杂多酸水溶液脱除烟气中SO_2新方法的研究(英文)

在孔板式吸收器 (孔板孔径 :5 0 μm～ 70 μm)中对杂多酸水溶液脱除烟气中SO2 的新方法进行了研究。在所考察的几种杂多酸中 ,H3PW1 2 O40 和H4SiW1 2 O40 对SO2 的脱除率较为接近 ,H7PMo2 W1 2 O49和Na2 HPMo1 2 O40 对SO2的脱除率相对较高 ,其中后者对SO2 的脱除率最高。杂多酸 (HPA)对SO2 的脱除率随HPA浓度的提高而增高 ,随进气中SO2 的浓度或吸收温度提高而减低。常温有利于HPA对SO2 的脱除。NaCl,NH4VO3,CuSO4及H3PO4这四种添加剂均能提高HPA对SO2 的脱除率。复配体系中 ,以上添加剂对HPA的最优配比为 :NaCl HPA∶H3PO4 HPA∶NH4VO3 HPA∶CuSO4 HPA =1 6∶1 8∶1 2∶1 4。进气中有NOx 存在下 ,HPA对SO2 的脱除率明显提高 ,当进气中NOx的质量浓度超过SO2 时 ,HPA对SO2 的脱除率接近 10 0 %。提出了在NOx 存在下HPA对SO2 的脱除反应式 ,这些反应式能够很好地说明NOx 的作用效果。以上结果表明 :HPA水溶液具有很好的烟气脱硫应用前景     

H3PO4—BF3／ZrO2及H3PO4—BF3—H2SO4／ZrO2催化剂的酸性及结构研究

本文研究了固体酸烷基化反应催化剂H3PO4－BF3／ZrO2及H3PO4－BF3－H2SO4／ZrO2的酸性及其结构。用指示剂法及正丁胺滴定法测定了催化剂的酸强度及酸量；用吸附吡啶的红外光谱法研究了催化剂的表面酸类型；用FT－IR、XPS、XRD、DTA－TG及TPDE等方法研究了催化剂的结构。结果表明；两种催化剂表面均只有Broensted酸，酸强度为－8．2＜H0≤-5.6。H3PO4-BF3/ZrO2中，活性组分强能是以H2PO4^-：BF3的形态存在，BF3通过与H2O4^-的络合作用是催化剂的活性增强。H3PO4－BF3／ZrO2中，存在H2SO4与ZrO2的成盐作用，同时亦有可能存在H2SO4与H3PO4、BF3之间的相互作用。催化剂在下焙烧失活的主要原因是H2PO4^-失水生成P2O7^4－，使催化剂表面质子酸量大幅度降低所致。     

快速测定COD最佳催化消解体系研究

通过正交试验 ,确定了测定环境水样中COD的最佳回流消解条件。以CuSO4作催化剂 ,KAl(SO4) 2 Na2 MoO4作助催化剂 ( 0 1 8gCuSO4·5H2 O 0 1 0gKAl(SO4) 2 ·1 2H2 O 0 1 0gNa2 MoO4·2H2 O) ,在H2 SO4 H3PO4体系中可很好地实现对样品的消解。该体系将回流时间由国标法的 2h缩短至 2 0min ,实现了快速测定的目的且大幅度降低测定成本。样品 1 0次平行测定的相对标准偏差为 1 1 % ;加标回收率为 97 7%～ 1 0 3 3% ,均与国标法无显著性差异     

第22届IChO理论题答案

无机化学1.反应方程（1）Ca3（PO4）2+4H3PO4→ 3Ca（H2PO4）2（2）CaF2+2H3PO4→ Ca（H2PO4）2+2HF↑ （3）CaCO3+2H3PO4→ Ca（H2PO4）2+CO2↑+H2O （4）Ca3（PO4）2+2H2SO4+4H2O →2CaSO4·2H2O     

Brφnsted酸性离子液体催化合成阿司匹林

用Brφnsted酸性离子液体[Hmim]BF4、[bmim]HSO4和[bmim]H2PO4代替浓H2SO4为催化剂催化乙酸酐对水杨酸的乙酰化,合成阿司匹林。考察了反应温度、反应时间、催化剂用量、酐/醇摩尔比对水杨酸酰化反应产率的影响和离子液体的重复使用性能。选择了最佳反应条件,以[bmim]H2PO4作为催化剂,催化剂用量为0.28g(1.18×10-3mol),水杨酸2.762g(0.02mol),乙酸酐4.083g(0.04mol),n(酐)∶n(醇)=2∶1,反应时间30min,反应温度70℃,产率最高达63.43%,并且[bmim]H2PO4溶于水后通过过滤和旋蒸脱水,重复使用3次,产率无明显变化。     

氧化环境和比例对改性Hummers法制备氧化石墨烯的影响

以鳞片石墨(GR)为原料,采用改性Hummers液相氧化法制备氧化石墨,通过超声剥离获得片状的氧化石墨烯(GO),探讨了H2SO4环境与H2SO4+H3PO4混酸环境和KMn O4与GR的比例对GO制备的影响。采用FT IR,UV,TG,XRD,SEM,Raman和XPS等分析手段对制备的GO进行分析。结果表明,GO外貌呈褶皱片状,在片层上主要有C=O、C—OH、—COOH和C—O—C等官能团,以共价键形式存在石墨层间;通过Raman,TG和XPS数据分析表明在H2SO4+H3PO4混酸环境下制备的GO含氧官能团较多,并且KMn O4与鳞片石墨的最佳比例是1∶4。     

参考答案

单元练习一参考答案及提示一、二、三选择题四、27．（1）变为紫红色;（2）5PbO2＋2MnSO4＋2H2SO4=4PbSO↓＋Pb（MnO4）2＋2HO,酸性;（3）不能,PbO2+4HCl=Pbcl2+Cl↑+2H2O28．（1）H3PO4;（2）Ba2－;（3）H2PO;（4）产生白色沉淀;（5）生成难清的Ba3（PO4）2和难电离的水,使溶液中离子浓度降低五、29．（1）（2）Li3N＋3H2O=3LiOH+NH3↑（3）小于30．H7IO731．Cu2（OH）2CO3+4CH3COOH=2（CH3COO）2Cu+CO2↑+3H2O,Fe＋（CH3COO）2Cu=（CH3COO）2Fe＋Cu,复分解反应,置换反应32．（1）2、5－n、2…     

氢氧化镁共沉淀法测定海水中纳摩尔级活性磷酸盐

利用海水中Mg(2+)与OH-生成沉淀时会共沉淀PO(3-4)的特性,富集海水中PO(3-4),富集后的Mg(OH)2沉淀用酸溶解,应用磷钼蓝-分光光度法测定.对试剂用量、离心速度及时间、Mg(OH)2,溶解用酸种类、H/Mo等实验参数和条件进行了优化.并采用与常规磷钼蓝法介质一致的H2SO4作为Mg(OH)2沉淀溶解...     

新试剂2-(2-苯并噻唑偶氮)-5-氨基苯甲酸与铂(Ⅳ)的显色反应研究

合成了新试剂2-(2-苯并噻唑偶氮)-5-氨基苯甲酸(BTABA),研究了新试剂与铂(Ⅳ)的显色反应,先后在pH 4左右的乙酸盐缓冲及H2SO4和H3PO4混合介质中,在表面活性剂CTMAB存在下,形成了配位比为Pt(Ⅳ)∶BTABA=1∶2的红褐色配合物,其最大吸收波长为612 nm,表观摩尔吸光系数为1.12×105L.mol-1.cm-1。铂含量在0~30.0μg/25 mL范围内服从比耳定律。应用于Pt-C催化剂中铂的测定,结果满意。     

三维超分子化合物[H_2(C_4H_(10)N_2)](SO_4)(H_2O)的制备、晶体结构及差热-热重性质研究

用MnSO4H2O和哌嗪在水-甲醇混合溶剂中反应得到了1个超分子化合物[H2(C4H10N2)](SO4)(H2O) (C4H14N2O5S)。 该晶体属单斜晶系, 空间群为P21/n, 晶胞参数为: a = 6.386(1), b = 11.695(2), c = 11.680(2) ? = 101.06(3), V = 856.1(3) 3, Z = 4, Mr =202.23 , Dc = 1.569 g/cm3, F(000) = 432, ?= 0.368 mm-1。 该化合物是由[H2(C4H10N2)]2+、SO42-、H2O通过氢键自组装而形成的。 其中[H2(C4H10N2)]2+存在2种椅式构象:一种[H2(C4H10N2)]2+与4个SO42-、2个H2O通过氢键相连, 另一种[H2(C4H10N2)]2+则与6个SO42-相连。 它们分别沿着b、c方向交替排列展开, 通过SO42-桥联成二维的层状结构;层与层之间在NH…O、CH…O、OH…O氢键的作用下互相连接, 形成了具有网状结构的三维超分子化合物。 差热及热重测试表明:该化合物从92℃开始分解,首先失去1个H2O, 然后再失去[H2(C4H10N2)]2+和SO4 2-。     

杂多酸水溶液脱除烟气中SO2新方法的研究

在孔板式吸收器（孔板孔径：50μm-70μm）中对杂酸水溶液脱除烟气中SO2的新方法进行了研究。在所考察的几种杂多酸中,H3PW12O40和H2SiW12O40对SO2的脱除率较为接近,H7PMo2W12O49和Na2HPMo12O40对SO2的脱除率相对较高,其中后者对SO2的脱除率最高。杂多酸（HPA）对SO2的脱除率随HPA浓度的提高而增高,随进气中SO2的浓度或吸收温度提高而减低。常温有利于HPA对SO2的脱除。NaCl,NH4VO3,CuSO4及H3PO4这四种添加剂均能提高HPA对SO2的脱除率。复配体系中,以上添加剂对HPA的最优配比为：NaCl/HPA:H3PO4/HPA:NH4VO3/HPA:CuSO4/HPA=1/6:1/8:1/2:1/4。进气中有NOx存在下HPA对SO2的脱除反应式,这些反应式能够很好地说明NOx的作用效果。以上结果表明：HPA水溶液具有很好的烟气脱硫应用前景。     

Determination of traces of chloride and fluoride in H2SO4, H3PO4 and H3BO3 by in situ analyte distillation-ion chromatography

A simple dual vessel in situ analyte distillation (IAD) system has been developed for suppressed ion chromatographic determination of chloride and fluoride ions in complex matrices. In IAD system, water vapours generated from the outer vessel reacts with sulfuric acid generating heat, thus favouring the quantitative distillation of chloride and fluoride within 30 min on water bath temperature (approximately 80 degrees C). The distilled analytes, as their respective acids in water, were directly injected into an ion-chromatograph. This newly developed method has been applied for analysis of trace impurities in H2SO4, H3PO4 and H3BO3. The detection limits for chloride is 8, 80 and 70ppb (w/w) for H2SO4, H3PO4 and H3BO3, respectively. For fluoride the detection limits are 6 and 60 ppb (w/w) for H2SO4 and H3PO4, respectively. The recovery of spikes for both the analytes ranged between 87 and 100%.     

Cr2O72-/Cr3+间接氧化环己醇合成己二酸

以Cr2O72-/Cr3+作为间接氧化剂电氧化环己醇制备己二酸.应用正交实验优化工艺条件,得出在原料比n(环己醇)∶n(Cr2O72-)=0.4∶1,t=35℃和CH2SO4=5mol.L-1条件下己二酸的收率可达70.29%.同时研究了Ag2SO4、(NH4)2SO4、H2SO4浓度、电流密度对Cr3+电氧化为Cr2O72-的影响,Cr3+的转化率可达82.52%.     

A novel ligand-free palladium catalytic system with SO3H-functional ionic liquids as cocatalyst for amidocarbonylation reaction

Effects of Lewis acid BF3·OEt2, and BrCnsted acids TsOH, CF3COOH, H3PO4, and HCIO4 as cocatalyst respectively on the ligand-free palladium-catalyzed amidocarbonylation were investigated. SO3H-functional ionic liquids 1-methyl-3-（4-sulfonic acid）butylimidazolium hydrosulfate [MIm（CH2）4803H][HSO4] and 1-methyl-3-（4-sulfonic acid）butylimidazolium triflate [MIm（CH2）4SO3H][OTf] were firstly employed as cocatalysts instead of these Lewis acid and Brφnsted acids. By using a ligand-free and weak corrosive catalyst in situ prepared form PdBr2, LiBr.H2O, and [MIm（CH2）4SO3H][OTf], the arnidocarbo- nylation of benzaldehyde, acetamide, and CO could proceed smoothly and afford N-acetyl-α-phenylglycine with yield of 58% in [C6mim]PF6 medium.     

Comparison of sulfuric acid- or phosphoric acid-modified CeO2 and the influence of surface acidity and redox property on its activity toward NH3-SCR

Research on Chemical Intermediates - A series of CeO2 prepared with H2SO4 (C–S), H3PO4 (C–P) and H2SO4?+?H3PO4 (C–P–S) were investigated in selective catalytic...     

过渡金属甲基磺酸盐催化醇的四氢吡喃化反应

以过渡金属甲基磺酸盐［Mn(CH₃SO₃)₂·2H₂O, Cu(CH₃SO₃)₂·4H₂O, Co(CH₃SO₃)₂·4H₂O和Zn(CH₃SO₃)₂·4H₂O］为催化剂,在室温条件下催化醇的四氢吡喃化反应,并对反应条件进行了优化。结果表明：当醇用量为30 mmol,醇和3,4-二氢吡喃摩尔比为1.0 ：1.1,甲基磺酸盐用量为1 mmol,二氯甲烷20 mL时,可高效催化醇的四氢吡喃化反应。与路易斯酸催化活性相比,过渡金属甲基磺酸盐催化醇的四氢吡喃化反应效果最好,催化酚的效果较差。用Mn(CH₃SO₃)₂·2H₂O和Cu(CH₃SO₃)₂·4H₂O催化正丁醇的四氢吡喃化反应,重复使用5次,收率分别为89%和92%。     

Synthesis and characterization of octa- and hexanuclear polyoxomolybdate wheels: role of the inorganic template and of the counterion

Eight new compounds based on [O3PCH2PO3]4- ligands and {MoV2O4} dimeric units have been synthesized and structurally characterized. Octanuclear wheels encapsulating various guests have been isolated with different counterions. With NH4+, a single wheel was obtained, as expected, with the planar CO32- guest, (NH4)12[(MoV2O4)4(O3PCH2PO3)4(CO3)2].24H2O (1a), while with the pyramidal SO32- guest, only the syn isomer (NH4)12[(MoV2O4)4(O3PCH2PO3)4(SO3)2].26H2O (2a) was characterized. The corresponding anti isomer was obtained with Na+ as counterions, Na12[(MoV2O4)4(O3PCH2PO3)4(SO3)2]39H2O (2b), and with mixed Na+ and NH4(+) counterions, Na+(NH4)11[(MoV2O4)4(O3PCH2PO3)4(SO3)2].13H2O (2d). With [O3PCH2PO3]4- extra ligands, the octanuclear wheel Li12(NH4)2[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].31H2O (4a) was isolated with Li+ and NH4+ counterions and Li14[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].34H2O (4c) as a pure Li+ salt. A new rectangular anion, formed by connecting two MoV dimers and two MoVI octahedra via methylenediphosphonato ligands with NH4+ as counterions, (NH4)10[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2(HO3PCH2PO3)2].15H2)O (3a), and Li9(NH4)2Cl[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2]. 22H2O (3d) as a mixed NH4+ and Li+ salt have also been synthesized. The structural characterization of the compounds, combined with a study of their behavior in solution, investigated by 31P NMR, has allowed a discussion on the influence of the counterions on the structure of the anions and their stability. Density functional theory calculations carried out on both isomers of the [(MoV2O4)4(O3PCH2PO3)4(SO3)2]12- anion (2), either assumed isolated or embedded in a continuum solvent model, suggest that the anti form is favored by approximately 2 kcal mol(-1). Explicit insertion of two solvated counterions in the molecular cavity reverses this energy difference and reduces it to less than 1 kcal mol(-1), therefore accounting for the observed structural versatility.     

H3PO4-BF3/ZrO2及H3PO4-BF3H2SO4/ZrO2催化剂上异丁烷/丁烯的烷基化反应

研究了H₃PO₄-BF₃/ZrO₂及H₃PO₄-BF₃-H₂SO₄/ZrO₂催化剂对异构烷烃烷基化反应的催化作用。就载体的焙烧温度、活性组分的浓度、BF₃及H₂SO₄的添加及反应温度对催化剂活性的影响进行了较为详尽的研究。     

催化甘油脱水反应的酸活化蒙脱石负载WOx催化剂的研究

甘油是一种可由生物资源生产、可持续的、可降解的平台化学品,是生物柴油、肥皂化工等工业生产过程中的主要副产物.催化甘油脱水反应生产丙烯醛,有望能替代丙烯等石油裂解产物合成丙烯醛的传统工业路线.丙烯醛是一种重要的化工中间体,被用于合成蛋氨酸、丙烯酸、3-甲基吡啶和1,3-丙二醇,并被广泛地应用于农药、医药、高分子材料等领域.随着全球可持续能源发展,生物柴油生产迅速发展,将产生大量的副产物甘油.利用甘油为原料,通过合适的催化剂的催化脱水反应生成丙烯醛,是近十多年来国内外工业催化的研究热点之一.用于催化甘油脱水合成丙烯醛的酸催化剂有杂多酸、金属氧化物、沸石与酸性粘土矿物等.钨磷杂多酸(H3PW12O40)负载的催化剂虽然具有较强的酸性,有利于催化甘油脱水,但容易导致结焦,而且热稳定差,容易失活.钨磷杂多酸负载于SiO2,TiO2,Al2O3,SiO2-Al2O3,K-10蒙脱石上表现出不同的催化活性,表明催化剂和载体的表面酸性和孔结构影响催化性能.近来研究发现,负载于ZrO2,Al2O3的钨氧化物(WOx)催化剂热稳定性好、酸性高,在甘油脱水反应生成丙烯醛中表现出良好的催化性能.但有关钨氧化物(WOx)结构、催化活性受载体组成、酸性影响的本质和规律一直不清楚.本文采用20 wt%的硫酸、盐酸、磷酸和乙酸对蒙脱石进行酸改性,并在磷酸改性的蒙脱石上负载W含量为4–16 wt%的WOx作为催化剂,用于甘油气相脱水反应.X-射线衍射(XRD)、热重-差热法(TG-DTG)、氨程序升温脱附(NH3-TPD)、红外光谱(FT-IR)和紫外漫反射可见光谱(DR UV-vis)等表征,探讨了酸改性和负载WOx的蒙脱石对催化剂催化性能的影响.蒙脱石经过20wt%的硫酸、盐酸、磷酸和乙酸的活化,酸性增加.四种酸改性的蒙脱石对甘油气相脱水反应均有催化活性,这是因为在蒙脱石酸活化过程中,H+经过阳离子交换反应进入蒙脱石层间,同时蒙脱石八面体中的部分Al3+被浸出,使层板上出现不饱和Al3+,为催化剂提供了L酸位,蒙脱石硅氧四面体上的Si?OH以及[AlO4]上吸附的H3O+提供了B酸位.XRD分析表明,负载WOx的蒙脱石表面存在WO2.72,WO2.9和WO3三种不同类型的WOx,当钨负载量从12 wt%增至16 wt%,孤立的单斜晶系WO3晶粒增多.NH3-TPD和DR UV-vis结果表明,WOx负载在蒙脱石表面以[WO5/WO6](B酸位)、[WO4]和单斜晶系WO3相(L酸位)形式存在.蒙脱石上负载WOx能够调节催化剂的酸强度、酸量和酸位.随着钨负载量从4 wt%增至12 wt%,丙烯醛收率从40.9%增加到67.3%;进一步增加钨负载量到16 wt%,丙烯醛收率降为50.7%.结果发现,随着钨负载量的增加,催化活性组分含量增加,[WO5/WO6](B酸位)增加,使催化活性增加;当W负载量达到16 wt%时,WOx分散性降低,且在催化剂表面形成孤立的单斜晶系WO3相(L酸位),不利于提高丙烯醛选择性.当反应温度为320 oC,甘油水溶液浓度为15 wt%时,磷酸活化蒙脱石负载12 wt%W的催化剂上甘油转化率为89.6%,丙烯醛收率达到73.3%.     

The effect of acidification on the determination of organic carbon, total nitrogen and their stable isotopic composition in algae and marine sediment

We investigated the effects of sample acidification on the stable carbon and nitrogen isotopic composition (delta13C and delta15N), as well as the organic carbon (OC) and total nitrogen (TN) composition, of an algal culture and a marine sediment. Replicate measurements of untreated and acid-treated samples were made using 1 M, 2 M and 6 M HCl, 6% H2SO3 and 1 M H3PO4. For all treatments the precision of the analysis for the acid-treated sample was equal to or less than that in the non-acidified sample. For the algae, analysis of variance (ANOVA) indicated no significant differences in the mean OC and TN concentration, or delta13C and delta15N composition, between any acid treatment and non-acidified samples. For the sediment sample a comparison could only be made between the different acid treatments because the untreated contained significant amounts ( approximately 30%) of carbonate carbon. ANOVA indicated that the mean OC determined in sediment samples after the 1 M HCl treatment and the mean delta13C values after the 6% H2SO3 and 1 M H3PO4 treatments were significantly different (p < 0.013 and < .05, respectively) from all other treatments. Mass balance calculations indicate that in some instances delta13C values were biased due to a contribution from unreacted carbonate carbon. There were no significant differences in the mean TN between any acid-treated and non-acidified samples. The mean delta15N values after 6 M HCl, 6% H2SO3 and 1 M H3PO4 treatments were significantly different from the untreated sediment sample (p < 0.044). Based on the significant bias observed for the delta15N and delta13C values, a weak (1-2 M) HCl solution is confirmed as the most appropriate acid for the removal of inorganic carbon from natural materials requiring elemental and isotopic analysis.