Adsorption Kinetics of Methylene Blue from Aqueous Solutions onto Palygorskite

The adsorption kinetics of methylene blue from aqueous solutions on purified palygorskite was investigated. The kinetics data related to the adsorption of methylene blue from aqueous solutions are in good agreement with the pseudo-second order equation in ranges of initial concentration of 120-210 mg/L, oscillation speed of 100-200 r/min and temperature of 298-328K. The experimental results show that methylene blue is only adsorbed onto the external surface of purified palygorskite, and the apparent adsorption activation energy is 13.92 kJ/mol. The relatively low apparent adsorption activation energy suggests that the adsorption of methylene blue involves in not only a chemical, but also a physical adsorption process, and it is controlled by the combination of chemical adsorption and fiquid-film diffusion.

Improvement of CO2 capture performance of calcium-based absorbent modified with palygorskite

Limestone can be used for CO_2 capture and sequestration(CCS) in flue gas effectively. However, its CCS capability will dramatically decline after several cycles due to the surface "sintering". In this work, the limestone was modified with palygorskite to reduce sintering phenomenon between the absorbent particles during the CCS process and the carbonation rate of the limestone can be enhanced effectively. Palygorskite is a natural mineral with nano-fibrous structure which can reduce the mutual contact of limestone particles during the CCS process. The results were detected by TGA, SEM, MIP, FTIR and particle size analyzer respectively. The best CO_2 capture performance of modified absorbent was 13.11% improvement with only 5 wt% palygorskite added during the CCS process after 15 cycles compared with natural absorbent. It was found that excellent microscopic structures of absorbent modified with palygorskite was created, and the surface sintering was postponed leading to CO_2 capture performance enhanced under the same conditions.

Preparation of Palygorskite-based Phase Change Composites for Thermal Energy Storage and Their Applications in Trombe Walls

Palygorskite/paraffin phase-change composites were prepared by the combination of purified palygorskite clay and sliced paraffin. Then, this composite was used in the Trombe wall to improve its energy storage ability. Further, its energy storage ability was compared to that of ordinary concrete wall through contrastive test. The experiments show that palygorskite clay is a type of clay mineral with strong adsorption ability, and the purity of natural palygorskite clay can reach up to 97.1% after certain purification processes. Paraffin is well adsorbed by palygorskite, and the test results show that the optimal adsorption ratio is palygorskite： paraffin = 2：1（mass ratio）. Palygorskite/paraffin phase change composites can be obtained by using palygorskite as the adsorbing medium to adsorb paraffin. The composite materials exhibit good heat storage（release） performance, which can store heat with increasing environment temperature and release heat with decreasing temperature. This property not only increases the inertia to environment temperature change, but also promotes the energy migration in different time and space, thus achieving a certain energy-saving effect. The application of palygorskite/paraffin phase change composite materials to the Trombe wall can significantly reduce the fluctuation of indoor temperature and enhance the thermal inertia of indoor environment. From the aspect of energy storage effect, the Trombe wall fabricated using PCMs is significantly superior to the concrete wall with the same thickness.

SAED and HRTEM Investigation of Palygorskite

The microstructure of palygorskite from Longwang Mountain of Xuyu County, Jiangsu Province, was studied by energy dispersive X-ray analysis （EDX）, selected-area electron diffraction （SAED） and high-resolution transmission electron microscopy （HRTEM）. The average composition of the palygorskite studied is （Si7.38A10.62） （A10.96Fe^3＋ 0.62Mg2.86 0.56）Ca0.03K0.06O20（OH）2（OH2）4, which is rich in Mg. Several SAED patterns from a single crystal of palygorskite were obtained with different zone axes. The polymorphs （monoclinic and orthorhombic） are unequivocally distinguished by distant interplanar angles, even though they possess similar sets of d-values. High-resolution images of three principal zones （[010], [100] and [110]） were obtained. The lattice fringes on HRTEM images along [010] have spacings of 0.319 nm. These fringes are interpreted as periodic alterations of two tetrahedral （T） sheets and one octahedral （O） sheet （-TT-O-TT-O-）. We have directly observed trioctahedral and dioctahedral individual palygorskite particles along [100]. They are all presented as dark lines along [001], but the width of dark lines corresponding to trioctahedral crystals （0.913 nm） is twice that of the dioctahedral ones （0.456 nm）. This is because the trans.sites are occupied by cations in trioctahedral palygorskite. The width of dark lines along [110] is 1.024 nm, a bit thinner than the theoretical spacing （1.044 nm）. This is because water molecules quickly leave the structure upon the irradiation by the electron beam.

Mechanism for Cu^(2+) Sorption on Palygorskite

A single-factor experiment of copper ion adsorption on pure palygorskite was carried out to understand the Cu2+ sorption of palygorskite—an important clay mineral in soil and sedimentary rock. In addition, pH of the solution and the surface microstructure of palygorskite were investigated before and after adsorption. The experimental results indicated that efficiency of Cu2+ removal was related to the oscillation rate of the specimen shaker, sorption time, initial pH value and the amount of adsorbent added. Palygorskite induced Cu2+ hydrolysis and interaction between copper hydroxide colloids and palygorskite surfaces, as observed with transmission electron microscopy (TEM), were the main contributions to palygorskite removal of Cu2+. This mechanism was different from adsorption at the mineral-water interface. It was proposed that surface hydrolysis of palygorskite raised the alkalinity of the palygorskite-water interface and suspension system. Thus, the induced pH of the solution was then high enough for Cu2+ hydrolysis on the mineral surface and in solution.

Distribution of Palygorskite in the Lingtai Profile of Chinese Loess Plateau:Its Paleoclimatic Implications

Palygorskite is a typical indicator mineral of the arid and strong evaporation environment. Distribution of palygorskite in loess-red clay sequences may act as an important indicator for reconstruction of the paleoenvironment and paleoclimate. In this paper, field emission scanning electron microscope and high-resolution transmission electron microscope observations on the red clay-loess-paleosol of the Renjiapo profile at Lingtai, Gansu Province indicate that palygorskite occurs widely in red clay sequences formed before 3.6 Ma, but no occurrence has been found in eolian sediments since 3.2 Ma. Micromorphological features and microstructure of palygorskite show that it is an autogenic mineral formed during pedogenesis, and transformed from iilite-montmorilionite under the pore water action. In the Lingtai profile, the disappearance horizon of palygorskite is consistent with those of increasing magnetic susceptibility, dust flux and depositional rate. The distribution of palygorskite in the profile indicates that the interval of around 3.6 Ma was an important transformation period of the East Asian paleomonsoon, when changes took place in the East Asia paleoclimate pattern, i.e. a high-frequency strong fluctuation alternative evolution of the environment. Therefore, palygorskite is a key indicator mineral of the East Asian paleomonsoon evolution of that time.

Enhanced adsorptive removal of Cr(VI)in aqueous solution by polyethyleneimine modified palygorskite

Polyethyleneimine(PEI)modified palygorskite(Pal)was used for the adsorption of Cr(VI)in aqueous solution.The absorbent was characterized by Fourier transform infrared spectroscopy(FT-IR)and thermogravimetric analysis(TGA).Characterized results confirmed that the Pal has been successfully modified by PEI.The modification of PEI increased the Cr(VI)adsorption performance of the Pal by the adsorption combined reduction mechanism,and amino groups of the adsorbent play the main role in the enhanced Cr(VI)adsorption.The maximum adsorption capacity was 51.10 mg·g^-1 at pH4.0 and 25°C.The adsorption kinetics of Cr(VI)on the adsorbent conforms to the Langmuir isotherm model.The maximum adsorption occurs at pH3,and then the adsorption capacity of PEI-Pal was decreased with the increase of p H values.The adsorption kinetics of Cr(VI)on PEI-Pal was modeled with pseudo-second-order model.The addition of Cl^-,SO4^2-and PO4^3-reduced the Cr(VI)adsorption by competition with Cr(VI)for the active sites of PEI-Pal.The Cr(VI)saturated PEI-Pal can be regenerated in alkaline solution,and the adsorption capacity can still be maintained at 30.44 mg·g^-1 after 4 cycles.The results demonstrate that PEI-Pal can be used as a potential adsorbent of Cr(VI)in aqueous solutions.

Structures and Properties Characterization of Acrylonitrile-butadiene-styrene /Organo-palygorskite Clay Composites

Palygorskite （PGS） and vinyl tris-（2-methoxyethoxy） silane （KH-172） modified palygorskite （OPGS） were used to prepare acrylonitrile-butadiene-styrene （ABS）/clay composites. Thermal stability of the composites was evaluated by using thermogravimetric analysis （TGA）. The morphology of the fractured surface and the degree of dispersion of the clay in the ABS matrix were observed by scanning electron microscopy （SEM）. X-ray diffraction （XRD） analysis results showed the variation of the crystal structure. Measurements of the tensile properties of the ABS/clay composites proved that the ABS/OPGS composited material represented the most excellent tensile property, because of good compatibility and dispersion of ABS with OPGS.

Ethylene Polymerization with Palygorskite Supported Nickel-Diimine Catalyst

A nickel-diimine catalyst [N, N'-bis(2,6-diisopropylphenyl)-1,4-diaza-2,3-dimethyl-1, 3-butadiene nickel dibromide, DMN] was supported on palygorskite clay for ethylene slurry polymerization. The effect of supporting methods on the catalyst impregnation was studied and compared. Pretreatment of the support with methylalumi-noxane (MAO) followed by DMN impregnation gave higher catalyst loading and catalytic activity than the direct impregnation of DMN. Catalyst activity as high as 5.42×105g PE·molNi-1·h-1 was achieved at ethylene pressure of 6.87×105 Pa and polymerization temperature of 20℃. In particular, the morphological change of the support during MAO treatment was characterized and analyzed. It was found that nano-fiber clusters formed during the support pretreatment, which increased the surface area of the support and favored the impregnation of the catalyst. The investigation of polymerization behavior of supported catalyst revealed that the polymerization rate could be kept at a relatively high level for a long time, different from the homogeneous catalyst. By analyzing the SEM photographs of the polymer produced by the supported catalyst, the morphological evolution of polymer particles was preliminarily studied.

Synthesis of magnetically modified palygorskite composite for immobilization of Candida sp. 99–125 lipase via adsorption

Magnetically modified palygorskite composites were synthesized with γ-Fe2O3 dispersing on the external surface of clay mineral. The magnetic clay was characterized with Fourier transform infrared, X-ray diffrac- tion, transmission electron microscopy, and vibrating sample magnetometer. Candida sp. 99-125 lipase was immobilized on magnetic palygorskite composites by physical adsorption with enzyme loading of 41.5 mg· g^-1 support and enzyme activity of 2631.6 U· （g support）^-1. The immobilized lipase exhibit better thermal and broader pH stability and excellent reusabilitV compared with free lipase.

Preparation and properties of a low-cost porous ceramic support from low-grade palygorskite clay and silicon-carbide with vanadium pentoxide additives

Alow-cost porous ceramic support was prepared from low-grade palygorskite clay(LPGS) and silicon carbide(SiC)with vanadium pentoxide(V_(2) O_(5)) additives by a dry-press forming method and sintering.The effects of SiC-LPGS ratio,pressing pressure,carbon powder pore-forming agent and V_(2) O_(5) sintering additives on the microstructure and performance of the supports were investigated.The addition of an appropriate amount of SiC to the LPGS can prevent excessive shrinkage of the support during sintering,and increase the mechanical strength and open porosity of the supports.The presence of SiC(34.4%) led to increases in the open porosity and mechanical strength of 40.43% ± 0.21% and(17.76 ± 0.51) MPa,respectively,after sintering at 700℃ for 3 h.Because of its low melting point,V_(2) O_(5) can melt to liquid during sintering,which increases the mechanical strength of the supports and retains the porosity.Certainly,this can also encourage efficient use of the LPGS and avoid wasting resources.

Superficial performance and pore structure of palygorskite treated by hydrochloric acid

In order to amend the superficial performance of palygorskite and improve its application, the natural palygorskite(NP) was treated in the dipping and ionic exchanging experiments using 6mol/L hydrochloric acid treatment. The performance and pore structure of the treated palygorskite(TP) were investigated by means of microscope analyses, FT-IR, XRF, BET-SSA and full hole distribution analytical techniques. The results show that the hydrochloric acid treatment can make the gracile and aggregating compact crystal bundles inside palygorskite clay broken and dispersed, the roughness of microcrystalline surface increases, which not only can dissolve or remove dolomite but vary the superficial performance of palygorskite to some degree. The specific surface area and pore volume increase a lot, while the mean pore size decreases. The pore structure of TP changes remarkably compared with that of NP after 6mol/L hydrochloric acid treatment, and the relevant physicochemical performance can be improved.

Relationship between the geochemistry of organic matter and the generation of palygorskite in Jiangsu-Anhui border and Gansu Province,China

Soluble organic matter had been separated from several palygorskite and bentonite samples in the Ji-angsu-Anhui border area(across Jiangsu Province and Anhui Province) and Linze County in Gansu Province of China and was analyzed with the techniques and methods of organic geochemistry.The composition and distribution of hydrocarbons were analyzed by gas chromatography(GC).Organic stable carbon isotopic ratios(δ13C) in typical samples were determined.The abundance of soluble organic matter in all clay samples analyzed was low.In Ji-angsu-Anhui samples,the preservation states of organic matter are different;hydrocarbons in organic matter have some features of aquatic plankton but are short of the input of terrigenous higher plants;organic δ13C in a palygor-skite of Yongxiaoshan in Xuyi County,Jiangsu Province,is-6.72‰.These features may be typical of a sedimentary environment of closed or semi-closed and relatively isolated different waters near coast or seashore.On the contrary,in samples from Gansu,the preservation states of organic matter are good;the GC graphs of hydrocarbons show that the precursors of the organic matter are from a mixed source of aquatic organisms and land-sourced higher plants;organic δ13C of a palygorskite from Yangtai of Gansu is-15.62‰.It indicated that the sedimentary environment may be an inland salty lake.Preliminary results suggest that palygorskite minerals in the Jiangsu-Anhui area may be evolved from rapidly accumulated fine material or volcanic ash,but clays in Gansu Province may be transformed from terrigenous inorganic clastic components carried to the lake through river and then deposited.The generation process of the samples studied in the paper seems to be related to salty water.

Solar Photocatalysis of TiO2 Supported Natural Palygorskite Nanofibers Elaborated by a One_Pot Mechanochemical Route

This study reports the successful synthesis of supported TiO2_Palygorskite nanocomposites by a one-pot dry mechanochemical route. Indeed, the elaboration procedure involved an in-situ reaction between accessories carbonates present in raw fibrous palygorskite clay and titanyl sulfate (TiOSO4) precursor under variable grinding conditions, essentially ball/solid matter mass ratio and rotation velocity. This yielded after air annealing at 600%C for 1 h to the immobilization of anatase TiO2 nanoparticles (≈8 nm of average size) as evidenced by XRD and TEM analyses. Once the conditions of elaboration were optimized, the photocatalytic properties were evaluated under 3 conditions: artificial UV radiation, artificial solar radiation (UV + visible range) and under dynamic solar illumination taking into account the discontinuities of the solar resource. The results allowed the estimation and comparison of the catalyst’s capabilities and showed its ability to work under natural irradiation. The so developed supported photocatalysts TiO2/Palygorskite exhibited a good activity towards the removal of Orange G (OG) dye from aqueous media under artificial UV and natural solar radiations.

Solution Blowing of Palygorskite-Based Nanofibers for Methylene Blue Adsorption

Palygorskite(PG)adsorbent with superior adsorption property and ion-exchange ability is highly desired in the field of dye removal.However,it generates high amounts of precipitation due to the granular form,resulting in secondary pollution after adsorption.Herein,the novel high porosity PG-based nanofibers that are easy for operating and retrieving have been fabricated using effective solution blowing and subsequent calcination.The obtained highly efficient adsorption nanofibers exhibit large specific surface area about 170.50 m^(2)/g with average diameter from 243 nm to 365 nm.Based on the abovementioned nanofibrous structure and negatively charged PG,the solution blowing of PG-based nanofibers(SBPNs)showed high adsorption capacity for methylene blue(MB)(112.36 mg/g).In addition,the adsorption of SBPNs is well described by the Langmuir isotherm model.This work provides new SBPNs forming process for the fields of dye removal,which may achieve the production of PG adsorbents at the industrial level.

盱眙、明光、临泽坡缕石的八面体阳离子占位及对其性能的影响

坡缕石是一种2:1型链层状结构含水富镁铝硅酸盐矿物,具有重要的资源和材料属性。不同成因、产状坡缕石八面体中类质同象替代有很大差别,而八面体类质同象替代对坡缕石性能的影响未见研究报道。本文以中国最具代表性的安徽明光、江苏盱眙、甘肃临泽坡缕石为研究对象,研究了三种坡缕石的Al、Mg、Fe含量及在八面体中的占位,并探讨了八面体的Al、Mg、Fe占位对坡缕石中水的种类和含量、表面电位和酸位以及对Pb^(2+)、Cd^(2+)吸附性能的影响。结果表明:明光坡缕石相对富镁,八面体主要被Mg^(2+)占据,具有三八面体特征;盱眙、临泽坡缕石相对富铝、铁,八面体主要被Al^(3+)占据,表现出更多的二八面体特征。盱眙坡缕石由于M1位置空位较多,结构水含量较低;坡缕石类质同象替代对Zeta电位影响不大;具有二八面体特征的盱眙、临泽坡缕石由于八面体中Al含量较高,酸位较多,催化性能较好。在重金属吸附实验中,明光坡缕石对Cd^(2+)的吸附效果最好,盱眙坡缕石对Pb^(2+)的吸附效果最好,临泽坡缕石吸附性能较差。本文可为坡缕石的改性和应用提供指导和参考。

复合生物炭-坡缕石对Cd污染土壤的钝化修复

为实现重金属污染土壤的高效、环保修复,采用慢氧限制热解法制备生物炭-坡缕石复合材料(BC/PAL)。考察BC/PAL对土壤理化性质、Cd的浸出毒性和在土壤中的赋存形态、玉米生长状况及Cd的富集转运影响,从而评价该材料对土壤中Cd的潜在生态风险改善及稳定效果。结果表明,添加BC/PAL后土壤pH显著增加,当投加量为8%时,pH较对照组(CK)升高1.14。当BC/PAL投加量为6%和8%时,土壤中Cd的毒性特征浸出程序(TCLP)浸出毒性较CK下降60%以上。添加BC/PAL后,Cd在土壤中的赋存状态从活泼趋于稳定。BC/PAL可减轻Cd对玉米的胁迫,促进玉米生长,当投加量为6%时,玉米鲜重增加221.43%。BC/PAL大大降低了土壤中Cd的潜在生态风险及生物有效性,是一种高效、环保的土壤修复材料。

腐植酸钠改性坡缕石对甲基紫吸附性能的研究

坡缕石(又名凹凸棒石,简写PAL)是一种天然的2:1型的层链状含水富镁、铝硅酸盐黏土矿物,由于其独特的一维棒状晶体形貌和纳米孔道结构,已广泛应用在吸附领域。在水热条件下,将PAL添加到腐植酸钠溶液中,制备了PAL吸附剂。采用电子扫描电镜(FESEM)、X射线衍射(XRD)、热重分析(TG)等表征手段系统研究了水热改性对PAL吸附剂微观结构和理化性能的影响,并评价了PAL吸附剂对甲基紫的吸附性能。考察了改性剂浓度、溶液pH、振荡时间对甲基紫吸附量的影响。结果表明,PAL材料可以完全去除100 mg/L染料溶液中的甲基紫,去除率达到98%以上,相比原天然PAL,去除率提高了51%。

改性凹凸棒石对海兰褐蛋鸡生产性能、卵巢抗氧化能力和繁殖性能的影响

【目的】研究在基础日粮中添加改性凹凸棒石(MPal)对蛋鸡产蛋高峰前生产性能、卵巢抗氧化能力和繁殖性能的影响,为MPal在生产中的合理应用提供依据。【方法】将512只92日龄的海兰褐蛋鸡分为4组,每组8个重复,每个重复16只鸡,分别饲喂添加0、250、500、1000 mg·kg^(-1)MPal的日粮。试验从蛋鸡92日龄开始至168日龄结束,共77 d。【结果】(1)MPal二次提高了144~168日龄蛋鸡的产蛋率(P<0.05);(2)MPal二次增加了168日龄蛋鸡输卵管的长度(P<0.05),线性增加了140日龄蛋鸡白卵泡的数量和168日龄蛋鸡黄样卵泡的数量(P<0.05),二次增加了140日龄蛋鸡小黄卵泡的数量(P<0.05),线性和二次增加了140日龄蛋鸡黄样卵泡、总卵泡的数量和168日龄蛋鸡中黄卵泡的数量(P<0.05);(3)MPal线性提高了140日龄蛋鸡卵巢的总超氧化物歧化酶(T-SOD)活性、总抗氧化能力(T-AOC)、谷胱甘肽过氧化物酶(GSH-Px)活性和168日龄蛋鸡卵巢T-AOC、T-SOD活性(P<0.05),线性增加了140日龄蛋鸡卵巢还原型谷胱甘肽(GSH)含量(P<0.05),二次提高了140日龄蛋鸡卵巢T-AOC和168日龄蛋鸡卵巢T-AOC、GSH-Px活性(P<0.05);(4)MPal线性提高了140日龄蛋鸡血清孕酮水平和168日龄蛋鸡血清促黄体生成素、促卵泡激素水平(P<0.05),线性和二次提高了140日龄蛋鸡血清雌二醇、促黄体生成素、促卵泡激素水平和168日龄蛋鸡血清雌二醇、孕酮水平(P<0.05);(5)MPal线性和二次降低了168日龄蛋鸡卵巢细胞凋亡率(P<0.05);(6)MPal线性上调了140日龄蛋鸡卵巢雌激素受体α(ERα)、雌激素受体β(ERβ)、孕酮受体(PR)、卵泡刺激素受体(FSHR)、雄激素受体(AR)的表达水平和168日龄蛋鸡卵巢FSHR、AR的表达水平(P<0.05),线性和二次上调了140日龄蛋鸡卵巢促黄体素受体(LHR)、细胞色素P450家族19亚家族A成员1(CYP19A1)的表达水平和168日龄蛋鸡卵巢ERα、ERβ、LHR的表达水平(P<0.05)。【结论】MPal对海兰褐蛋鸡开产后的生产性能、卵巢抗氧化能力和繁殖性能有积极作用;MPal在海兰褐蛋鸡日粮中的推荐添加量为500 mg·kg^(-1)。