Nickel-Exchanged Zincosilicate Catalysts for the Oligomerization of Propylene

Two nickel-containing zincosilicates (Ni-CIT-6 and Ni–Zn-MCM-41) and two nickel-containing aluminosilicates (Ni-HiAl-BEA and Ni-USY) are synthesized and used as catalysts to oligomerize propylene into C_(3n) (C_6 and C_9) products. Both Ni-CIT-6 and Ni-HiAl-BEA have the *BEA topology and are investigated to assess the effects of framework zinc versus aluminum because the former gives two framework charges per atom, whereas the latter, only one. Ni-CIT-6 and Ni–Zn-MCM-41 enable the comparison of a microporous to a mesoporous zincosilicate. Ni^2+ ion-exchanged into zeolite Y has been previously reported to oligomerize propylene and is used here for comparison. Reaction data are obtained at 180 and 250 °C, atmospheric pressure, and WHSV = 1.0 h^–1 in a feed stream of 85 mol % propylene (in inert). At these conditions, all catalysts are capable of oligomerizing propylene with steady-state conversions ranging from 3 to 16%. With the exception of Ni-HiAl-BEA, all catalysts have higher propylene conversions at 250 °C than at 180 °C. Both *BEA materials exhibit similar propylene conversions at each temperature, but Ni-HiAl-BEA is not as selective to C_3n products as Ni-CIT-6. Zincosilicates demonstrate higher average selectivities to C_3n products than the aluminosilicates at both reaction temperatures tested. Hexene products other than those expected by simple oligomerization are present, likely formed by double-bond isomerization catalyzed at acid sites. Additionally, both of the aluminosilicate materials catalyzed cracking reactions, forming non-C_3n products. The reduced acidity of the zincosilicates relative to the aluminosilicates likely accounts for higher C_(3n) product selectivity of the zincosilicates. Zincosilicates also exhibited higher linear-to-branched hexene isomer ratios (typically 1.0–1.5) when compared with the aluminosilicates, which had ratios on the order of 0.3. The mesoporous zincosilicate shows the best reaction behavior (including C_(3n) product selectivity: ∼99% at both temperatures for Ni–Zn-MCM-41) of the catalytic materials tested here

Facile Preparation of Aluminosilicate RTH across a Wide Composition Range Using a New Organic Structure-Directing Agent

RTH type zeolite (aluminosilicate) is a potentially useful catalytic material that is limited by the inability to easily prepare the material over a wide composition range. Here, we report the use of pentamethylimidazolium to prepare aluminosilicate RTH across a wide range of compositions in both fluoride and hydroxide inorganic systems. RTH type zeolites are crystallized with a calcined product Si/Al of 7–27 from fluoride media and 6–59 from hydroxide media. The use of this new, simple organic structure-directing agent that can be prepared in one step allows for dramatic improvement in the compositional space where aluminosilicate RTH can be formed. RTH is tested as a catalyst for the methanol-to-olefins reaction and at complete conversion shows a high propylene/ethylene ratio of 3.9 at a propylene selectivity of 43%

Organic-Free Synthesis of CHA-Type Zeolite Catalysts for the Methanol-to-Olefins Reaction

Chabazite (CHA)-type zeolites are prepared from the hydrothermal conversion of faujasite (FAU)-type zeolites, dealuminated by high-temperature steam treatments (500–700 °C), and evaluated as catalysts for the methanol-to-olefins (MTO) reaction. The effects of temperature and partial pressure of water vapor during steaming are investigated. Powder X-ray diffraction (XRD) and Ar physisorption data show that the steam treatments cause partial structural collapse of the zeolite with the extent of degradation increasing with steaming temperature. ^(27)Al MAS NMR spectra of the steamed materials reveal the presence of tetrahedral, pentacoordinate, and octahedral aluminum. NH_3 and i-propylamine temperature-programmed desorption (TPD) demonstrate that steaming removes Brønsted acid sites, while simultaneously introducing larger pores into the CHA materials that make the remaining acid sites more accessible. Acid washing the steamed CHA-type zeolites removes a significant portion of the extra-framework aluminum, producing an increase in the bulk Si/Al ratio as well as the adsorption volume. The proton form of the as-synthesized CHA (Si/Al = 2.4) rapidly deactivates when tested for MTO at a reaction temperature of 400 °C and atmospheric pressure. CHA samples steamed at 600 °C performed the best among the samples tested, showing increased olefin selectivities as well as catalyst lifetime compared to the unsteamed CHA. Both lifetime and C_2–C_3 olefin selectivities are found to increase with increasing reaction temperature. At 450 °C, CHA steamed at 600 °C reached a combined C_2–C_3 olefin selectivity of 74.2% at 100% methanol conversion, with conversion remaining above 80% for more than 130 min of time-on-stream (TOS) before deactivating. More stable time-on-stream behavior is observed for 600 °C-steamed CHA that underwent acid washing: conversion above 90% for more than 200 min of TOS at 450 °C with a maximum total C_2–C_3 olefin selectivity of 71.4% at 100% conversion

Synthesis of RTH-Type Zeolites Using a Diverse Library of Imidazolium Cations

RTH-type zeolites are promising catalytic materials for applications that include the important methanol-to-olefins (MTO) and NO_x reduction reactions. Here, RTH-type zeolites are prepared using a wide-range of imidazolium-based, cationic organic structure directing agents (OSDAs), that greatly expand the methodologies and compositions that can be used to synthesize these materials. The abilities of the OSDAs to produce RTH-type zeolites agree well with results from molecular modeling studies of predicted stabilization energies of the OSDAs in the RTH framework. The RTH-type zeolites are stable to steaming up to 900 °C and are shown to be active MTO catalysts

Facile Synthesis and Catalysis of Pure-Silica and Heteroatom LTA

Zeolite A (LTA) has many large-scale uses in separations and ion exchange applications. Because of the high aluminum content and lack of high-temperature stability, applications in catalysis, while highly desired, have been extremely limited. Herein, we report a robust method to prepare pure-silica, aluminosilicate (product Si/Al = 12–42), and titanosilicate LTA in fluoride media using a simple, imidazolium-based organic structure-directing agent. The aluminosilicate material is an active catalyst for the methanol-to-olefins reaction with higher product selectivities to butenes as well as C_5 and C_6 products than the commercialized silicoalumniophosphate or zeolite analogue that both have the chabazite framework (SAPO-34 and SSZ-13, respectively). The crystal structures of the as-made and calcined pure-silica materials were solved using single-crystal X-ray diffraction, providing information about the occluded organics and fluoride as well as structural information

Highly Active Mixed-Metal Nanosheet Water Oxidation Catalysts Made by Pulsed-Laser Ablation in Liquids

Surfactant-free mixed-metal hydroxide water oxidation nanocatalysts were synthesized by pulsed-laser ablation in liquids. In a series of [Ni-Fe]-layered double hydroxides with intercalated nitrate and water, [Ni_(1–x)Fe_x(OH)_2](NO_3)_y(OH)_(x−y)·nH_2O, higher activity was observed as the amount of Fe decreased to 22%. Addition of Ti^(4+) and La^(3+) ions further enhanced electrocatalysis, with a lowest overpotential of 260 mV at 10 mA cm^(–2). Electrocatalytic water oxidation activity increased with the relative proportion of a 405.1 eV N 1s (XPS binding energy) species in the nanosheets

I. Nickel-Exchanged Zincosilicate Catalysts for the Oligomerization of Propylene and II. Organic SDA-Free Catalysts for the Methanol-to-Olefins Reaction

Nickel-containing catalysts are developed to oligomerize light olefins. Two nickel-containing zincosilicates (Ni-CIT-6 and Ni-Zn-MCM-41) and two nickel-containing aluminosilicates (Ni-HiAl-BEA and Ni-USY) are synthesized as catalysts to oligomerize propylene into C3n (C6 and C9) products. All catalysts oligomerize propylene, with the zincosilicates demonstrating higher average selectivities to C3n products, likely due to the reduced acidity of the Zn heteroatom. To test whether light alkanes can be incorporated into this oligomerization reaction, a supported homogeneous catalyst is combined with Ni-containing zincosilicates. The homogeneous catalyst is included to provide dehydrogenation/hydrogenation functions. When this tandem catalyst system is evaluated using a propylene/n-butane feed, no significant integration of alkanes are observed. Ni-containing zincosilicates are reacted with 1-butene and an equimolar propylene/1-butene mixture to study other olefinic feeds. Further, other divalent metal cations such as Mn2+, Co2+, Cu2+, and Zn2+ are exchanged onto CIT-6 samples to investigate stability and potential use for other reactions. Co-CIT-6 oligomerizes propylene, albeit less effectively than Ni-CIT-6. The other M-CIT-6 samples, while not able to oligomerize light olefins, may be useful for other reactions, such as deNOx. Molecular sieves are synthesized, characterized, and used to catalyze the methanol-to-olefins (MTO) reaction. The Al concentration in SSZ-13 samples is varied to investigate the effect of Al number on MTO reactivity when compared to a SAPO-34 sample with only isolated Si Brønsted acid sites. These SSZ-13 samples display reduced transient selectivity behavior and extended reaction lifetimes as Si/Al increases; attributable to fewer paired Al sites. MTO reactivity for the higher Si/Al SSZ-13s resembles the SAPO-34 sample, suggesting that both catalysts owe their stable reaction behavior to isolated Brønsted acid sites. Zeolites CHA and RHO are prepared without the use of organic structure-directing agents (OSDAs), dealuminated by steam treatments (500°C-800°C), and evaluated as catalysts for the MTO reaction. The effects of temperature and steam partial pressure during steaming are investigated. X-ray diffraction (XRD) and Ar physisorption show that steaming causes partial structural collapse of the zeolite, with degradation increasing with steaming temperature. 27Al MAS NMR spectra of steamed materials reveal the presence of tetrahedral, pentacoordinate, and hexacoordinate aluminum. Proton forms of as-synthesized CHA (Si/Al=2.4) and RHO (Si/Al=2.8) rapidly deactivate under MTO testing conditions (400°C, atmospheric pressure). CHA samples steamed at 600°C performed best among samples tested, showing increased olefin selectivities and catalyst lifetime. Acid washing these steamed samples further improved activity. Reaction results for RHO were similar to CHA, with the RHO sample steamed at 800°C producing the highest light olefin selectivities. Catalyst lifetime and C2-C3 olefin selectivities increase with increasing reaction temperature for both CHA-type and RHO-type steamed samples.</p