PICA法合成介孔二氧化硅研究

以硅酸钠为硅源,在酸性条件下,通过尿素和甲醛的缩聚反应,用诱导聚合胶体团聚法(PICA)制备出单分散脲醛/SiO2复合微球,并经高温煅烧制得介孔二氯化硅。通过X射线衍射(XRD)、氮气脱吸附、透射电镜(TEM)和高分辨透射电镜(HRTEM)等手段对介孔二氧化硅进行了表征。结果表明,通过PICA法制得的介孔二氧化硅有序性好,孔径较大、孔壁较厚、孔径分布均匀。     

Water‐free synthesis of temperature‐sensitive polyacrylamide microgels and pore modeled oil recovery performance

Polymer gel treatments can improve sweep efficiency and reduce water production during oil recovery operations. In this article, a novel suspension polymerization method was developed to synthesize a temperature‐sensitive microgel. The microgel was prepared by suspension polymerization above the melting point of the monomer in a nonpolar solvent without water. Dry microspheres were obtained, which can be readily used without post‐treatment. Two different crosslinkers were employed in the suspension polymerization synthesis to give the particles thermally responsive aqueous swelling properties. After entering pore channels, gel particles expand to engineered size to realize flow profile changes within in a reservoir formation. When dispersed into water under lower temperatures (ambient to 40 °C), the original dry particles can swell about 18 times their original size. Exposure to a harsher environment (e.g., 80 °C) resulted in cleavage of the labile crosslinking agent and some chain cleavage gave a further size expansion. A Millipore film filtration model system was adopted to evaluate pore occlusion performance of the gel particles. It was found that the nuclear pores were effectively sealed by swollen microgels only when gel particle sizes were similar to or smaller than the membrane pores and interpore separation distance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44581.     

环保型无机沉淀转向剂性能特点及调驱能力研究

为了实现海上油田环保高效水驱开发，满足深部液流转向技术需求，开展了环保型无机沉淀体系性能及其影响因素实验研究。结果表明，硅酸钠溶液与渤海油田高矿化度区块注入水中的钙镁离子自发反应，生成沉淀悬浮体起到液流转向作用。从沉淀物生成量、药剂费用和矿场注入工艺等考虑，推荐浓度为0.02～0.05 mol/L，采取交替注入方式开展物模实验。结果表明，随着渗透率增加，封堵效果提高；随着钙镁离子和硅酸钠浓度增加，沉淀物生成量增加，封堵和调剖效果提高。微观可视化实验表明，体系在储层孔隙内一旦接触就会发生反应，生成沉淀物，使孔隙过流断面减小，渗流阻力增加，注入压力升高，中低渗透层吸液压差增大，吸液量增加，达到液流转向和扩大波及体积效果。在海上及其他作业空间受限的高矿化度油田有很大的应用推广价值。     

Adsorption Behavior of Cadmium(II) and Lead(II) on Mesoporous Silicate MCM‐41

Abstract

This investigation examines metal ion adsorption on mesoporous silicate, MCM‐41, synthesized from sodium silicate solution and cethyltrimethylammonium bromide (CTAB). MCM‐41 has potential as an adsorbent material, with a regular hexagonal pore structure, large specific surface area, and large pore volume. The MCM‐41 synthesized for this investigation is characterized using powder X‐ray diffraction and nitrogen adsorption and desorption isotherms data. The adsorption behavior for cadmium(II) and lead(II) onto MCM‐41 was studied by contacting the mesoporous silicate with an aqueous solution of metal salts and acetylacetone. Both Cd²⁺ and Pb²⁺ were found to quantitatively adsorb onto MCM‐41. The results of this study suggest that MCM‐41 may have applications in the recovery of toxic metals from waste waters.     

Amino-Modified Polylactic Acid Nanofibre Microspheres as Drug Sustained Release Carriers for Alendronate

Amino-modified polylactic acid (EPLA) nanofibre microspheres with a high porosity, large specific surface area, strong adsorption capacity, and rich in active amino groups were developed for drug delivery applications. Alendronate, a well-known antiresorptive agent, was chosen as a model drug to evaluate the loading capacity and release properties of the prepared EPLA microspheres. SEM micrographs clearly showed that the drug was loaded into the microspheres within the pores between the nanofibers and as well as being adsorbed on their surface. XRD and FTIR spectra analyses also confirmed drug loading. UV/Vis-absorption spectrophotometry was used to study the impact of various parameters, including adsorption time and initial concentration and pH value of the alendronate solution, on the microsphere drug-loading capacity. Under optimum conditions, EPLA microspheres exhibited a high alendronate adsorption capacity of up to 503?mg/g. In vitro release studies showed that alendronate-loaded EPLA nanofibre microspheres exhibited a perfect release performance, with alendronate being released in a sustained manner for approximately 15 days without any obvious initial burst. Therefore, EPLA nanofibre microspheres hold great potential as efficient, controlled release drug delivery carriers of alendronate.     

Preparation of Magnetic Porous Microspheres and Their Ability to Remove Oils

Magnetic, porous poly (tripropylene glycol diacrylate) (PTPGDA) microspheres are successfully prepared using a combination of microfluidic emulsification and free‐radical polymerization. The porous structure can be precisely controlled by controlling the amount of the oil‐phase emulsifier polyglycerol polyricinoleate (PGPR). The effects of PGPR content and pH on the contact angle of the microspheres is investigated. The contact angle of the microspheres increases with the raise of PGPR content, and the hydrophobicity of the microspheres remains stable at different pHs. The microstructure, magnetic properties, and oil adsorption abilities of the microspheres are also studied. The as‐prepared microspheres perform adsorption well, the higher the PGPR content, the more pore structures and larger contact angle occurres on the microspheres, which improves the adsorption capacity. In addition, the adsorption capacity of the microspheres for diesel can reach 3.38 g·g^?1 when the mass fraction of PGPR in oil phase is 50% w/v. After adsorbing oil, the microspheres can be separated, recovered, and reused by applying an external magnetic field. The magnetic microspheres have good oil adsorption abilities and recyclability, which shows their potential for use in oil removal.     

A simple room temperature synthesis of MCM-41 with enhanced thermal and hydrothermal stability

Highly ordered mesoporous silica samples were synthesized in less than 3 h using a simple synthesis methodology at room temperature with surfactant to silica ratio 0.1, using sodium silicate as a source of silica and cetyltrimethylammonium bromide (CTAB) as structure directing agent. Powder X-ray diffraction and N₂ adsorption studies exemplified addition rate of sodium silicate solution is critical on the final properties of the materials. Remarkable thermal and hydrothermal stabilities of the samples prepared through this route were seen in contrast with the conventional methodology. Optimization of conditions surmised HCl as neutralizing agent and silicate addition time of 10 min is appropriate for obtaining a well crystalline and stable material. Slower rate of silicate addition might have facilitated better condensation of oligomeric silica on the preformed silica-surfactant aggregates responsible for such high thermal and hydrothermal stabilities. Development of such simple and easily expandable methodologies for these mesoporous materials will pave ways for their practical applications. Electronic supplementary material  The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

松香基磁性微球的结构表征及其对Cr(Ⅵ)的吸附性能

以马来松香乙二醇丙烯酸酯和甲基丙烯酸为单体,Fe₃O₄为磁源,通过悬浮聚合和酰胺化反应制备出松香基磁性微球。利用热重分析仪、红外光谱、比表面积与孔隙度分析仪、扫描电镜及磁天平对磁性微球进行表征,并通过静态吸附法研究了其对Cr(Ⅵ)的吸附性能。结果显示：松香基磁性微球既具有顺磁性(磁化率为9.123×10^-4 cm³/g),又具有功能基团(氨基),比表面积、孔体积和平均孔径分别为29.73 m²/g、0.396 cm³/g和18.023 nm,表面和内部均有大量孔洞。当磁性微球粒径为72~108 μm时,在50 mL质量浓度为0.5 g/L Cr(Ⅵ)溶液中,调节pH值为2,吸附剂用量为0.8 g,25 ℃下振荡吸附,吸附平衡时间为4 h时,平衡吸附量为67.5 mg/g。动力学方程拟合结果显示吸附速率符合准一级动力学方程,吸附过程受液膜扩散和颗粒内部扩散共同影响。磁性微球循环使用5次,去除率仍达第一次吸附的85%以上,具有很好的循环使用性能。     

甲基纤维素湿敏水凝胶中溶菌酶微球性质的体外评价

Long-terrn injectable microspheres have some inherent disadvantages such as migration of microspheres from the originalsite an.d the burst effect. In order to avoid these problems, microsphere-loaded thermosensitive, hydrogel system was designed and expected to achieve a zero-order release Of biomolecular drugs in relativehigh initial drug loadings. Lysozyme, an antibacterial protein usually used to reduce prosthetic valve endocarditis,was selected as the model drug. Poly （DL-lactide-co-glycolide） （PLGA） microspheres, prepared by solvent evaporation method, were employee to encapsulate lysozyme and dispersed into thermosensitive pre-gel solution containing methylcellulose （MC）, polyethylene glycol （PEG）, sodium citrate （SC）, and sodium alginate （SA）. The mixture could act asadrug reservoir by.performing sol-gel transition rapidly if the temperature was raised from roomtemperature to 37℃. The in vitro release results showed that the burst effect was avoided due to strengthening ofdiffusion resistance in the gel. The formulation was able.to deliver lysozy.me for over.30 daysin a nearly zero-order release profile with a rate of 32.8μg.d^-1 which exhibits its remarkable potential for effective aoolication in long-term drug delivery.     

海藻酸盐/壳聚糖复合微球的制备及其控制释放作用

采用喷雾干燥法将活性成分包载到海藻酸钠微凝胶中,再经钙离子和壳聚糖交联得到复合微球。以维生素B₂为模型药物探讨了微球的控制释放效果和机理。扫描电镜分析表明海藻酸钠微凝胶经复合交联后形成了团聚体结构。与单一钙离子交联的海藻酸盐微球相比,复合微球对维生素B₂释放更慢,半数释放时间(t₅₀)延长约6倍,且交联时间越长、交联剂用量越高,维生素B₂释放越慢。当载药量介于16.0%～35.6%时,维生素B₂释放时间达24 h以上,释放过程主要受费克扩散控制。     

羟基磷灰石微球的制备及废水除氟性能评价

以壳聚糖为模板,通过反向乳液聚合制备得到羟基磷灰石微球（CTS-HAP）,在利用X射线衍射（XRD）、扫描电镜（SEM）、能谱（EDS）、红外光谱（FT-IR）对改性和吸附前后微球进行微观分析基础上,测定其在氟化钠溶液中的平衡吸附量为17.8 mg/g（吸附pH=4）,微球对氟离子吸附符合多层分子吸附模型——Freundlich模型。针对氟离子质量浓度为2 789.2 mg/L、pH为1.7的酸性高含氟废水,设计二阶段除氟。初步除氟阶段氢氧化钙用量为10 864 mg/L,剩余氟离子质量浓度为200.6 mg/L,去除率为92.81%;深度除氟采用CTS-HAP微球吸附法,CTS-HAP微球用量为24 g/L,去除率为95.2%,满足处理后废水氟离子浓度要求。     

磷酸中添加剂对核桃壳活性炭性能的影响

采用磷酸活化法制备核桃壳颗粒活性炭,研究了在磷酸浸渍液中加入不同种类和含量添加剂对活性炭性能的影响。以亚甲基蓝和碘吸附值表征活性炭的吸附性能,并对活性炭的孔结构参数、机械强度和微晶结构进行了测试分析。结果表明：在磷酸中分别添加柠檬酸、柠檬酸钠、硼酸和糖精浸渍处理核桃壳原料,所得活性炭的亚甲基蓝吸附值都得到提高,而碘吸附值降低,说明添加剂促使活性炭中的微孔扩大为中孔。其中,添加0.5%的柠檬酸钠得到最佳的亚甲基蓝和碘吸附值,分别达到236.5和744.1 mg/g。此外,磷酸中添加1%硼酸后得到的活性炭结构中含坚固的炭微晶,起到了增强孔结构的作用,机械强度为85.8%;而添加1%糖精得到的活性炭中的炭微晶几乎全部发生了石墨化转变,生成质软的石墨,使强度下降,机械强度仅为80.1%;添加0.5%柠檬酸钠的活性炭由于发达的孔隙结构且没有炭微晶的加固而强度较低(82.5%)。     

粉煤灰基地质聚合物微球吸附水中铜（Ⅱ）的研究

以粉煤灰为原料,以氢氧化钾溶液为碱激发剂,将二者按照优化配比（氧化钾与氧化铝物质的量比为1.5、水与氧化钠物质的量比为18）混合均匀后,采用悬浮固化法制备粉煤灰基地质聚合物微球,将微球用于吸附含铜废水中的铜（Ⅱ）。通过X射线衍射（XRD）仪、比表面积与孔径分析仪、BT-99型水质分析仪对微球进行了表征,探究了吸附时间、微球用量、吸附温度、铜（Ⅱ）溶液pH、铜（Ⅱ）溶液质量浓度等因素对微球吸附铜（Ⅱ）的影响。结果表明,粉煤灰基地质聚合物微球较粉煤灰原料具有更大的孔径和比表面积,具有更好的对铜（Ⅱ）的吸附效果,在最优条件下[微球用量为0.20 g、溶液pH为5、铜（Ⅱ）初始质量浓度为100 mg/L、溶液体积为100 mL、吸附温度为40℃、吸附时间为24 h]微球对铜（Ⅱ）的吸附量为45.62 mg/g、去除率达到91.46%,吸附过程遵循准二级动力学方程。     

Studies on the removal of Neutral Red on sand from aqueous solution and its kinetic behavior

Neutral Red (NR) dye in aqueous solution present as a pollutant material in textile waste water was removed by adsorption on sand at 298 K. Local sand sample which was used as an adsorbent in this work was initially characterized for its textural properties including surface area, mean pore radius and total pore volume. These properties were examined from the low-temperature adsorption of nitrogen on sand samples at 77 K. Later on the conditions of maximum adsorption of the dye on characterized sand sample were optimized. It was seen that under optimized conditions, up to 85% dye could be removed from solution onto the sand surface. The adsorption data were fitted to Freundlich and Lagergen equation for the calculation of various adsorption parameters. The Freundlich constants n and A were determined to be 0.997 and 0.2001 mol/g, respectively. The rate constant for adsorption of Neutral Red on sand sample as calculated by using the Lagergen equation was estimated to be 3.85 min⁻¹. The application of Boyd's equation revealed that particle diffusion was not operative in this case and thus does not control the kinetics of dye adsorption on sand. The adsorption behavior of the dye was also investigated in terms of added cations and anions. It was found that the dye adsorption decreased in the presence of chloride, sodium and copper ions.     

鄂尔多斯盆地油房庄地区长8储层孔隙结构研究

通过对油房庄地区长8储层孔隙结构的研究,发现该区储层的孔隙中孔隙和小孔隙为主,粒间孔和长石溶孔作为重要的储集空间.吼道已缩颈型和片状喉道为主,其次是弯曲状河道和孔隙缩小型喉道.储层排驱压力、中值压力逐渐降低,中值半径、最大进汞饱和度、退汞效率、平均孔径逐渐增大,储层物性逐渐变好.     

矿渣基轻质多孔地质聚合物的制备与孔结构研究

以矿渣微粉为主要原料,硅酸钠和氢氧化钠混合溶液为碱性激发剂,铝粉为发泡剂,制备地质聚合物基轻质多孔材料,系统研究了发泡剂、水灰比以及萘系减水剂对材料孔结构与物理性能的影响。结果表明,Al粉在碱性激发剂作用下快速反应生成H₂,促使地质聚合物浆体泡沫化形成多孔材料,且材料的干密度和抗压强度随Al粉掺量的增加迅速降低。当Al粉掺量超过0.40%(质量分数,下同),泡孔急剧增大,导致泡孔聚并,强度显著降低。提升水灰比可降低泡孔生长阻力,促使密度快速减小。但水灰比＞0.40后,浆体黏度和激发剂浓度显著降低,凝结时间延长,孔径增大,结构劣化,其最优水灰比为0.35。此外,萘系减水剂可有效调节多孔地质聚合物的孔结构,仅添加0.4%的萘系减水剂即可促使孔径分布均一,孔壁完整性提升,试样抗压强度提升。     

Polymer intrusion into narrow pores at the interface between a poor solvent and adsorbing and non-adsorbing surfaces

We report thermodynamic and conformational properties of collapsed polymer globules in a poor solvent close to adsorbing and non-adsorbing surfaces containing a cylindrical pore that is either smaller or larger than the coil size in bulk solution. Configurational Bias Monte Carlo simulations at infinite dilution were used for this purpose. We find that above the critical adsorption transition changing from good solvent to poor solvent conditions causes an increase of the partition coefficient due to cooperative monomer adsorption on the pore wall. Below the adsorption transition, the reverse effect is observed. The radius of gyration components as well as conformational (free) energies and entropies as a function of the chain centre of mass (CM) position along the pore axis reveal strong anomalies in the vicinity of the pore entrance. Below the adsorption transition, the dense globule in a poor solvent swells and deforms when penetrating the pore and recollapses once it is fully confined. Above the adsorption transition in solvents above and below the Θ-point, minima occur in the free energy at chain CM positions just in front of the pore entry causing a barrier upon pore penetration. Upon approaching the small pore from the bulk poor solvent region, the chain conformational entropy and energy run through a maximum below and above the adsorption transition.     

Flow Properties of Majolica Slip with a Thinning Additive Based on Sodium Polyacrylate

The effect of a new thinning agent, namely 40% sodium polyacrylate (SPA), on flow properties of majolica slip and the effect of hardness of water on changes in suspension moisture are considered. The use of 40% SPA makes it possible to reduce its content in slip by nearly half, compared to sodium silicate solution, to improve the slip flow properties, and to insignificantly decrease its moisture. An optimum content of 40% SPA in thinning a polymineral clay slip from the Gzhel'skoe deposit and a majolica mixture is determined.     

包埋型单宁酸铁制备及吸附催化脱氮性能研究

单宁酸铁(TA-Fe)具有吸附催化脱氮性能,包埋型TA-Fe可解决其固液分离问题。采用海藻酸钠(SA)制备包埋型SA/TA-Fe,并对其特性进行表征,同时评价SA/TA-Fe的吸附催化脱氮性能,以及制备条件对SA/TA-Fe的吸附催化脱氮性能的影响。结果表明,SA/TA-Fe具有明显孔隙结构且TA-Fe存在于孔隙表面,但比表面积明显下降。SA/TA-Fe对NH4⁺-N和NO₂^--N均具有吸附能力,但吸附能力低于TA-Fe,同时对NH4⁺-N的吸附能力大于NO₂^--N。包埋后TA-Fe对吸附NO₂^--N的影响更为显著。SA/TA-Fe对NH4⁺-N和NO₂^--N具有吸附催化能力,可同步提高NH4⁺-N和NO₂^--N的去除量。采用20 g/L的SA溶液,按照TA-Fe和SA质量比为2:1,交联时间为12 h,制得的SA/TA-Fe对NH4⁺-N和NO₂^--N的吸附催化去除效果最佳。     

Optimized pore structure and high permeability of metakaolin/fly-ash-based geopolymer foams from Al– and H2O2–sodium oleate foaming systems

Geopolymer foams have been widely studied as adsorbents owing to their high specific surface areas, high heavy metal immobilization efficiencies, low cost, environmental friendliness, and resource-recycling benefits. In this study, geopolymer foams with different pore structures were prepared from Al– and H₂O₂–sodium oleate foaming systems, and their chemical properties, pore structures, and permeabilities were characterized. The effects of the foaming agent type and surfactant content on the crystal structure and chemical bonding of the materials were analyzed by X-ray diffraction analysis and Fourier-transform infrared spectroscopy, and the pore morphology and structural characteristics were characterized by morphological observations, three-dimensional (3D) reconstruction, and compression tests. Numerical simulations were also carried out to study the structural characteristics of the 3D-reconstructed pores. Furthermore, variations in the permeability coefficient and flow characteristics were tested and analyzed by experiments and simulations. The pores in the geopolymer from the H₂O₂–sodium oleate foaming system tended to be more connected, whereas those in the Al–sodium oleate geopolymers were more complete and closed. The highly connected pore structure facilitates the even diffusion of the solution and effectively increases the amount of adsorption sites. These properties are significant for adjusting the adsorption capacity of geopolymer foams as adsorption monoliths.