Ni-P-mCMC/mCS双极膜技术在成对电解制备糠醇、糠酸中的应用

以磷酸化试剂改性羧甲基纤维素钠(mCMC)制备了阳膜层,以戊二醛改性壳聚糖(mCS)制备了阴膜层溶胶,将阴膜层溶胶流延于阳膜层上,制备了P-mCMC/mCS双极膜,而后以化学镀方法在阳膜层表面镀镍,制备了Ni-P-mCMC/mCS双极膜,并应用于成对电合成糠醇(阴极室中)、糠酸(阳极室中)。在电场的作用下,双极膜中水电离后生成的H+透过mCMC阳离子膜进入阴极室,促进糠醛电还原生成糠醇过程的进行;OH-透过mCS阴离子膜进入阳极室,与糠醛电氧化生成糠酸过程中产生的H+结合生成H2O,以增大正向反应的速度。在电流密度为2.5×10-2A/cm2,30℃下电解,阴阳两极室的电解效率分别为83.0%和77.4%,电解槽电压稳定在3.0V左右。     

Ni-mSA-mCS双极膜的制备及其在电合成TGA中的应用

通过用Ca2+改性海藻酸钠(SA)和用戊二醛改性壳聚糖(CS)制备Ni-mSA-mCS(m: modified)双极膜. 镍网预先埋在mSA膜表面作为阴极, 不仅增强了膜的机械性能, 而且降低阴极电解液的IR降, 实现零极距. 测定了膜的红外光谱、电镜扫描、机械性能. 将Ni-mSA-mCS双极膜应用于电还原制备巯基乙酸(TGA). 实验结果表明, 电流密度为10 mA·cm-2, 常温电解, 电流效率可达66.7%. 与传统的Zn还原法相比, 不仅省去了昂贵的金属还原剂的消耗, 而且消除了锌泥对环境的污染.     

四磺酸基铜酞菁-海藻酸钠/壳聚糖双极膜的制备与表征

分别用Fe3+和戊二醛作为交联剂对海藻酸钠(SA)阳离子交换膜和壳聚糖(CS)阴离子交换膜进行改性,制备了四磺酸基铜酞菁(CuTsPc)-海藻酸钠/改性壳聚糖双极膜(CuTsPc-SA/mCSBPM).在海藻酸钠阳膜层中添加四磺酸基铜酞菁,以提高阳膜层的离子交换容量,促进双极膜中间层中水的解离.采用X射线光电子能谱(XPS)对CuTsPc-SA阳离子交换膜进行了表征.实验结果表明,改性后SA阳膜层的离子交换容量、H+透过率均获得提高.与Fe3+改性或二茂铁离子改性的mSA/mCS双极膜相比,CuTsPc-SA/mCS双极膜的阻抗及电阻压降(即膜IR降)均下降.当电流密度为120mA/cm2时槽电压仅为5.6V.当CuTsPc含量为2.5%(质量分数)时CuTsPc-SA/mCS双极膜在H+离子浓度小于8mol/L的酸溶液中具有稳定的工作性能.     

CoPc(COOH)8-SA/mCS双极膜的制备及表征

分别用Fe3+离子和戊二醛作为交联剂对海藻酸钠(SA)阳膜层和壳聚糖(CS)阴膜层进行改性, 制备了八羧基钴酞菁-海藻酸钠/改性壳聚糖(CoPc(COOH)8-SA/mCS)双极膜(BPM). 在海藻酸钠阳膜层中添加八羧基钴酞菁以提高阳膜的离子交换容量, 促进中间层水的解离. 用傅立叶红外(FT-IR)光谱、扫描电镜(SEM)等方法对制备的双极膜进行了表征. 实验结果表明, 经八羧基钴酞菁改性后, 阳离子交换膜层的离子交换容量、H+离子透过率均获得提高. 与Fe3+离子改性或二茂铁离子改性的mSA/mCS双极膜相比, CoPc(COOH)8-SA/mCS双极膜的交流阻抗、电阻压降(IR降)和溶胀度降低. 当电流密度高达105 mA·cm-2时, CoPc(COOH)8-SA/mCS双极膜的IR降仅为0.7 V.     

mCMC-PEG-CS双极膜在电还原制备巯基乙酸中的应用

以Fe3+改性羧甲基纤维素(CMC)和聚乙二醇(PEG)共混物为阳膜, 以戊二醛改性壳聚糖(CS)和聚乙二醇共混物为阴膜, 制备了mCMC-PEG-CS双极膜, 并将其用作电解还原制备巯基乙酸(TGA)电解槽中阴阳两室间的隔膜. 以硫代硫酸钠法合成的巯基乙酸(TGA)和二硫代二乙酸(DTDGA)混合物为原料, 研究了酸浓度、温度及电解电流密度对电还原DTDGA制备TGA的生成量和电流效率的影响. 实验结果表明, 在TGA初始合成质量分数为2.79%, 电流密度为10 mA/cm2, 35 ℃电解时, 阴极室电还原产物巯基乙酸的电流效率为74.69%, 电解过程中的平均电流效率为54.02%. 与传统的金属还原法还原DTDGA制备的TGA相比, 不仅避免了昂贵的金属还原剂锌的消耗, 而且消除了反应副产物锌泥对环境的污染.     

双极膜技术在电氧化制备3-甲基-2-吡啶甲酰胺中的应用

分别以戊二醛和Fe3+改性壳聚糖和海藻酸钠并分别与柔性链聚乙烯醇(PVA)共混, 制备了Fe-SA-CS-GA/PVA聚合物双极膜. 测定膜的红外光谱, I-V工作曲线, Na+与Cl-透过双极膜的迁移数, 离子交换容量及阴阳两极室中OH-及H+的变化, 并以扫描电镜观察膜表面和界面层形态. IR与接触角分析结果表明, CS经GA/PVA改性后其亲水性能得到显著提高. 将SA-CS/PVA双极膜及Nafion膜应用于电氧化制备3-甲基-2-吡啶甲酰胺. 实验结果表明, 以SA-CS/PVA双极膜为隔膜合成3-甲基-2-吡啶甲酰胺的产率达到49.8%, 高于以Nafion膜为隔膜的产率.与传统的的方法相比, 该方法的反应条件温和且能有效利用能源.     

八羧基铜酞菁修饰海藻酸钠阳膜层制备CuPc(COOH)8-SA/mCS双极膜及其表征

在海藻酸钠(SA)中添加八羧基铜酞菁(CuPc(COOH)₈),并分别用Fe³⁺离子和戊二醛作为交联剂对海藻酸钠-八羧基铜酞菁阳膜层和壳聚糖(CS)阴膜层进行改性,制备了八羧基铜酞菁-海藻酸钠/改性壳聚糖双极膜(CuPc(COOH)₈-SA/mCS BPM)。在海藻酸钠中添加八羧基铜酞菁以促进中间层中水的解离。用FTIR、SEM等对制备的CuPc(COOH)₈-SA/mCS双极膜进行了表征。作为比对,制备了Fe³⁺离子改性的Fe-SA/mCS双极膜和二茂铁(Fc)离子改性的Fc-SA/mCS双极膜。实验结果表明,CuPc(COOH)₈-SA阳离子交换膜的离子交换容量、H⁺离子透过率均获得提高。与Fe³⁺离子改性或二茂铁离子改性的mSA/mCS双极膜相比,CuPc(COOH)₈-SA/mCS双极膜的阻抗、电阻压降(IR降)和溶胀度降低,在H+离子浓度低于8 mol·L^-1的酸溶液中具有稳定的工作性能。     

钨酸盐/过钨酸盐体系阴极间接电氧化合成红曲黄色素

以自制SBS-g-(AA/StSO3Na)/SBS-g-DMAEMA双极膜作电解槽阴阳两极室的隔膜,借助正交试验确定阴极电还原氧气产生过氧化氢的最优条件,进而利用钨酸钠/过钨酸钠体系由阴极间接电氧化红曲红制备红曲黄色素.实验表明:以石墨作电极,阳极液为10%硫酸溶液,阴极液为0.5g·L-1红曲红丙酮水溶液,添加钨酸钠(浓度15mmol/L),调节pH至3,在通氧速率65cm3/min,电流密度5.78mA.cm-2下电解2h,阴极平均电流效率可达72.39%.电解产物经红外表征和紫外跟踪分析,证实了红曲红烯键环氧化反应的发生.     

mPAM/mCMC双极膜电解槽中MnO2电催化氧化制备甘油醛

分别以FeCl3和戊二醛等对羧甲基纤维素(CMC)和聚丙烯酰胺(PAM)进行改性, 制备了mPAM/mCMC双极膜. 测定了PAM、CMC胶体的电荷密度, mPAM/mCMC双极膜离子交换能力、I-V工作曲线等参数. 用扫描电镜和红外光谱对膜形貌与成分作表征, 膜厚≈260 μm, 中间界面层厚为纳米级. 热重分析表明膜具有较好的热稳定性. 以mPAM/mCMC双极膜为电解槽的隔膜, 间接电氧化甘油为甘油醛. 在电场的作用下, 双极膜中间层中的水离解产生H＋和OH−, OH−及时地传输入阳极室, 中和了电生成甘油醛时生成的H＋, 促进了正向反应的进行. 槽电压稳定, 产率达91.6%, 电流效率为65.5%.     

固定床反应器电合成乙醛酸的研究

以过饱和草酸水溶液为阴极液 ,盐酸为阳极液 ,在固定床电解槽中草酸电还原得到乙醛酸 .考察改变固定床的结构、电解温度及电流密度对生成乙醛酸电流效率和产率的影响 .结果表明 ,以铅粒作阴极 ,石墨板作阳极 ,电流密度 96 .3A·m- 2 ,阴极液空速 0 .5 0 5m·s- 1,电解温度 32℃时 ,在固定床双阳极室内反应 4 5min ,乙醛酸的电流效率仍达到 6 6 .2 % ,浓度 2 .0 2 %     

Electro-generation of TGA by Ni-mSA-mCS bipolar membrane

Ni-mSA-mCS bipolar membrane (BM) was prepared by sodium alginate (SA) and chitosan (CS),which were modified by Ca~(2 ) and glutaraldehyde as linking reagents,respectively,mSA-mCS membrane was characterized by FTIR,SEM,TG and used as a separator in the electrolysis cell to produce thioglycolic acid (TGA).The experiment results show that TGA was prepared effectively by electro-reduction of dithiodiglycolic acid (DTDGA) with the mixture of TGA and DTDGA in the cathodic chamber.The current efficiency was up to 66.7% at the room temperature (25℃) during the current density of 10 mA/cm~2.Compared with the traditional metal reduction method,the electro-reduction technology saves the zinc powder and eliminates the pollution to environment. (?)2007 Zhen Chen.Published by Elsevier B.V.on behalf of Chinese Chemical Society.All rights reserved.     

程序升温还原法研究氧化对煤中硫形态及结构的影响

用程序升温还原法研究了三种不同硫含量的煤被空气和HNO3氧化后含硫气体的逸出规律。结果表明，空气和HNO3氧化后，尽管煤中有机硫总量变化不大，但煤中H2S的释放量有所下降，而COS和SO2的生成量明显增加，这说明氧化作用使得煤中弱的有机硫变成S=O和SO2结构。与以往的研究结果不同的是，发现CS2的生成与FeS密切相关，同时对HNO3氧化后的煤来说，CS2的生成主要以气相中H2S和COS的反应为主。空气氧化后煤中CS2的生成量与原煤的差不多，但HNO3氧化后煤中释放出的CS2有所下降。提出通过（COS+SO2）/H2S的比值来研究煤及其中硫被氧化的程度，并对比了不同煤种及氧化后样品的气相含硫化合物发现：随变质程度的提高和煤中噻吩硫含量的增加，煤被氧化的程度下降。对同一煤种而言，HNO3的氧化程度要高于空气氧化的。     

GC/ITMS measurement of carbonyls and multifunctional carbonyls in PM2.5 particles emitted from motor vehicles.

A method was developed and tested to identify and quantitate carbonyls and multifunctional carbonyls in fine particulate matter (PM2.5; <2.5 microm aerodynamic diameter). The method relies on ultrasonic extraction of particulate matter on filters at -8 degrees C; derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA), and PFBHA along with bis (trimethylsilyl) trifluoroacetamide (BSTFA); and detection of the derivatives by gas chromatography/ion trap mass spectrometry. Ultrasonic extraction of model compounds from enriched particles was affected by solvent polarity (water > methylene chloride > toluene-isopropanol (2 + 1, v/v). Water provided the highest recovery for dihydroxy acetone, pyruvic acid, and hydroxy acetone, compared to methylene chloride, and toluene-isopropanol. Lowering the ultrasonication bath temperature from 0 degrees to -8 degrees C improved the recoveries of the less water soluble and more volatile species-methacrolein, methyl vinyl ketone, 2,3-butanedione, and tolualdehyde. The power of the method was demonstrated by identification and quantitation of carbonyls and multifunctional carbonyls in sample extracts of fine particulate matter (PM2.5) collected in the Caldecott tunnel, CA. The identities of crotonaldehyde, 2,3-butanedione, glyoxal, 9H-fluoren-9-one, glycolaldehyde, glyoxylic acid, levulinic acid, and 3-hydroxybenzaldehyde were confirmed by comparing the relative retention time and mass spectra of the analyte in the sample extract with an authentic standard. Quantitation of crotonaldehyde, glyoxal, 2,3-butanedione, glyoxylic acid, and levulinic acid was accomplished. This is the first report of glyoxylic acid, levulinic acid, and 3-hydroxybenzaldheyde in PM2.5 particles sampled in a roadway tunnel. It is also the first report of a C10 carbonyl with the molecular formula of C10H16O2, a hydroxy carbonyl with the molecular formula of C17H21NO2, and a hydroxy or dihydroxy carbonyl with the molecular formula of C16H14O2 or C9H10O3. The high-molecular weight hydroxy carbonyls, which were found only in the heavy-duty (diesel) bore, may be tracers of diesel emissions in air.     

阴极冷却反应器电合成乙醛酸

以过饱和草酸水深液为阴极液 ,盐酸溶液为阳极液 ,在阴极冷却电化学反应器内草酸电解合成乙醛酸 .考察了电极温度、电解液温度、电流密度和电极材料对合成乙醛酸的时空产率和电流效率的影响 .结果表明 ,阴极冷却反应器既节省能耗 ,又可使电解过程在较高草酸浓度下进行 ,提高电流效率和时空产率 .用石墨板做阳极 ,铅做阴极 ,电流密度为 4 0 9.4 6A·m-2 ,阴极液流速 μ=1 .0 8m·s-1,电解温度为 2 0℃左右时 ,电解 3 .70h ,可得到质量分数为 3 .52 %的乙醛酸溶液 ,平均时空产率为 0 .0 3 2kg·dm-3·h     

Salicylic acid-induced effects in the mixed-lipid (dipalmitoyl phosphatidylcholine-dipalmitoyl phosphatidylethanolamine) model membrane

The effect of the keratolytic drug salicylic acid (SA) on the thermotropic properties and fluidity of the mixed lipid membrane dipalmitoyl phosphatidylcholine (DPPC)-dipalmitoyl phosphatidylethanolamine (DPPE) had been studied using DSC, (1H and 31P) NMR, SAXS, and dynamic light scattering. The membrane was in multilamellar vesicular (MLV) and unilamellar vesicular (ULV) form with SA/(DPPC+DPPE) molar ratios, R(m), in the range from 0 to 0.5. It was found that the mechanism of interaction of SA with the lipid mixture exhibited similar patterns in both ULV and MLV. Both the NMR and DSC studies indicated that the drug molecules were probably localized in the lipid-water interfacial region neighboring the lipid headgroups or the glycerol moiety. The presence of the drug increased the fluidity of the membrane and the acyl chain order. However, studies on MLV showed that the presence of the drug in high concentration (R(m)0.2), caused destabilization of the DPPC-DPPE mixture, as indicated by the appearance of two endothermic transitions. DSC studies indicated that prolonged equilibration of the membrane led to reduced interaction between the lipid headgroups and the SA molecules. This reduced interaction could be due to the sequestering of the drug molecules into the lipid-water interfacial region, out of proximity to the polar headgroup or glycerol moiety. Effect of inclusion of cholesterol in the membrane systems was also studied.