废选择性催化还原脱硝催化剂中金属钨和钒的萃取分离及回收

以三正辛胺(TOA)+异癸醇的煤油溶液为萃取剂,对废选择性催化还原(SCR)脱硝催化剂中的钨和钒进行萃取分离及回收。考察了萃取时间、有机相(萃取剂)与液相(酸浸液)(O/A)体积比、浸出液pH值、萃取剂浓度等对W、V萃取率的影响。结果表明:当酸浸液pH值为2.5,TOA体积分数为12%,O/A体积比为0.1,萃取时间为15 min条件下,W与V的萃取率可分别达到98.78%和94.94%。同时以Na OH为反萃取剂,对萃取有机相中W和V进行反萃取。结果发现:W几乎被完全从有机相中反萃出来,反萃取率高达99.99%,V的反萃取率可达88.05%。通过向反萃取溶液中加入H2SO4溶液并阶段性的调节其pH值,使W和V分别以H_2WO_4和NH_4VO_3形式沉淀,并将沉淀物在500℃煅烧,分别得到纯度均大于99%的W和V的氧化物WO_3和V2O5。     

伯胺N1923从废SCR催化剂碱浸出液中萃取分离钨的研究

为回收利用废弃选择性催化还原(SCR)催化剂，采用酸化伯胺N1923从钠化焙烧废SCR催化剂的浸出碱液中萃取分离钨(W)，并对萃取参数进行了优化。结果表明，在溶液pH为10、N1923质量分数为10%、水相和有机相的相比为1、时间为4 min和温度为25℃时，W的单级萃取率高达99.28%；溶液中的其他元素P、V和Si的萃取率分别为55.44%、96.70%和55.00%；用硫酸洗涤除去共萃的杂质元素P、V和Si,W的损失可忽略不计，氨水可以从有机相中反萃出96.89%的W得到钨酸铵溶液。利用傅里叶红外光谱仪分析了萃取过程，N1923经H₂SO₄预酸化后转化为伯胺盐(RNH₃⁺)，通过阴离子交换萃取了WO₄^2-。     

铁钨复合氧化物用于NH_3选择性催化还原NO

采用共沉淀法制备铁钨复合氧化物催化剂,用于NH3选择性催化还原NO,考察了Fe/W物质的量之比、反应空速、SO2和H2O对催化剂脱硝活性的影响,同时运用SEM、XRD、BET、NH3-TPD等表征手段对催化剂的微观形貌、晶型、比表面积、孔结构参数及表面酸性进行了分析。实验结果表明当n(Fe)∶n(W)=4∶1时,催化剂的反应活性最佳,其在300~400℃温度范围内及GHSV=75 000 h-1条件下NO转化率仍保持在90%以上,同时其也显示出较强的抗SO2和H2O中毒性能。通过表征发现Fe与W之间强烈的相互作用,较大的比表面积和催化剂较强的酸性是催化剂催化活性较好的主要原因。     

巯基乙酸萃取工艺的研究

通过对若干种有机溶剂的比较,选定磷酸三丁酯(TBP)作为萃取剂,甲基异丁基甲酮(M IBK)作为稀释剂,对巯基乙酸(TGA)的萃取进行研究。同时考察了TGA浓度、萃取温度、pH等条件对TGA萃取分配系数的影响。实验结果表明,采用V(M IBK)∶V(TBP)=1∶9的混合萃取剂,控制V(有机相)∶V(水相)=1∶2,在室温下萃取TGA合成液两次,TGA萃取率达98.31%。萃取后有机相中含有无机酸杂质H2SO4和有机酸杂质二硫代二乙酸(DTDGA),可采用w(NaOH)=20%的水溶液洗涤去除。洗涤时控制n(NaOH)/n(DTDGA)=7,洗涤后无机酸杂质H2SO4去除率达100%,有机酸杂质DTDGA去除率达80.3%,TGA损失率2.6%,有机相中m(杂质)/m(TGA)=0.007 3。     

AlH3P2W18O62?nH2O/MCM-41的制备、表征及催化合成阿斯匹林性能研究

通过浸渍法制备了MCM-41负载Dawson型磷钨酸铝催化剂(Al H3P2W18O62·n H2O/MCM-41),并用于催化合成阿司匹林,采用FTIR、XRD、SEM、EDS、NH3-TPD、Py IR、N2吸附-脱附及TG-DSC对其结构进行表征。探讨了磷钨酸铝负载量、催化剂用量、水杨酸与乙酸酐摩尔比、反应时间、反应温度及催化剂重复使用次数对阿司匹林收率的影响。结果表明,Al H3P2W18O62·n H2O均匀地负载在MCM-41载体上,负载后仍保持Dawson结构。与Al H3P2W18O62·n H2O相比,负载型催化剂(30%Al H3P2W18O62·n H2O/MCM-41)呈"蜂巢状",比表面积明显增大、热稳定性提高,同时具有Lewis酸中心和Brnsted酸中心,但酸强度降低。在优化反应条件下:即Al H3P2W18O62·n H2O负载量为30%(质量分数),w(30%Al H3P2W18O62·n H2O/MCM-41)=4.1%(基于反应物的质量),水杨酸与乙酸酐摩尔比1∶1.5,80℃反应30 min,产物收率为96.3%。催化剂可重复使用,第6次使用时产物收率达80.6%。30%Al H3P2W18O62·n H2O/MCM-41具有良好的催化活性和稳定性。     

过渡金属取代钨锰三元杂多酸盐的合成表征及催化活性

采用直接合成法合成K6[MnCu(H2O)W11O39],K5[MnFe(H2O)W11O39],K6[MnCo(H2O)W11O39],K6[MnZnH2(O)W11O39],K6[MnNi(H2O)W11O39],K6[MnCd(H2O)W11O39]等6种过渡金属取代的钨锰杂多酸盐,利用红外光谱、紫外光谱对合成产物的结构进行了表征。结果表明,6种杂多阴离子具有Keggin结构。利用酯化反应考察了所合成催化剂的催化活性,并且确定了最佳催化反应条件:酸醇物质的量比1∶1,催化剂用量占原料总量的1.5%,反应时间4h,反应温度控制在120℃。结果表明,过渡金属取代钨锰三元杂多酸对乙酸正丁酯的催化产率95%以上。     

钨掺杂二氧化钒/石墨烯复合物的制备及性能

以氧化石墨烯粉末(GO)、五氧化二钒(V2O5)、草酸(C2H2O4·2H2O)和钨酸铵〔(NH4)10H2(W2O7)6〕为原料，用水热法制备了一系列钨掺杂二氧化钒/石墨烯复合物，考察了钨掺杂量、氧化石墨烯复合量对复合材料的相变温度及导热率的影响。通过XRD、SEM、DSC、FTIR、激光导热系数测量仪对复合材料的结构形貌、相变性能等进行了表征。结果表明：石墨烯复合后二氧化钒粒子团聚情况得到有效改善，并均匀复合在石墨烯表面。当钨的原子百分比含量为2.5%、氧化石墨烯含量为4%（以五氧化二钒质量为基准）时，形成的钨掺杂二氧化钒/石墨烯复合物与纯二氧化钒相比，相变温度由66 ℃降低到32.2 ℃，导热率由0.700 W/(m·K)提升到16.341 W/(m·K)，该复合材料能同时满足良好的隔热性与高导热等性能要求，取得了隔热性与散热性这一矛盾的对立与统一。     

镁合金钼酸盐/磷酸盐复合转化膜的制备

研究了镁合金钼酸盐/磷酸盐复合转化膜,分析了影响复合转化膜性能的因素.结果表明:当钼酸盐/磷酸盐复合转化液pH值为5,n(MoO2-4)/n(H2PO-4)为1/2时,镁合金钼酸盐/磷酸盐复合转化膜腐蚀电流最低,耐蚀性能较好,微观表面呈均匀"蜂窝"状,具有最佳防腐蚀性能;并且当Ca2 和Mn2 同时存在时,膜层的极化电阻最大.     

硝基T酸萃余硫酸溶液纳滤膜法净化技术

H酸的中间体硝基T酸生产中产生大量废酸,通过叔胺类萃取剂N235处理该废酸,再采用纳滤膜脱除萃余液中残留萃取剂及可溶性萘系磺化物。适宜的纳滤前处理萃取条件:在萃取油相中不添加正辛醇;N235体积分数为33%,W/O(水油比)为2:1。经过二级萃取后,CODCr去除率为79%。二级萃余液采用纳滤膜浓缩至1/6体积,平均通量可达9.9~20.9 L·m-2·h-1,纳滤后可回收27%浓度的硫酸,CODCr总去除率为94%~97%,总色度去除率99%。大幅降低污染物排放量。     

Hβ沸石催化合成2-叔丁基对甲酚

合成了n(S iO2)/n(A l2O3)分别为20、25和38的Hβ沸石,并用XRD和NH3-TPD对其物相和酸性质进行了表征。以Hβ沸石为催化剂,在固定床反应器上考察了对甲酚与甲基叔丁基醚(MTBE)合成2-叔丁基对甲酚的反应,讨论了反应温度、液时空速(WHSV)、MTBE与对甲酚的配比和Hβ沸石的n(S iO2)/n(A l2O3)对转化率和收率的影响,最优反应条件为:Hβ〔n(S iO2)/n(A l2O3)=20〕为催化剂,反应温度120℃,n(MTBE)/n(对甲酚)=1.5,液时空速1.02 mL/h,对甲酚转化率为68%,2-叔丁基对甲酚的收率为64%。     

Separation of vanadium and tungsten in roasting-acid leaching solutions of the spent selective catalytic reducing denitration catalyst by co-extraction using hydroxyoxime extractant-quaternary ammonium salt extractant LIX984–N263 extractant

This study presents a synergistic extraction and recovery of vanadium and tungsten by mixed extractants (LIX984 and N263) from an acid leaching solution which was obtained from spent denitrification catalysts by chlorination heat treatment and acid leaching. Through thrice counter-flow extraction, 99.5% V and 99.7% W were extracted, while 3.0% Fe, 2.9% Ti, 2.1% P, and 3.3% Mg were co-extracted at a LIX984:N263 volume content of 22.0%, the phase ratio of 2.5 and the mother liquor's pH of 2.5. Then, at 0.80 mol/l NaOH and a phase ratio of 1, 99.9% tungsten and 99.1% vanadium were stripped from the organic phase to the aqueous phase. Subsequently, the aqueous phase's tungsten of 99.3% and vanadium of 98.1% were separated as calcium tungstate and ammonium metavanadate, respectively. In contrast, the residual solutions containing tungsten and vanadium can be returned to the following purification separation process to recover the valuable metals from the solution. Roasting converts the precipitated calcium tungstate and ammonium metavanadate to V₂O₅ and WO₃ products. In addition, the thermodynamic analysis found the separation and recovery of tungsten and vanadium from the acid leach solution with LIX984:N263 to be an exothermic process. This method can be effectively extended for the separation of vanadium and tungsten from spent denitrification catalysts by the proposed process and validates the conclusion that metals with similar properties can be extracted using a mixture of extractants.     

Electrodeposition of noncrystalline cobalt–tungsten alloys from citrate electrolytes

Induced electrodeposition of Co–W alloys onto steel substrates from acid citrate baths has been investigated. The effects of some plating parameters, such as current density, pH and temperature on the potentiodynamic cathodic polarization curves, cathodic current efficiency of the alloy and the percentage tungsten in the alloy were studied. Highly adherent and compact Co–W alloys codeposited from citrate baths containing up to 28 mass % tungsten were obtained. The percentage W (w/w) in the alloy increases with increasing pH, bath temperature and Co²⁺ ion concentration. On the other hand, the percentage W in the alloy decreases with increasing current density. Anodic linear stripping voltammetry (ALSV) indicated that the alloy might consist of one phase solid solution. These alloys were determined to be noncrystalline by X-ray diffraction analysis.     

复合萃取剂提取林可霉素机理及填料萃取塔中试研究

以中试填料萃取塔为设备研究了复合萃取剂（正辛醇和煤油）萃取林可霉素的宏观特性及传质强化。使用斜率法确定萃合物的结构和反应平衡常数以指导改进设备和强化传质;为了提高林可霉素萃取效果,考察了溶液pH值、相比（W/O）、填料类型、分布盘的使用等因素对提取林可霉素效果的影响。结果表明：以正辛醇为萃取剂萃取林可霉素的过程中,反应平衡常数K为0.072;复合萃取剂中正辛醇最佳含量为0.8（体积分数）;萃取林可霉素的最佳pH值为10～11,最佳相比（W/O）为3;规整填料和散装填料萃取效果有限,分布盘可以大大加强传质,同时加装分布盘的填料萃取塔的单位体积处理量是混合澄清槽的12.8倍,萃取剂循环量大大减少。研究结果对复合萃取剂的萃取机理和填料萃取塔提取林可霉素的实际应用具有一定指导意义。     

含氧酸根检测方法的研究现状及质谱法在钨钼分离中的应用前景

溶剂萃取法具有操作简单、回收率高、产品纯度高等优点，被广泛应用于钨钼分离。分离过程中钨钼离子形态会影响与萃取剂的结合方式及萃取历程，因而研究钨钼的离子形态变化有助于深入了解钨钼分离机理，进而指导工业生产。在水溶液中，钨钼的离子形态以钨钼含氧酸根形式存在，研究钨钼离子形态的本质即研究不同钨钼含氧酸根形式对萃取分离过程的影响。本工作综述了水溶液中含氧酸根离子形态的仪器分析方法，发现ESI-MS(电喷雾质谱法)在监测萃取过程中钨钼离子形态转化路径中具有潜在应用，并对ESI-MS在湿法冶金领域中监测钨钼离子形态及其转化规律的应用进行了展望，旨在为今后深入了解钨钼分离机理、定向调控钨钼分离过程及工业生产提供理论指导。     

二(2-乙基己基)磷酸萃取L-苯丙氨酸

以二（2-乙基己基）磷酸（D2EHPA）-正辛烷萃取L-苯丙氨酸为对象,研究了D2EHPA浓度、L-苯丙氨酸初始浓度以及pH值对萃取平衡分配系数的影响。不同pH值下负载有机相的红外谱图分析表明,D2EHPA与L-苯丙氨酸形成的萃合物结构与pH值无关。提出了在萃取过程中同时存在着离子交换反应和质子转移反应的观点。1个氨基酸分子与2个二（2-乙基己基）磷酸二聚体相结合。本文建立的萃取平衡分配系数关联式,拟合精度令人满意。     

Dissolution kinetics of WO3 in acidic solutions

Potentiostatic polarization and rotating disk electrode techniques were used to obtain the rate constant for the dissolution of electrochemically-formed (at 1 V) WO₃ on tungsten (W) in acidic solutions. The corresponding rate constant for the chemical dissolution of WO₃(s) powder was found by measuring the dissolved tungsten concentration as a function of time and pH. The chemical dissolution experiments supported the view that the rate-determining step in the anodic reaction of W in acidic solution is the chemical dissolution of WO₃(s) formed on the metal surface. Zeta potential measurements gave the isoelectric point (iep) of the WO₃(s) powder as pH 1.5, a value that was somewhat smaller than the point of zero charge (pzc) of WO₃(s) formed on W metal (pH 2.5). This difference was attributed to the highly hydrated nature of the oxide film formed on W metal in aqueous systems.     

疏水性离子液体-中性磷氧萃取剂萃取稀土元素的应用

液液萃取广泛应用于稀土元素的分离回收，为了便于相的分离，通常采用疏水性萃取剂。基于液液萃取的特性，通过微波辅助法合成了疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[BMIM][PF₆]）。分别探究了[BMIM][PF₆]搭配不同中性磷氧萃取剂对稀土元素中Nd³⁺和Pr³⁺的萃取研究。结果表明1-丁基-3-甲基咪唑六氟磷酸盐-三正辛基氧化磷（[BMIM][PF₆]-TOPO）为最适宜萃取体系。在最适宜萃取体系下，探究了时间、温度、pH值、V（A）/V（O）（水相稀土离子/有机相萃取体系）和萃取组分体积比对萃取效率的影响。结果表明：萃取时间为20 min、温度为25℃、pH值=6.0、V（A）/V（O）=1.0、V_[BMIM][PF6]：V_TOPO=1：1，体系对于Nd³⁺的萃取效果最佳，萃取率可达97.8%；萃取时间为25 min、温度为25℃、pH值=6.0、V（A）/V（O）=1.0、V_[BMIM][PF6]：V_TOPO=1：1，体系对于Pr³⁺的萃取效果最佳，萃取率可达94.2%；萃取过程为放热反应，反应焓变分别为ΔH（Nd³⁺）=-38.43 kJ·mol^-1，ΔH（Pr³⁺）=-28.76 kJ·mol^-1。     

废SCR催化剂钠化焙烧回收钨和钒的机理探究

文章从热力学角度,分别以温度和碳酸钠加入量为变量,用热力学软件HSC Chemistry计算了蜂窝状废SCR催化剂钠化焙烧的过程,得到了相应的相图,并分析了其对钨和钒浸出率的影响。研究了不同动力学条件下钨和钒的浸出率,得到最佳焙烧条件为：碳酸钠加入量为30%、焙烧温度为800 ℃、粒度为75～100 μm、焙烧时间为2～2.5 h。采用XRD和SEM进行物相和形貌分析。从理论和实验上探究了失效SCR催化剂钠化焙烧过程的机理。     

Easy removing of phenol from wastewater using vegetable oil-based organic solvent in emulsion liquid membrane process

Phenol is considered as pollutant due to its toxicity and carcinogenic effect.Thus,variety of innovative methods for separation and recovery of phenolic compounds is developed in order to remove the unwanted phenol from wastewater and obtain valuable phenolic compound.One of potential method is extraction using green based liquid organic solvent.Therefore,the feasibility of using palm oil was investigated.In this research,palm oil based organic phase was used as diluents to treat a simulated wastewater containing 300×10~(-6) of phenol solution using emulsion liquid membrane process(ELM).The stability of water-in-oil(W/O) emulsion on diluent composition and the parameters affecting the phenol removal efficiency and stability of the emulsion;such as emulsification speed,emulsification time,agitation speed,surfactant concentration,pH of external phase,contact time,stripping agent concentration and treat ratio were carried out.The results of ELM study showed that at ratio7 to 3 of palm oil to kerosene,5 min and 1300 r·min~(-1) of emulsification process the stabile primary emulsion were formed.Also,no carrier is needed to facilitate the phenol extraction.In experimental conditions of500 r·min~(-1) of agitation speed,3%Span 80,pH 8 of external phase,5 min of contact time,0.1 mol·L~(-1) NaOH as stripping agent and 1:10 of treat ratio,the ELM process was very promising for removing the phenol from the wastewater.The extraction performance at about 83%of phenol was removed for simulated wastewater and an enrichment of phenol in recovery phase as phenolate compound was around 11 times.     

场激活燃烧合成碳化钨和碳化钨钴反应机理

在场激活下燃烧合成碳化钨和碳化钨-钴复合材料，采用燃烧过程中切断电场的方法，得到了一系列不同相组成的燃烧产物，通过对样品从反应物端到产物端形貌和相组成的分析,研究了场激活下钨碳燃烧反应机制，WC的形成是通过钨碳之间的固-固反应进行的，首先生成W2C，然后再形成WC，W2C是反应的中间相。金属钴产生液相，促进了W2C的形成和W2C向WC的转化并与W和W2C作用形成WxCyCoz类化合物。