阳离子交换树脂分离纯化石杉碱甲的工艺研究

研究了5种离子交换树脂对石杉碱甲的吸附量和解吸率。结果表明,C004阳离子交换树脂的效果最好,其最佳工艺参数为:上柱液pH=3.0,上柱流速为3 BV/h,洗脱剂用3 mol/L氨水-70%乙醇,洗脱剂体积3 BV,洗脱速率1 BV/h。在此优化条件下,产品中的石杉碱甲含量可达5%。     

001×7阳离子交换树脂用于水处理过程中变红、变棕、粉碎对工作交换容量的影响

分析了 0 0 1× 7阳离子交换树脂用于水处理过程中变红、变棕和粉碎对工作交换容量的不同影响程度。提出了正常使用变红、变棕和非受冻粉碎后的树脂的可使用性与受冻粉碎后工作交换容量的不可恢复性。　　 [关键词 ]阳离子交换树脂 ;粉碎 ;工作交换容量     

Fabrication of cation exchange membrane from polyvinyl alcohol using lignin sulfonic acid: Applications in diffusion dialysis process for alkali recovery

We report polyvinyl alcohol (PVA)-based hybrid membranes composed of salt of lignin sulfonic acid (LSA) and tetraethyl orthosilicate. The concentration of LSA with respect to PVA varied from 10% to 40%. The hybrid membranes showed water uptake (W_U) in the range of 122–210%, ion exchange capacities in the range of 0.32–0.75 mmol g^?1, dialysis coefficient (U_OH) from 0.0068 to 0.0119 m h^?1, and selectivity (S) from 15 to 26. The hybrid membranes also showed thermal and mechanical stability.     

Selectivity and competitive mechanism of cation exchange resin for Fe,Mg, and Al ions in phosphoric acid

The presence of iron, magnesium, and aluminum elements as the primary impurities in wet-process phosphoric acid (WPA) adversely affects the industrial phosphoric acid and subsequent phosphorus chemical products. This study aims to investigate the selectivity and competition mechanism of Sinco-430 cation exchange resin for Fe, Mg, and Al ions in phosphoric acid solution. By studying the effects of different process conditions on the removal efficiency, the suitable conditions for the static removal of metal ions from Fe-Mg, Al-Mg, and Fe-Al binary systems were determined: solid–liquid mass ratio (S/L) of 0.3, phosphoric acid concentration of 27.61 wt.%, system temperature of 50°C, and rotational speeds of 200, 400, and 200 rpm, respectively. By calculating the selectivity coefficients of the resin for metal ions under different experimental conditions and mutual replacement experiments, the semi-empirical formulas for the selectivity coefficients were derived and order of selectivity was determined as follows: Mg²⁺ > Fe²⁺ > Al³⁺. Visual MINTEQ 3.1 software and density functional theory (DFT) calculations demonstrated that at low pH, the main forms of Fe, Mg, and Al present in phosphoric acid were FeH₂PO₄⁺, Mg²⁺, and AlH₂PO₄²⁺, respectively. This finding explained the differences in selectivity of the resin for Fe, Mg, and Al. The dynamic removal of metal ions from phosphoric acid was investigated. The order of metal ion selectivity of the resin by the dynamic method is the same as that of the static method, and the dynamic exchange behaviour was most consistent with the Yan model.     

Studies on syntheses and permeabilities of special polymer membranes: 50. Transport of metal ions against their concentration gradient through water-insoluble poly(styrene sulphonic acid) membrane

Water-insoluble cation exchange membranes were prepared by heat treating membranes made of poly(styrene sulphonic acid) and poly(vinyl alcohol). Transport of metal ions through the above cation exchange membrane against their concentration gradient was investigated under various conditions. The transport in this system, where one side of the membrane in a diaphragm cell was acidic and the other alkaline, was influenced significantly by the initial H⁺ ion concentration on the acidic side. The selectivity of metal ions in diffusive transport depended on the size of their hydrated ions and that in transport against their concentration gradient was due to the affinity between the metal ions and the carrier fixed to the membrane.     

The pH,temperature, and protein structure effect on β‐lactoglobulin A and B separation in anion‐exchange chromatography

The effect of pH and temperature on separating a mixture of similar proteins, namely β‐lactoglobulin A (LGA) and β‐lactoglobulin B (LGB) in anion‐exchange chromatography is explored. The proteins carry a slight difference in negative charge at basic pH, providing a separation basis on an Q Sepharose Fast Flow anion‐exchange resin. They were separated at different temperatures and pH values, and the separation factor was evaluated. The experimental results were matched to a theoretical model to compute the equilibrium constant K_A. The data shows that an increase in temperature and pH leads to an increase in the retention time of the proteins. The results were correlated with the net charge of the molecule for the separation so that the elution can be simulated for any condition that was studied. The tertiary structures of LGA and LGB are analyzed to illustrate the structure effect on the separation. © 2018 American Institute of Chemical Engineers AIChE J, 64: 1928–1937, 2018     

Modeling the protein partitioning in aqueous polymer two-phase systems: influence of polymer concentration and molecular weight

Aqueous polymer two-phase system provides a powerful method for separation and purification of biomaterials. Among various factors, polymer concentration and polymer molecular weight are essential and have strong impact on the protein partitioning in these systems. Based on the modified Pitzer's model, a simple expression has been obtained for correlating protein partitioning in aqueous polymer two-phase systems with varying polymer concentration and different polymer molecular weights. Using only one group of parameters for each target protein, the partition coefficients of five proteins (lysozyme, chymotrypsinogen-A, bovine serum albumin, transferrin and catalase) in 16 sets of polyethylene glycol (PEG)/dextran systems were correlated. In addition, partition behavior of lactate dehydrogenase in PEG/hydroxypropyl starch systems were measured, correlated and partially predicted. A comparison of calculated and experimental data indicated that the model provides good correlation and prediction abilities on the protein partitioning in aqueous polymer two-phase systems with a wide range of polymer concentration and molecular weight.     

Preparation of highly H+ permeable sulfonated poly(ether ether ketone) cation exchange membranes and their applications in electro‐generation of thioglycolic acid

BACKGROUND: Sulfonated poly(ether ether ketone) (SPEEK) was successfully synthesized from sulfonated 4,4′‐difluorobenzophenone, 4,4′‐difluorobenzophenone and bisphenol A. SPEEK cation exchange membranes were prepared by the casting method. The composition and morphology of SPEEK were characterized using Fourier transform infrared and ¹H NMR spectroscopies, respectively. The ion exchange capacity (IEC), water uptake and degree of swelling of the membranes were also investigated. SPEEK120 was used as a separator in an electrolysis cell to produce thioglycolic acid (TGA). RESULTS: SPEEK polymerization was carried out at 145 and 175 °C for 10 h. The IEC of the SPEEK membranes was measured as 0.24–2.02 meq g^?1 and the water uptake as 2.26–26.45%. The degree of swelling of the membranes was 1.71–15.28%. TGA was effectively prepared by electro‐reduction of dithioglycolic acid. The current efficiency peaked at 58.31% at room temperature with a current density of 15 mA cm^?2. CONCLUSION: SPEEK120 membrane shows good dimensional stability and H⁺ permeability. Compared to the traditional metal‐reduction method, the current electro‐reduction technique avoids the use of zinc powder and so reduces environmental pollution. Copyright © 2009 Society of Chemical Industry     

离子交换色谱法与反相液相色谱法测定精对苯二甲酸中微量杂质的比较

对比了用反相液相色谱法与离子交换色谱法定量分析精对苯二甲酸中的对羧基苯甲醛和对甲基苯甲酸含量的异同,有助于在实际工作中根据不同的情况选择仪器,了解了对羧基苯甲醛和对甲基苯甲酸的液相色谱测定方法,提高测定工作的准确性。     

Coupling of diffusion and chemical stress: The case of ion exchange in glass

The chemical strengthening of glass results from an ion exchange process in which smaller alkali ions in a glass are replaced with larger alkali ions from a molten salt bath. This interdiffusion process leads to a buildup of chemical stress in the glass. However, traditional modeling of the ion exchange process has not fully accounted for interaction effects between mass diffusion and the chemical stress developed during the process. In this study, we develop the general theory of coupling between diffusion and stress, resulting in a single flux equation with a concentration- and stress-dependent interdiffusion coefficient. We apply the theory to the specific cases of chemically strengthened soda lime silicate and aluminosilicate glasses, demonstrating the impact of interaction terms on concentration profiles and interdiffusion coefficient. Following a phenomenological approach, this study demonstrates the effect of the interdiffusion on stress generation and vice versa to account for deviations from the simple expressions published hitherto in the literature.     

Development and evaluation of an improved soil test for phosphorus: 1. The influence of phosphorus fertilizer solubility and soil properties on the extractability of soil P

The objective of this work was to develop and evaluate a soil test suitable for estimating the phosphorus status of soils whether they were fertilized with soluble or sparingly soluble P fertilizers or both. Four New Zealand soils of contrasting P sorption capacity and exchangeable Ca content were incubated alone or with monocalcium phosphate (MCP), reactive North Carolina (NC) phosphate rock or unreactive Florida (FRD) rock, at 240 mg P kg^–1 soil, to allow the P sources of different solubilities to react with each soil and provide soil samples containing different amounts of extractable P, Ca and residual phosphate rock. The phosphorus in the incubated soils was fractionated into alkali soluble and acid soluble P fractions using a sequential extraction procedure to assess the extent of phosphate rock dissolution. Eight soil P tests [three moderately alkaline — Olsen (0.5M NaHCO₃) modified Olsen (pretreatment with 1M NaCl) and Colwell; three acid tests — Bray 1, modified Bray 1 and Truog; and two resin tests — bicarbonate anion exchange resin (AER) and combined AER plus sodium cation exchange resin (CER)] were assessed in their ability to extract P from the incubated soils.The 0.5M NaHCO₃ based alkaline tests could not differentiate between the Control and FRD treatments in any soil nor between the Control, NC and FRD treatments in the high P sorption soils. The acid extractants appeared to be affected by the P sorption capacity of the soil probably because of reabsorption of dissolved P in the acid medium. The AER test gave results similar to Olsen. Only the combined AER + CER test extracted P in amounts related to the solubility of the P sources incubated with each soil. Furthermore, when soil samples were spiked with FRD and NC and extracted immediately, the P extracted by the AER + CER test, over and above the control soils, increased with the amount and chemical reactivity of the rocks. There was no extraction of rock P by any of the alkaline extractions.Increases in the amounts of P extracted (P) by each soil test from the fertilized soils, over and above the control soils were compared with the amounts ofP dissolved from the fertilizers during incubation (measured by P fractionation). Soil P sorption capacity had least influence on the amounts of P extracted by the AER + CER and Colwell tests. However, the Colwell test was unable to differentiate between all P sources in all four soils and suffered from the disadvantage of producing coloured extracts. The AER + CER test appeared to have the potential to assess the available P status of soils better than the other tests used because of its ability to extract a representative portion of residual PR (in accordance with the amount and reactivity) and dissolved P, and thus to differentiate between fertilizer treatments in all four soils.     

Studies on chitosan and poly(acrylic acid) interpolymer complex. I. Preparation,structure, pH-sensitivity,and salt sensitivity of complex-forming poly(acrylic acid): Chitosan semi-interpenetrating polymer network

A novel semi-interpenetrating polymer network (semi-IPN) membrane composed of crosslinked chitosan(cr-CS) and poly(acrylic acid) (PAA) was prepared. Evidence from infrared spectra proved the formation of polyelectrolyte complex through electrostatic interaction between groups from CS and COO⁻ groups from PAA. The semi-IPN membrane swelled at high pH and at low pH exhibited a typical pH-sensitivity. Its swelling degrees in different salt solutions with the same ionic valence and equal ionic strength were on similar levels. Under certain ionic strength (I = 1.5 mol/L), the degree of swelling increased with increased metal ionic valence. Furthermore, the elongation of the semi-IPN membrane could vary reversibly by immersion into CaCl₂ solution and KCl solution alternately. Reasons for the chemomechanical behavior are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1445–1450, 1997     

Initial activity/selectivity of H-gallosilicate (MFI) in propane aromatization: influence of H+ exchange and thermal/hydrothermal pretreatments

Initial activity/selectivity of H-gallosilicate (MFI) zeolite with different degrees of H⁺ exchange and pretreated under different thermal and hydrothermal conditions in propane aromatization (at 500C) has been determined using a pulse microreactor connected to GC. It is found to be strongly influenced by the degree of H⁺ exchange, calcination temperature and hydrothermal treatment at different temperatures and concentrations of steam. There exists a close relationship between the acidity (measured in terms of pyridine chemisorbed at 400 C) of the gallosilicate and its initial propane conversion and aromatization activity. Presence of strong acidic sites (attributed to FW Ga) at high concentration is essential for the well dispersed non-FW Ga oxide species to be active for dehydrogenation in the propane aromatization over the zeolite.     

Fabrication of inorganic/polymer nanocomposite membranes containing very high silica content via in situ surface grafting reaction and reactive dispersion of silica nanoparticles: Proton conduction,water uptake,and oxidative stability

In this study, we present a new fabrication process for proton exchange membranes based on inorganic/organic nanocomposite using in situ surface grafting reaction and reactive dispersion of silica nanoparticles in the presence of reactive dispersant, urethane acrylate nonionomer (UAN). Through in situ surface grafting reaction of silica nanoparticles, urethane acrylates were chemically introduced on the surface of silica nanoparticles, which were dispersed in DMSO solutions containing UAN and sodium styrene sulfonate (NaSS). After urethane linkage and copolymerization of NaSS, UAN and urethane acrylate moieties of silica nanoparticles, the solutions were converted to silica nanoparticle‐dispersed proton exchange membranes where silica particles were chemically connected with organic polymer chains. 5.89–29.45 wt % of silica nanoparticles could be dispersed and incorporated in polymer membranes, which were confirmed by transmittance electron microscopy (TEM) measurement. On varying weight % of silica nanoparticles dispersed within the membranes, water uptake and oxidative stability of nanocomposite membranes were largely changed, but membranes showed almost the same proton conductivity (greater than 10⁻² S cm⁻¹). At 5.89 wt % of silica nanoparticles, nanocomposite membranes showed the lowest water uptake and excellent oxidative stability compared to the sulfonated polyimide membranes fabricated by us. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The removal of iron and cobalt from aqueous solutions by ion exchange with Na‐Y zeolite: batch,semi‐batch and continuous operation

The removal of single component and binary mixtures of divalent cobalt and iron from water by ion exchange with synthetic Y zeolite has been studied in batch, semi‐batch and continuous modes of operation; the initial metal solution concentration did not exceed 2 mmol dm^?3. Binary Co/Na and Fe/Na ion exchange equilibrium isotherms (294 K) are presented wherein exchange site heterogeneity is evident in the case of the iron treatment. Under conditions of stoichiometric ion exchange, removal efficiencies for both cobalt and iron decrease with increasing metal concentration (0.2–2 mmol dm^?3) and the values were similar for both metals. Removal of cobalt under transient conditions was found to be temperature dependent. In the fixed bed operation, break‐through behavior was sensitive to changes in both flow rate and inlet concentration. The break‐through profiles for both metals under competitive and non‐competitive conditions are presented; iron removal is lower in the presence of cobalt and vice versa. An in situ regeneration of the fully loaded zeolite by back exchange with sodium is considered and the exchange capacity of the regenerated zeolite is reported. The feasibility of employing cycles of heavy metal uptake/zeolite regeneration is addressed. © 2002 Society of Chemical Industry     

Multicomponent ion exchange isotherms in NaX zeolite: evaluation of Cr/Ca/Mg,Cr/Ca/K and Cr/Mg/K systems

BACKGROUND: One of the most important heavy metals is Cr³⁺, which is commonly found together with Ca²⁺, Mg²⁺ and K⁺ ions in tannery wastewaters. Such metals can be removed through ion exchange process using zeolite NaX. Unfortunately, with single exchange mechanisms it is impossible to predict muti‐component and competitive interactions. This work is aimed at overcoming this problem. Ion exchange isotherms of Cr³⁺, Mg²⁺, Ca²⁺ and K⁺ in ternary mixtures (Cr/Mg/Ca, Cr/Ca/K, Cr/Mg/K) using NaX zeolite at 30 °C, 45 °C and 60 °C are studied and reported. RESULTS: Ion exchange is dependent on temperature, and on the nature and interaction of ingoing cations. Sequential ion exchange occurs where one cation is able to displace another already located in the site. Values of the equilibrium constant of all cations investigated are close to each other, which indicates a weak preference for Cr⁺³. The affinity order is as follows: for Cr/Ca/Mg–NaX isotherms, Cr³⁺ > Ca²⁺ > Mg²⁺ at 30 °C, Ca²⁺ > Cr³⁺ > Mg²⁺ at 45 °C and Ca²⁺ > Mg²⁺ > Cr³⁺ at 60 °C. For Cr/Ca/K–NaX isotherms the sequence is Cr³⁺ > Ca²⁺ > K⁺ for the three temperatures and for Cr/Mg/K–NaX isotherms, Cr³⁺ > Mg²⁺ > K⁺ at 30 and 45 °C and Mg²⁺ > K⁺ > Cr³⁺ at 60 °C. CONCLUSION: It can be concluded that ions with a high charge such as Cr³⁺ are not always preferentially removed from multi‐component solution. Therefore, exchanges in NaX zeolite are useful when there is no need to have high chromium removal when compared to the competitive cations investigated here. Copyright © 2008 Society of Chemical Industry     

Nitrogen-promoted active carbons as catalytic supports: 2. The influence of Mn promotion on the structure and catalytic properties in SCR

Catalytic properties of active carbons treated with N-compounds and promoted with manganese oxides were studied in selective catalytic reduction of NO with ammonia. The following elements of the preparation had a beneficial effect on activity and selectivity of the catalysts: pre-oxidation of active carbon prior to the introduction of N-species, the choice of N-compound, together with the post-treatment procedure, and the optimisation of the amount of active material. Apart from the introduction of N-surface groups, it was important to control the amount of acidic surface species which in turn determined the distribution of MeO_x and reducibility of the samples, thus influencing the formation of undesired by-product (N₂O).