473 K, P = 40 bar下和0.08 h的接触时间τ中进行低聚实验,涉及烯烃。
在图1中,将如本专利中所述的采用ITQ-39沸石材料获得随反应时间(TOS)进行的丙烯转化率变化与在与ITQ-39相同条件下测试的商用ZSM-5(Si/Al = 11, 通过TRICAT以铵形式供应)的那种比较。可以清楚地看出ITQ-39如何最初更有活性,并且相比于商用ZSM-5随着TOS以较低的去活速度去活。
在图2中示出在反应器出口处收集的,在0至3小时和3至6小时TOS的反应时间内累积的液体产品中的不同馏分的选择性。结果示出基于沸石ITQ-39的催化剂比商用ZSM-5对于需要的柴油馏分更具选择性。
Claims (19)
1.制备烃的烯烃低聚方法,其特征在于该方法包括至少:
a.在反应器中引入包含至少沸石材料ITQ-39的催化剂;
b.向该反应器进料包含至少一种烯属化合物的料流,所述烯属化合物选自乙烯、丙烯、丁烯类、戊烯类、己烯类或其混合物;
c.使包含至少所述ITQ-39材料的催化剂与所述料流接触。
2.根据权利要求1的方法,其特征在于所述烯属化合物以10-100重量%的浓度存在于所述料流中。
3.根据权利要求1或2的方法,其特征在于所述沸石材料ITQ-39为其酸形式。
4.根据权利要求1或2的方法,其特征在于所述沸石材料ITQ-39改性形成另外的中孔隙。
5.根据权利要求1或2的方法,其特征在于所述沸石材料ITQ-39的外表面采用表面改性剂处理选择性去活化。
6.根据权利要求5的方法,其特征在于所述沸石材料ITQ-39通过采用草酸处理选择性去活化。
7.根据权利要求5的方法,其特征在于所述沸石材料ITQ-39通过采用乙二胺四乙酸处理选择性去活化。
8.根据权利要求1或2的方法,其特征在于所使用的催化剂包含通过至少一种选自非晶氧化物、低结晶度氧化物和其组合的氧化物形成的基质。
9.根据权利要求8的方法,其特征在于所述氧化物选自氧化铝、二氧化硅-氧化铝、二氧化硅、粘土、氧化镁、氧化钛、氧化硼、氧化锆、和其组合。
10.根据权利要求9的方法,其特征在于所述基质为γ-氧化铝。
11.根据权利要求9的方法,其特征在于所述基质包含至少磷酸铝、磷酸锆、煤、铝酸盐和其组合。
12.根据权利要求1或2的方法,其特征在于所述催化剂包含至少一种第VIII族氢化金属,所述金属选自铱、钌、铑、铼、钯、铂、铁、钴、镍和其组合。
13.根据权利要求1或2的方法,其特征在于所述催化剂包含至少促进剂,该促进剂选自磷、硼和其组合。
14.根据权利要求13的方法,其特征在于所述促进剂为磷。
15.根据权利要求1或2的方法,其特征在于所述催化剂包含至少第VIIA族元素。
16.根据权利要求12的方法,其特征在于所述催化剂包含至少第VIIA族元素。
17.根据权利要求1或2的方法,其特征在于该方法在100至500℃的温度,在0.1至200bar的压力下并在0.1-100h-1的重时空速下进行。
18.根据权利要求1或2的方法,其特征在于该方法在氢气存在下进行。
19.包含至少沸石材料ITQ-39的催化剂在选自乙烯、丙烯、丁烯类、戊烯类、己烯类或其混合物的烯烃低聚的方法中的用途。
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PCT/ES2013/000172 WO2014013102A1 (es) | 2012-07-19 | 2013-07-12 | Proceso de oligomerización de alquenos utilizando la zeolita itq-39 |
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