High-Performance Carbon Molecular Sieve Membranes Derived from a PPA-Cross-linked Polyimide Precursor for Gas Separation.

Carbon molecular sieve (CMS) membranes have emerged as attractive gas membranes due to their tunable pore structure and consequently high gas separation performances. In particular, polyimides (PIs) have been considered as promising CMS precursors because of their tunable structure, superior gas separation performance, and excellent thermal and mechanical strength. In the present work, polyphosphoric acid (PPA) was employed as both cross-linker and porogen, it created pores within the PI polymeric matrix, while it also effectively acting as a cross-linker to regulate the ultramicropores of the CMS membranes, thus simultaneously improving both permeability and selectivity of the CMS membranes. By employing PI/PPA hybrid with PPA content of 5 wt % as a precursor, the obtained CMS membrane exhibited a CO2 and He permeability of 1378.3 Barrer and 1431.4 Barrer, respectively, which was an approximately 10-fold increase compared to the precursor membrane. Under optimized conditions, the CO2/CH4 and He/CH4 selectivity of the obtained CMS membrane reached 81.5 and 89.9, respectively, which was 278% and 307% higher than that of the pristine PI membrane. In addition, the membrane exhibited good long-term stability during a one-week continuous test. This study clearly denoted PPA can be used for precisely tailoring the ultramicroporosity of CMS membranes.

Preparation of Manganese Blending-Modified Activated Coke for Flue Gas Desulfurization.

In this study, the preparation and desulfurization application of MnO2 and pyrolusite blending-modified activated cokes (ACM and ACP) were studied. Thermodynamic calculation shows that the blended metal oxides could be reacted with the solid carbon and gaseous products H2, CO, and CO2 for activation. The physicochemical properties of the blending-modified ACP and ACM responded considerably differently to preparation conditions. The blended metal oxide significantly improved the mesoporous structure of the modified activated cokes, as well as the surface acidic and basic functional groups. Different metal oxides played different roles in the pore structure and surface functional group evolution, and the current investigation indicates that MnO2 is more favorable than pyrolusite. The enhanced acidic and basic functional groups, coupled with the catalysis of metal oxides, improved the desulfurization performance of the modified activated cokes. The sulfur capacities of the prepared ACP and ACM were 47.9-208.9 and 119.4-205.9 mg/g, respectively, which were much greater than the sulfur capacity of the fresh activated coke.

Spinal Cord Diffuse Midline Gliomas With H3 K27m-Mutant: Clinicopathological Features and Prognosis.

BACKGROUND: "Diffuse midline glioma, H3 K27M-mutant" (DMG) mainly arises within the pontine, thalamic, and spinal cord regions. Because of the rarity of spinal cord gliomas, the general knowledge surrounding DMGs is mainly based on pontine and thalamic gliomas, whereas tumor location tends to influence the clinicopathological features and prognosis. OBJECTIVE: To determine the clinicopathological characteristics and molecular profiles of DMGs located in the spinal cord. METHODS: The clinical and molecular pathologic features and prognosis were comprehensively analyzed in a series of 44 patients with spinal cord DMGs. RESULTS: The median age was 36 yr, and 88.7% of patients (39/44) were adults (≥18 yr). Histopathologically, malignant grades included grade II (16 cases), grade III (20 cases), and grade IV (8 cases). Compared with patients with histological grade IV, patients with lower histological grade (grade II/III) were older (37 vs 24 yr, P = .020) and were associated with longer overall survival (24.1 vs 8.6 mo, P = .007). All 30 tested tumors were isocitrate dehydrogenase (IDH) wild type, and 96% of cases (22/23) presented with unmethylated O6-methylguanine-DNA methyltransferase. Univariate and multivariate analyses showed that histological grade and presurgery McCormick Scale scores were independent prognostic factors for overall survival, whereas extensive surgical resection and chemoradiotherapy were not significantly associated with improved survival. The most frequent anatomic locations were the cervical enlargement (C4-T1, n = 16) and conus medullaris (T12-L1, n = 13), which exhibited distinctive clinical characteristics and molecular features. CONCLUSION: The findings provide guidelines for the evidence-based practice of the specialized management of spinal cord DMGs.

Co-blending modification of activated coke using pyrolusite and titanium ore for low-temperature NOx removal.

Activated coke (AC) has great potential in the field of low-temperature NO removal (DeNOx), especially the branch prepared by blending modification. In this study, the AC-based pyrolusite and/or titanium ore blended catalysts were prepared and applied for DeNOx. The results show blending pyrolusite and titanium ore promoted the catalytic performance of AC (Px@AC, Tix@AC) clearly, and the co-blending of two of them showed a synergistic effect. The (P/Ti-1/2)15@AC performed the highest NO conversion of 66.4%, improved 16.9% and 16.0% respectively compared with P15@AC and Ti15@AC. For the (P/Ti-1/2)15@AC DeNOx, its relative better porous structure (SBET = 364 m2/g, Vmic = 0.156 cm3/g) makes better mass transfer and more active sites exposure, stronger surface acidity (C-O, 19.43%; C=O, 4.16%) is more favorable to the NH3 adsorption, and Ti, Mn and Fe formed bridge structure fasted the lactic oxygen recovery and electron transfer. The DeNOx of (P/Ti-1/2)15@AC followed both the E-R and L-H mechanism, both the gaseous and adsorbed NO reacted with the activated NH3 due to the active sites provided by both the carbon and titanium.

Clinicopathological characteristics and survival of spinal cord astrocytomas.

BACKGROUND: Due to their rarity, the clinicopathological characteristics and prognostic factors of spinal cord gliomas are still unclear. Here, we aimed to clarify these issues in a cohort of 108 spinal cord astrocytomas. METHODS: We characterized the clinicopathological characteristics, including 2016 World Health Organization (WHO) grade, age, sex, location, segment length, resection, pre- and postsurgery, Modified McCormick Scale (MMS), radio- and chemotherapy, and Ki-67 and H3 K27M mutations, in 108 spinal cord astrocytomas through heatmaps. The Cox regression analysis and Kaplan-Meier curves were used to study the prognostic value of these clinicopathological features. RESULTS: There are a total 38 H3 K27M-mutant tumors, including 31 cases with histological grade II/III tumors. The age of low-grade astrocytoma patients (WHO grade I/II, n = 54) was significantly younger (27.0 vs 35.5 years, P = .001) than those with high-grade tumors (WHO grade III/IV, n = 54). All patients underwent surgical resection with neurophysiological monitoring, and the surgery did not result in significant changes in MMS. The presurgery MMS was associated with overall survival in the high-grade subgroup (P = .008) but not in the low-grade subgroup (P = .312). While, the high content of resection improved the survival of only patients with low-grade astrocytomas (P = .016) but not those with high-grade astrocytomas (P = .475). Both the low-grade and high-grade astrocytomas had no obvious benefit from neither adjuvant chemotherapy nor radiotherapy (all P > .05). CONCLUSIONS: We characterized the clinicopathological characteristics and their prognostic values in 108 spinal cord astrocytomas, which could help with evidence-based management of spinal cord astrocytomas.

Simultaneous removal of NH3-N and COD from shale gas distillate via an integration of adsorption and photo-catalysis: A hybrid approach.

In view of the circulation cooling water (CCW) quality for refining and petrochemical enterprises, distillates obtained from shale gas produced water after alkali precipitation, filtration and multi-effect evaporation required further purification to remove NH3-N and COD. Illumination, adsorption, photocatalysis after adsorption equilibrium (AP) and integration of adsorption and photocatalysis (IOAP) were carried out to optimize the distillates treatment. AP and IOAP treatments were feasible for the simultaneous removal of NH3-N and COD from the target distillate, while IOAP treatment had much better adaptability and practicability due to its economic cost and easy operation. In IOAP, the removal rate of COD and NH3-N was high up to 59.0% and 88.9%, respectively, under Xenon lamp illumination (25 A) for 60 min with 10 g/L zeolite. The residual concentration of COD and NH3-N were 73.9 mg/L and 23.0 mg/L, respectively, which could well meet the CCW quality. Furthermore, the results of zeolites characterization (SEM-EDX, BET and FTIR) and kinetics analysis showed that the removal of COD in IOAP process mainly depended on the effect of photocatalysis excited by zeolite, while the removal of NH3-N was in virtue of the synergistic effect of photocatalysis and adsorption.

Preparation of high-yield N-doped biochar from nitrogen-containing phosphate and its effective adsorption for toluene.

Novel biochar was prepared from plant-based biomass by the addition of nitrogen-containing phosphates (NCPs), including ammonia phosphate (AP), ammonia polyphosphate (APP) and urea phosphate (UP). The results demonstrated that with the addition of NCPs, the yield of biochar could be significantly increased from about 30% to up to about 60%. The pore structure of the biochar was significantly improved, and the AP-prepared biochar obtained a higher S BET and V tot of 798 m2 g-1 and 0.464 cm3 g-1, respectively. Moreover, the surface chemistry of the NCP-prepared biochar was affected, and N heteroatoms could be successfully doped on the surface of biochar, up to 4.16%. Furthermore, through TG-FTIR and XPS analysis, some possible interactions between plant-based biomass and NCPs during the pyrolysis process were proposed to explore the mechanisms of the preparation process, including the P route and N route, in which the H3PO4 and NH3 gradually generated during the heating process played the dominant roles for the high yield N-doped biochar. All the NCP-prepared biochar presented good toluene adsorption capacities from 175.9 to 496.2 mg g-1, which were significantly higher than that of blank char (6.5 mg g-1).

The control of H2S in biogas using iron ores as in situ desulfurizers during anaerobic digestion process.

In this study, five kinds of iron ores, limonite, hematite, manganese ore, magnetite and lava rock, were used as the in situ desulfurizers in the anaerobic digestion reactors to investigate their effects on controlling H2S in biogas. The results show that the addition of the five iron ores could significantly control the content of H2S in biogas, with the best performance for limonite. As limonite dosages increase (10-60 g/L), the contents of H2S in biogas were evidently decreased in the digesters with different initial sulfate concentrations (0-1000 mg/L). After the anaerobic digestion, the removed sulfur was mostly deposited on the surface of limonite. A possible mechanism of H2S control in biogas by limonite was proposed preliminarily, including adsorption, FeS precipitation, and Fe (III) oxidation. The results demonstrated that limonite was a promising in situ desulfurizer for controlling H2S in biogas with low cost and high efficiency.

Physicochemical characteristics and desulphurization activity of pyrolusite-blended activated coke.

In this study, a novel activated coke (AC-P) was prepared by the blending method using bituminous coal as the raw material and pyrolusite as the catalyst. The physicochemical properties of prepared activated coke (AC) were characterized by BET, Fourier-Transform Infrared Spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The results indicated that the blended pyrolusite had a slight effect on the structural properties of AC, while the oxygenated functional groups on AC were increased and MnO2 and Fe2O3 in pyrolusite were reduced to MnO and Fe on the AC-P samples, respectively. All the AC-P samples significantly improved the removal of SO2, with the highest sulphur capacity (153 mg/g) for the AC blended with 8 wt% pyrolusite, which was 57.7% higher than that of the blank activated cock. This could be mainly attributed to the change in surface chemical properties of the AC-P samples and the active catalytic components in pyrolusite for the catalytic oxidation of SO2 in desulphurization process.

[Flue gas desulfurization by a novel biomass activated carbon].

A novel biomass columnar activated carbon was prepared from walnut shell and pyrolusite was added as a catalyst. The activated carbon prepared was used for flue gas desulphurization in a fixed-bed reactor with 16 g of activated carbon. The impact of operating parameters such as SO2 inlet concentration, space velocity, bed temperature, moisture content and O2 concentration on the desulfurization efficiency of activated carbon was investigated. The results showed that both the breakthrough sulfur capacity and breakthrough time of activated carbon decreased with the increase of SO2 inlet concentration within the range of 0.1% -0.3%. The breakthrough sulfur capacity deceased with the increase of space velocity, with optimal space velocity of 600 h(-1). The optimal bed temperature was 80 degrees C, and the desulfurization efficiency can be reduced if the temperature continue to increase. The presence of moisture and oxygen greatly promoted the adsorption of SO2 onto the activated carbon. The best moisture content was 10%. When the oxygen concentrations were between 10% and 13%, the desulfurization performance of activated carbon was the highest. Under the optimal operating conditions, the sulfur capacity of activated carbon was 252 mg x g(-1), and the breakthrough time was up to 26 h when the SO2 inlet concentration was 0.2%.

Simultaneous absorption of NOx and SO2 from flue gas with pyrolusite slurry combined with gas-phase oxidation of NO using ozone.

NO was oxidized into NO(2) first by injecting ozone into flue gas stream, and then NO(2) was absorbed from flue gas simultaneously with SO(2) by pyrolusite slurry. Reaction mechanism and products during the absorption process were discussed in the followings. Effects of concentrations of injected ozone, inlet NO, pyrolusite and reaction temperature on NO(x)/SO(2) removal efficiency and Mn extraction rate were also investigated. The results showed that ozone could oxidize NO to NO(2) with selectivity and high efficiency, furthermore, MnO(2) in pyrolusite slurry could oxidize SO(2) and NO(2) into MnSO(4) and Mn(NO(3))(2) in liquid phase, respectively. Temperature and concentrations of injected ozone and inlet NO had little impact on both SO(2) removal efficiency and Mn extraction rate. Specifically, Mn extraction rate remained steady at around 85% when SO(2) removal efficiency dropped to 90%. NO(x) removal efficiency increased with the increasing of ozone concentration, inlet NO concentration and pyrolusite concentration, however, it remained stable when reaction temperature increased from 20°C to 40°C and decreased when the flue gas temperature exceeded 40°C. NO(x) removal efficiency reached 82% when inlet NO at 750 ppm, injected ozone at 900 ppm, concentration of pyrolusite at 500 g/L and temperature at 25°C.

A pilot-scale jet bubbling reactor for wet flue gas desulfurization with pyrolusite.

MnO2 in pyrolusite can react with SO2 in flue gas and obtain by-product MnSO4 x H2O. A pilot scale jet bubbling reactor was applied in this work. Different factors affecting both SO2 absorption efficiency and Mn2+ extraction rate have been investigated, these factors include temperature of inlet gas flue, ration of liquid/solid mass flow rate (L/S), pyrolusite grade, and SO2 concentration in the inlet flue gas. In the meantime, the procedure of purification of absorption liquid was also discussed. Experiment results indicated that the increase of temperature from 30 to 70 K caused the increase of SO2 absorption efficiency from 81.4% to 91.2%. And when SO2 concentration in the inlet flue gas increased from 500 to 3000 ppm, SO2 absorption efficiency and Mn2+ extraction rate decreased from 98.1% to 82.2% and from 82.8% to 61.7%, respectively. The content of MnO2 in pyrolusite had a neglectable effect on SO2 absorption efficiency. Low L/S was good for both removal of SO2 and Mn2+ extraction. The absorption liquid was filtrated and purified to remove Si, Mg, Ca, Fe, Al and heavy metals, last product MnSO4 x H2O was obtained which quality could reach China GB1622-86, the industry grade standards.