Hierarchical porous mussel shells as soil amendment for oil spill remediation.

In this work, a new type of micromesoporous substance was prepared with fatty alcohol-polyoxyethylene ether (AEO) surfactant freezing penetration and pyrolysis using shells as raw materials. The obtained material exhibited good adsorbability and could be added to oil-contaminated soil to adsorb the pollutant, which resulted in the regeneration of the initially polluted soil. It was determined that the main component of the developed substance was CaCO3. Importantly, the conducted experiments revealed that the obtained mussel micromesoporous material displayed certain adsorption effects toward petroleum hydrocarbons in a diesel solution. Moreover, it was found that chemical adsorption was more optimal than physical adsorption. The soil remediation effect was the best when the content of the mussel micromesoporous material in the soil was 400 g/kg. Under these conditions, the removal rate of petroleum hydrocarbon was established at 49.38%. This study indicated that micromesoporous material has great potential in the application of oil contaminated soil remediation.

Assessment of the Multiphase Mechanical Properties of the Longmaxi Formation Shale Using Nanoindentation Tests.

Mechanical properties are some of the most important parameters for understanding well drilling and hydraulic fracturing designs in unconventional reservoir development. As an effective tool, nanoindentation has been used to determine the mechanical properties of rocks at the nanoscale. In this study, the Longmaxi Formation shale samples from the Yibin area of China were collected and analyzed to obtain the multiphase mechanical properties. The mineral compositions and organic geochemistry of the shale samples were studied using X-ray diffraction, energy-dispersive X-ray spectrometry, and a carbon/sulfur analyzer. The pore structures of the shale samples at the micro- and nanoscales were characterized by field-emission scanning electron microscopy. The mechanical parameters of the shale samples, such as the hardness and elastic modulus, were investigated using the nanoindentation method to identify three mineral phases: brittle minerals, soft matters, and complex minerals at the interfaces between brittle minerals and soft matters. The uncertainty characteristics of the mechanical parameters of the three mineral phases were evaluated using the Weibull model, and the factors interfering with the mechanical parameters were analyzed for the different shale samples. The results showed that the brittle minerals had the largest recovered elastic deformations and the smallest residual deformations, while the soft matters had the largest residual deformations and the smallest recovered elastic deformations. The analysis results of the coefficients of variation and the Weibull modulus both confirmed that the scatter of the hardness was higher than that of the elastic modulus because of the uncertain contact area, and the hardness and elastic modulus of the soft matters had the highest uncertainty among the three mineral phases. The elastic modulus increased nonlinearly with increasing hardness according to a power function for the whole shale sample. The elastic modulus and hardness both had a favorable linear relationship with the total organic carbon (TOC) content, illustrating that the TOC content was one of the significant factors that affected the mechanical parameters of the shale samples.

Experimental study on flow characteristics of gas transport in micro- and nanoscale pores.

Gas flow behavior in porous media with micro- and nanoscale pores has always been attracted great attention. Gas transport mechanism in such pores is a complex problem, which includes continuous flow, slip flow and transition flow. In this study, the microtubes of quartz microcapillary and nanopores alumina membrane were used, and the gas flow measurements through the microtubes and nanopores with the diameters ranging from 6.42 µm to 12.5 nm were conducted. The experimental results show that the gas flow characteristics are in rough agreement with the Hagen-Poiseuille (H-P) equation in microscale. However, the flux of gas flow through the nanopores is larger than the H-P equation by more than an order of magnitude, and thus the H-P equation considerably underestimates gas flux. The Knudsen diffusion and slip flow coexist in the nanoscale pores and their contributions to the gas flux increase as the diameter decreases. The slip flow increases with the decrease in diameter, and the slip length decreases with the increase in driving pressure. Furthermore, the experimental gas flow resistance is less than the theoretical value in the nanopores and the flow resistance decreases along with the decrease in diameter, which explains the phenomenon of flux increase and the occurrence of a considerable slip length in nanoscale. These results can provide insights into a better understanding of gas flow in micro- and nanoscale pores and enable us to exactly predict and actively control gas slip.

Enhanced Oil Recovery by a Suspension of Core-Shell Polymeric Nanoparticles in Heterogeneous Low-Permeability Oil Reservoirs.

Polymeric nanoparticle suspension is a newly developed oil-displacing agent for enhanced oil recovery (EOR) in low-permeability reservoirs. In this work, SiO2/P(MBAAm-co-AM) polymeric nanoparticles were successfully synthesized by a simple distillation-precipitation polymerization method. Due to the introduction of polymer, the SiO2/P(MBAAm-co-AM) nanoparticles show a favorable swelling performance in aqueous solution, and their particle sizes increase from 631 to 1258 nm as the swelling times increase from 24 to 120 h. The apparent viscosity of SiO2/P(MBAAm-co-AM) suspension increases with an increase of mass concentration and swelling time, whereas it decreases as the salinity and temperature increase. The SiO2/P(MBAAm-co-AM) suspension behaves like a non-Newtonian fluid at lower shear rates, yet like a Newtonian fluid at shear rates greater than 300 s-1. The EOR tests of the SiO2/P(MBAAm-co-AM) suspension in heterogeneous, low-permeability cores show that SiO2/P(MBAAm-co-AM) nanoparticles can effectively improve the sweep efficiency and recover more residual oils. A high permeability ratio can result in a high incremental oil recovery in parallel cores. With an increase of the permeability ratio of parallel cores from 1.40 to 15.49, the ratios of incremental oil recoveries (low permeability/high permeability) change from 7.69/4.61 to 23.61/8.46. This work demonstrates that this SiO2/P(MBAAm-co-AM) suspension is an excellent conformance control agent for EOR in heterogeneous, low-permeability reservoirs. The findings of this study can help to further the understanding of the mechanisms of EOR using SiO2/P(MBAAm-co-AM) suspension in heterogeneous, low-permeability reservoirs.

The kinetics of propene and hexene polymerisation with [(SBI)ZrR]+X-: evidence for monomer-dependent early or late transition states.

Whereas the rates of propene polymerisation catalysed by zirconocene ion pairs are strongly anion-dependent, hexene polymerisations are not; the findings demonstrate the existence of very different kinetic regimes for two closely related reactions.

Zirconocene-catalyzed propene polymerization: a quenched-flow kinetic study.

The kinetics of propene polymerization catalyzed by ansa-metallocenes were studied using quenched-flow techniques. Two catalyst systems were investigated, (SBI)ZrMe2/Al(i)Bu3/[Ph3C][CN[B(C6F5)3]2] (1:100:1) at 25.0 degrees C and (SBI)ZrCl(2)/methylalumoxane at 40.0 degrees C (Al:Zr = 2400:1) (SBI = rac-Me(2)Si(1-Indenyl)2). The aims of the study were to address fundamental mechanistic aspects of metallocene-catalyzed alkene polymerizations, catalyst initiation, the quantitative correlation between catalyst structure and the rate of chain propagation, and the nature of dormant states. One of the most important but largely unknown factors in metallocene catalysis is the distribution of the catalyst between dormant states and species actively involved in polymer chain growth. Measurements of polymer yield Y versus reaction time t for propene concentrations [M] = 0.15-0.59 mol L(-1) and zirconocene concentrations in the range [Zr] = (2.38-9.52) x 10(-5) mol L(-1) for the borate system showed first-order dependence on [M] and [Zr]. Up to t approximately 1 s, the half-life of catalyst initiation is comparable to the half-life of chain growth; that is, this phase is governed by non-steady-state kinetics. We propose a rate law which takes account of this and accurately describes the initial rates. Curve fitting of Y(t) data provides an apparent chain growth rate constant k(p)(app) on the order of 10(3) L mol(-1) s(-1). By contrast, the evolution with time of the number-average polymer molecular weight, which is independent of the concentration of catalyst involved, leads to a k(p) which is an order of magnitude larger, (17.2 +/- 1.4) x 10(3) L mol(-1) s(-1). The ratio k(p)(app)/k(p) = 0.08 indicates that under the given conditions only about 8% of the total catalyst is actively engaged in chain growth at any one time. The system (SBI)ZrCl(2)/methylalumoxane is significantly less active, k(p)(app) = 48.4 +/- 2.7 and k(p) = (6 +/- 2) x 10(2) L mol(-1) s(-1), while, surprisingly, the mole fraction of active species is essentially identical, 8%. Evidently, the energetics of the chain growth sequence are strongly modulated by the nature of the counteranion. Increasing the counteranion/zirconium ratio from 1:1 to 20:1 has no influence on catalyst activity. These findings are consistent with a model of closely associated ion pairs throughout the chain growth sequence. For the borate system, propagation is approximately 6000 times faster than initiation, while for the MAO catalyst, k(p)/k(i) approximately 800. Polymers obtained at 25 degrees C show 0.1-0.2 mol % 2,1-regioerrors, and end-group analysis identifies 2,1-misinsertions as the main cause for chain termination (66%), as compared to 34% for the vinylidene end groups. The results suggest that 2,1-regioerrors are a major contributor to the formation of dormant species, even at short reaction times.