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The quantitative structure-property relationship (QSPR) of constrained geometry catalysts (CGCs) has been analyzed by combining density functional theory (DFT) and multivariate linear regression (MLR). QSPR models for determining the reaction energy barriers of ethylene and 1-octene and molecular descriptors were established and validated with a testing set. At the initiation stage, the quaternary QSPR models for ethylene and 1-octene feature R² values of 0.90 and 0.82, respectively, while the corresponding leave-one-out Q² values for ethylene and 1-octene are determined to be 0.82 and 0.69. Using the generated QSPR models, the electronic effect was proven to be more critical for determining the energy barriers of ethylene and 1-octene insertion processes. At the propagation stage, the quaternary QSPR models for ethylene and 1-octene feature R² values of 0.97 and 0.96, respectively, while the corresponding leave-one-out Q² values for ethylene and 1-octene are determined to be 0.93. Particularly, the impact of the steric effect on the energy barriers of ethylene and 1-octene insertion is more pronounced. Furthermore, the correlation between the corresponding energy barriers and experimental activities with three series of CGCs was discussed, which revealed that theoretical calculations are consistent with the experimental results. [ABSTRACT FROM AUTHOR]

In order to reduce the waste heat emission and environmental impact of industrial processes, Organic Rankine Cycle (ORC) is gradually used for energy recovery. ORC is regarded as the most promising measure for converting low-grade heat into electricity, but commercial applications are still limited due to the high investments and poor economic returns. However, the simultaneous optimization of ORC and Heat Integration can improve system economy. This work proposes a techno-economic optimization model involving the area estimate of heat exchanger based on vertical heat transfer for optimization of ORC and Heat Integration. This model determines the selection of working fluids, the optimal operating parameters of ORC including temperatures, pressures, and flowrate of working fluids. Both of the supercritical and subcritical conditions can be considered in this model. To solve this optimization problem, a bi-level optimization approach is developed, where the outer level uses Genetic Algorithm to identify the promising working fluids and optimize the temperatures and pressures of ORC, and the inner level is an NLP model to find the optimal flowrate of ORC and the vertical matches of streams by minimizing total annual cost. The results represent the necessity of simultaneous optimization of Organic Rankine Cycle and Heat Integration. [ABSTRACT FROM AUTHOR]

Soluble poly[styrene- co-(acrylic acid)] (PSA) modified by magnesium compounds was used to support TiCl4. For ethylene polymerization, four catalysts were synthesized, namely PSA/TiCl4, PSA/MgCl2/TiCl4, PSA/( n-Bu)MgCl/TiCl4, and PSA/( n-Bu)2Mg/TiCl4. The catalysts were characterized by a set of complementary techniques including X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, and element analysis. Synthesis mechanisms of polymer-supported TiCl4 catalysts were proposed according to their chemical environments and physical structures. The binding energy of Ti 2p in PSA/TiCl4 was extremely low as TiCl4 attracted excessive electrons from COOH groups. Furthermore, the chain structure of PSA was destroyed because of intensive reactions taking place in PSA/TiCl4. With addition of ( n-Bu)MgCl or ( n-Bu)2Mg, COOH became COOMg- which then reacted with TiCl4 in synthesis of PSA/( n-Bu)MgCl/TiCl4 and PSA/( n-Bu)2Mg/TiCl4. Although MgCl2 coordinated with COOH first, TiCl4 would substitute MgCl2 to coordinate with COOH in PSA/MgCl2/TiCl4. Due to the different synthesis mechanisms, the four polymer-supported catalysts correspondingly showed various particle morphologies. Furthermore, the polymer-supported catalyst activity was enhanced by magnesium compounds in the following order: MgCl2 > ( n-Bu)MgCl > ( n-Bu)2Mg > no modifier. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 [ABSTRACT FROM AUTHOR]

Reactor blends of ultrahigh-molecular-weight polyethylene (UHMWPE) and low-molecular-weight polyethylene (LMWPE) were synthesized by two-step polymerization using a hybrid catalyst. To prepare the hybrid catalyst, styrene acrylic copolymer (PSA) was first coated onto SiO/MgCl-supported TiCl; then, ( n-BuCp)ZrCl was immobilized onto the exterior PSA. UHMWPE was produced in the first polymerization stage with the presence of 1-hexene and modified methylaluminoxane (MMAO), and the LMWPE was prepared with the presence of hydrogen and triethylaluminium in the second polymerization stage. The activity of the hybrid catalyst was considerable (6.5 × 10 g PE (mol Zr) h), and was maintained for longer than 8 h during the two-step polymerization. The barrier property of PSA to the co-catalyst was verified using ethylene polymerization experiments. The appearance of a lag phase in the kinetic curve during the first-stage polymerization implied that the exterior catalyst (( n-BuCp)ZrCl) could be activated prior to the interior catalyst (M-1). Furthermore, the melting temperature, crystallinity, degree of branching, molecular weight and molecular-weight distribution of polyethylene obtained at various polymerization times showed that the M-1 catalyst began to be activated by MMAO after 40 min of the reaction. The activation of M-1 catalyst led to a decrease in the molecular weight of UHMWPE. Finally, the thermal behaviors of polyethylene blends were investigated using differential scanning calorimetry. Copyright © 2011 Society of Chemical Industry A hybrid catalyst was supported on an inorganic/organic support for use in the preparation of polymer blends with ultrahigh-molecular-weight polyethylene in the first reaction stage and low-molecular-weight polyethylene in the second reaction stage. Fragmentation of the styrene acrylic copolymer (PSA) support was studied. [ABSTRACT FROM AUTHOR]

Hybrid titanium catalysts supported on silicapolystyrenecoacrylic acid SiO2PSA coreshell carrier were prepared and studied. The resulting catalysts were characterized by Fourier transform infrared FTIR spectroscopy, laser scattering particle analyzer and scanning electronic microscope SEM. The hybrid catalyst TiCl3MgCl2THFSiO2·TiCl4MgCl2PSA showed coreshell structure and the thickness of the PSA layer in the two different hybrid catalysts was 2.0 μm and 5.0 μm, respectively. The activities of the hybrid catalysts were comparable to the conventional titaniumbased ZieglerNatta catalyst TiCl3MgCl2THFSiO2. The hybrid catalysts showed lower initial polymerization rate and longer polymerization life time compared with TiCl3MgCl2THFSiO2. The activities of the hybrid catalysts were enhanced firstly and then decreased with increasing PH2PC2H4. Higher molecular weight and broader molecular weight distribution MWD of polyethylene produced by the coreshell hybrid catalysts were obtained. Particularly, the hybrid catalyst with a PSA layer of 5.0 μm obtained the longest polymerization life time with the highest activity 2071 kg PE mol−1Ti h−1 and the resulting polyethylene had the broadest MWD polydispersity index 11.5 under our experimental conditions. The morphology of the polyethylene particles produced by the hybrid catalysts was spherical, but with irregular subparticles due to the influence of PSA layer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [ABSTRACT FROM AUTHOR]

The coabsorptions of ethylene and iso‐pentane, and ethylene and n‐hexane were measured by the use of a pressure decay method. The solubility data of ethylene‐iso‐pentane and ethylene‐n‐hexane in semicrystalline polyethylene (PE) of crystallinity of 48.6% were obtained at temperatures 70, 80, and 90 °C, and the total pressure 2 MPa, iso‐pentane partial pressure 80–190 KPa, n‐hexane partial pressure 20–90 KPa. The presence of iso‐pentane or n‐hexane in the corresponding ternary system leads to increase the solubility of ethylene, while the solubility of iso‐pentane or n‐hexane remains unchanged with an increase of the ethylene partial pressure, even slightly decreases. Assumed that the presence of iso‐pentane or n‐hexane decreases the crystallinity of the polymer sample, a coabsorption model was built to model the solubility of each gas in the ternary systems. The relative root mean square errors of the coabsorption model for ethylene‐iso‐pentane‐PE system and ethylene‐n‐hexane‐PE system are 5.13% and 4.64%, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3654–3662, 2007 [ABSTRACT FROM AUTHOR]

Diffusion coefficients of four organic solvents: dichloromethane, trichloromethane, tetrachloromethane and n-hexane in polyethylene particles at infinite dilution were determined by use of inverse gas chromatography (IGC). The polymer particles were used as supplied by the producer to pack the chromatographic columns. This allowed a direct measurement of the interested properties in a particle with the same morphology obtained at the reactor outlet. The particle morphology was investigated and classical mathematical model for chromatographic process was adopted based upon the analysis of particle microstructure. It was found that the limitation step for mass transfer was in the polymer matrix rather than in macropores, and when interpreted in terms of diffusion coefficients for spherical particles, the measured diffusion coefficients compared favourably with predicted values from literature relationships and free volume theory. [ABSTRACT FROM AUTHOR]

An absorption model of gases in semicrystalline polymer was built that was based on the activity coefficient theory in polymer solution and associated with crystallinity dependent on temperature. The solubility of ethylene, isopentane, and n‐hexane in three types of polyethylene (PE) were obtained by the use of a pressure‐decay method at temperatures of 333–363 K and pressures of up to 2 MPa, 80–300 KPa, and 19–100 KPa, respectively. Experimental data from three gases in each PE sample were used for the single‐parameter fitting, and fitting error was within about 12%. It was found that a single parameter was merely dependent on the properties of PE used. It was shown that, unlike with the Flory–Huggins model and the UNIFAC–M‐H method, correlation between the crystallinity of the semicrystalline polymer and temperature had to be taken into account in order for the solubility data of alkane, olefin, and aromatic hydrocarbons in polyethylene to fit well, especially in the temperature range near the melting point of the polymer. The four free‐energy contributions to the total gas activity were experimentally determined to be about 47%–60% combined, the free‐volume contribution about 12%–25%, and the elastic effect about 22%–35%, but the interactional contribution was zero. The contributions changed with the size of the gas molecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1737–1744, 2007 [ABSTRACT FROM AUTHOR]

A letter to the editor is presented in response to the article "Unified Conceptual Approach to Targeting and Design of Water and Hydrogen Networks," by V. Agrawal and W. Shenoy that was published in a 2006 issue.