Catalytic cracking of 1-butene to propene and ethene on MCM-22 zeolite

Catalytic cracking of butene to propene and ethene was investigated over HMCM-22 zeolite. The performance of HMCM-22 zeolite was markedly influenced by time-on-stream (TOS) and reaction conditions. A rapid deactivation during the first I h reaction, followed by a quasi-plateau in activity, was observed in the process along with significant changes in product distributions, which can be attributed to the fast coking process occurring in the large supercages of MCM-22.

Butene catalytic cracking to propene and ethene over potassium modified ZSM-5 catalysts

Catalytic cracking of butene over potassium modified ZSM-5 catalysts was carried out in a fixed-bed microreactor. By increasing the K loading on the ZSM-5, butene conversion and ethene selectivity decreased almost linearly, while propene selectivity increased first, then passed through a maximum (about 50% selectivity) with the addition of ca. 0.7-1.0% K, and then decreased slowly with further increasing of the K loading. The reaction conditions were 620 degrees C, WHSV 3.5 h(-1), 0.1 MPa 1-butene partial pressure and 1 h of time on stream. Both by potassium modification of the ZSM-5 zeolite and by N(2) addition in the butene feed could enhance the selectivity towards propene effectively, but the catalyst stability did not show any improvement. On the other hand, addition of water to the butene feed could not only increase the butene conversion, but also improve the stability of the 0.7%K/ZSM-5 catalyst due to the effective removal of the coke formed, as demonstrated by the TPO spectra. XRD results indicated that the ZSM-5 structure of the 0.07% K/ZSM-5 catalyst was not destroyed even under this serious condition of adding water at 620 degrees C.

适用于裂解制造乙烯的气体动力学加热方法

对乙烷裂解制造乙烯的非平衡过程进行了分析，为了获得高的乙烯产率，需准确控制裂解停留时间并提高裂解反应温度。探讨了目前工业生产中普遍采用的管式裂解炉的特性及局限。这种管式裂解炉的性能虽已接近完善，但仍不能满足裂解工艺需求。对几种利用激波控制加热方法生产乙烯的发明及其不足进行了评述。提出新颖的反向超声速射流混合加热方法。该方法能满足裂解制造乙烯的要求。

Isoprene polymerization with indolide-imine supported rare-earth metal alkyl and amidinate complexes

Reaction of 7-{(N-2,6-R)iminomethyl)}lindole (HL1, R = dimethylphenyl; HL2, R = diisopropylphenyl) and rare-earth metal tris(alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), generated new rare-earth metal bis(alkyl) complexes LLn(CH2SiMe3)(2)(THF) [L = L-1: Ln = Lu. (1a), Sc (1b); L = L-2 : Ln = Lu (3a), Se (3b)] and mono(alkyl) complexes L-2 Lu-2(CH2SiMe3) (4a). Treatment of alkyl complexes 1a and 4a with N,N'-diisopropylcarbodiimide afforded the corresponding amidinates (LLu)-Lu-1{iPr(2)NC(CH2SiMe3) NiPr2}(2) (2a) and L-2 Lu-2{iPr(2)NC(CH2SiMe3)NiPr2} (5a), respectively.

Facile, Efficient Copolymerization of Ethylene with Bicyclic, Non-Conjugated Dienes by Titanium Complexes Bearing Bis(beta-Enaminoketonato) Ligands

Copolymerizations of ethylene with 5-vinyl-2-norbornene or 5-ethylidene-2-norbornene under the action of various titanium complexes bearing bis(beta-enaminoketonato) chelate ligands of the type, [(RN)-N-1=C(R-2)CH=C(R-3)O](2)TiCl2 (1, R-1=Ph, R-2=CF3, R-3=Ph; 2, R-1=C6H4F-p, R-2=CF3, R-3=Ph; 3, R-1=Ph, R-2=CF3, R-3=t-Bu; 4, R-1=C6H4F-p, R-2=CF3, R-3=t-Bu; 5, R-1=Ph, R-2=CH3, R-3=CF3; 6, R-1=C6H4F-p, R-2=CH3 R-3=CF3), have been shown to occur with the regioselective insertion of the endocyclic double bond of the monomer into the copolymer chain, leaving the exocyclic vinyl double bond as a pendant unsaturation. The ligand modification strongly affects the copolymerization behaviour. High catalytic activities and efficient co-monomer incorporation can be easily obtained by optimizing the catalyst structures and polymerization conditions.

Highly Active Neutral Nickel(II) Catalysts for Ethylene Polymerization Bearing Modified,beta-Ketoiminato Ligands

A series of novel neutral nickel complexes 4a-e bearing modified beta-ketoiminato ligands [(2,6-(Pr2C6H3)-Pr-i)N=C(R-1)CHC(2 '-R2C6H4)O]Ni(Ph)(PPh3) (4a, R-1 R-2 = H; 4b, R-1 = H, R-2 = Ph; 4c, R-1 = H, R-2 = Naphth; 4d, R-1 = CH3, R-2 = Ph; 4e, R-1 = CF3, R-2 Ph) have been synthesized and characterized. Molecular structures of 4b and 4e were further confirmed by X-ray crystallographic analysis. Activated with B(C6F5)(3), all the complexes are active for the polymerization of ethylene to branched polyethylenes. Ligand structure, i.e., substituents R-1 and R-2, greatly influences not only catalytic activity but also the molecular weight and branch content of the polyethylene produced. The phenyl-substituted complex 4b exhibits the highest activity of lip to 145 kg PE/mol(Ni)center dot h center dot atm under optimized conditions, which is about 10 times more than unsubstituted complex 4a (14.0 kg PE/mol(Ni center dot)h center dot atm). Highly branched polyethylene with 103 branches per 1000 carbon atoms has been prepared using catalyst 4e.

Synthesis and characterization of the titanium complexes bearing two regioisomeric trifluoromethyl-containing enaminoketonato ligands and their behavior in ethylene polymerization

A series of new titanium complexes bearing two regioisomeric trifluoromethyl-containing enaminoketonato ligands (3a-h and 6a-h), [PhN=CRCHC(CF3)O](2)TiCl2 (3a, R = Me; 3b, R = n-C5H11; 3c, R = i-Pr; 3d, R = Cy; 3e, R = t-Bu; 3f, R = CH=CHPh; 3g, R = Et; 3h, R = n-C11H23) and [PhN=C(CF3)CHC(R)O](2)TiCl2 (6a, R = Ph; 6b, R = n-C5H11; 6c, R = i-Pr; 6d, R = Cy; 6e, R = t-Bu; 6f, R = CH=CHPh; 6g, R = CHPh2; 6h, R = CF3) have been synthesized and characterized. X-ray crystal structures analyses suggest that complexes 3c-e and 6c-d all adopt a distorted octahedral geometry around the titanium center. Complexes 3c, 3d and 6c display a cis-configuration of the two chlorine atoms around the titanium center, while complex 6d shows a trans-configuration of the two chlorine atoms. Especially, the configurational isomers (cis and trans) of complex 3e were identified both in solution and in the solid state by NMR and X-ray analyses. With modified methylaluminoxane as a cocatalyst, all the complexes are active towards ethylene polymerization, and produce high molecular weight polymers.

Achiral lanthanide alkyl complexes bearing N,O multidentate ligands. Synthesis and catalysis of highly heteroselective ring-opening polymerization of rac-lactide

Alkane elimination reactions of amino-amino-bis(phenols) H2L1-4, Salan H2L5, and methoxy-beta-diimines HL6,7 with lanthanide tris(alkyl) s, Ln(CH2SiMe3)(3)(THF)(2) (Ln = Y, Lu), respectively, afforded a series of lanthanide alkyl complexes 1-8 with the release of tetramethylsilane. Complexes 1-6 are THF-solvated mono( alkyl) s stabilized by O, N, N, O-tetradentate ligands. Complexes 1-3 and 5 adopt twisted octahedral geometry, whereas 4 contains a tetragonal bipyramidal core. Bearing a monoanionic moiety L-6 (L-7), complex 7 ( 8) is a THF-free bis(alkyl). In complex 7, the O, N, N-tridentate ligand combined with two alkyl species forms a tetrahedral coordination core. Complexes 1, 2, and 3 displayed modest activity but high stereoselectivity for the polymerization of rac-lactide to give heterotactic polylactide with the racemic enchainment of monomer units P-r ranging from 0.95 to 0.99, the highest value reached to date. Complex 5 exhibited almost the same level of activity albeit with relatively low selectivity. In contrast, dramatic decreases in activity and stereoselectivity were found for complex 4. The Salan yttrium alkyl complex 6 was active but nonselective. Bis(alkyl) complexes 7 and 8 were more active than 1-3 toward polymerization of rac-LA, however, to afford atactic polylactides due to di-active sites. The ligand framework, especially the "bridge" between the two nitrogen atoms, played a significant role in governing the selectivity of the corresponding complexes via changing the geometry of the metal center.

Synthesis of the first rare earth metal bis(alkyl)s bearing an indenyl functionalized N-heterocyclic carbene

Treatment of indenyl-modified imidazolium bromide [C9H7CH2CH2(NCHCHN(C6H2Me3-2,4,6)CH)Br] ((IndH-NHC-H)Br) with rare earth metal tetra(alkyl) lithium (Ln(CH2SiMe3)(4)Li(THF)(4)) or with (trimethylsilylmethyl)lithium (LiCH2SiMe3) and rare earth metal tris(alkyl)s (Ln(CH2SiMe3)(3)(THF)(2)) sequentially afforded the first NHC-stabilized monomeric rare earth metal bis(alkyl) complexes (Ind-NHC)Ln(CH2SiMe3)(2) (1, Ln = Y; 2, Ln = Lu; 3, Ln = Sc) via double-deprotonation reactions. Complexes 1-3 are THF-free isostructural monomers. The monoanionic Ind-NHC species bond to the central metal ion in a eta(5):kappa(1) constrained geometry configuration (CGC) mode, which combine with the two cis-located alkyl moieties to form a tetrahedron ligand core, leading to the chirality of the complexes. Under the presence of activators AlEt3 and [Ph3C][B(C6F5)(4)], complex 2 showed catalytic activity toward the polymerization of isoprene to afford 3,4-regulated polyisoprene (91%).