氧压条件下硫酸溶液浸出锡铜渣试验研究

氧压条件下硫酸溶液浸出锡铜渣试验，开展了初始酸度、浸出液固比、反应温度、反应压力、反应时间以及浸出液返浸等技术参数对铜浸出率、锡入渣率的影响，试验结果表明：采用的技术参数为初始酸度150 g/L,液固比5∶1,反应温度130℃,反应压力1.2 MPa,反应时间4 h,浸出液可返浸，铜入液，锡入渣，浸出渣中的铜质量分数小于2%,锡入渣质量分数高达99%以上，浸出液可返浸，较好地实现锡铜分离，是处理锡铜渣的一种有效手段。     

富硼渣硫酸浸出实验研究

以硼铁精矿含碳球团还原熔分得到的富硼渣为原料,研究了其物相成分,并进行硫酸浸出实验,探究了硫酸用量、反应温度、反应时间及液固比对硼浸出率的影响。结果表明,该富硼渣中三氧化二硼的质量分数达到20%,主要含遂安石相和橄榄石相。硫酸浸出实验中,硼浸出率随着硫酸用量、反应温度和反应时间的增加而增大,随着液固比的增大而减小。当硫酸用量为理论用量的80%、液固体积质量比为8 mL/g、反应温度为40 ℃、反应时间为60 min时,富硼渣中硼的浸出率达到93.56%。     

常压碱溶法提取软锰矿酸浸渣中的硅

软锰矿经还原焙烧酸浸提取锰后,渣中二氧化硅质量分数超过60%,而且其他杂质较少,是较好的含硅原料。采用在常压下用氢氧化钠溶液浸出软锰矿酸浸渣中硅的工艺,通过正交实验和单因素实验,考察了反应温度、反应时间、氢氧化钠浓度和液固比等因素对硅浸出率的影响,并对浸出机理进行了探讨。结果表明：影响硅浸出率的主要因素依次为反应温度、液固比、反应时间和氢氧化钠浓度。当反应温度为120 ℃、液固比（溶液体积与软锰矿酸浸渣质量比,mL/g）为2∶1、反应时间为5.5 h、氢氧化钠浓度为20 mol/L时,硅的浸出率达到70.9%。     

电解锰硫化渣浸出低品位软锰矿的研究

以低品位软锰矿为研究对象,采用电解锰硫化渣浸出其中的锰,考察了搅拌速率、液固比、温度、硫化渣用量、硫酸用量和反应时间对锰浸出率的影响。结果表明,在搅拌速率为400 r/min,液固比为5,硫化渣用量3 g,硫酸浓度140 g/L,温度90℃,浸出时间3.5 h时,锰的浸出率达94.27%,实现了硫化渣的资源再利用。     

钒渣焙烧-水热碱浸提钒

实验研究了不同条件下钒渣焙烧与NaOH溶液水热浸出对钒浸出率的影响,并分析了过程机理. 结果表明,焙烧温度达700℃以上可实现钒铁尖晶石的氧化分解,850℃焙烧2 h是钒渣空白焙烧的最佳条件,浸出的最佳条件是反应温度180℃、钒渣粒度小于74 mm、反应时间2 h、液固比5 L/g、碱浓度30%(w)、搅拌速度500 r/min. 该条件下钒浸出率达95%以上,无有害气体产生.     

磷酸分解磷矿过程中金属元素的浸出规律研究

探究了以磷酸分解磷矿,关键酸解工艺参数对磷及Fe、Al、Mg、Pb、As浸出的影响规律,并从热力学角度进行了分析。结果表明,磷矿内磷及Fe、Al、Mg浸出率随磷酸质量分数、反应温度、反应时间和液固比的增大而增大,搅拌速度影响不明显;Pb浸出率随磷酸质量分数、反应温度和液固比的增大而增大,搅拌速度、反应时间影响不明显;As浸出率随反应温度升高呈先增大后减小趋势,随反应时间增加略有减小,磷酸质量分数、搅拌速度和液固比影响不明显。控制磷酸质量分数为30%（以P₂O₅计）、反应温度为80 ℃、搅拌速度为300 r/min、反应时间为150 min、液固质量比为10∶1,在此条件下,磷及Fe、Al、Mg、Pb、As的浸出率分别为98.65%、68.56%、48.54%、95.84%、32.85%和84.62%。通过热力学分析表明磷矿内Mg、As浸出率较高,Pb浸出率较低,而Fe、Al浸出率大小主要取决于磷矿中褐铁矿及高岭土含量。     

再生铅精炼碱渣中锡的富集研究

采用浸出-中和沉淀工艺回收富集再生铅精炼碱渣中锡。新产出碱渣在液固比3,反应时间1.5h,室温条件下浸出,锡浸出率达到93%以上;库存碱渣在液固比3,反应时间1.5 h,浸出温度60℃,氢氧化钠浓度100 g/L条件下锡浸出率达到68%的比较理想效果。通过对各种类型碱渣按照一定比例混合可以实现碱渣中锡的选择性浸出,浸出浆料中加入5‰的4‰PAM絮凝剂可以实现浸出浆料的快速液固分离。采用废旧铅酸电池拆解废硫酸对浸出液进行中和沉锡,在pH=6～8时浸出液中锡基本完全沉淀;中和沉淀物干燥后锡含量约为60%、铅小于2%、锑小于0.5%。     

石煤尾矿制备白炭黑的研究

利用石煤尾矿制备白炭黑,考察了氢氧化钠浓度、固液比、反应温度、反应时间对二氧化硅浸出率的影响。结果表明:在氢氧化钠浓度为4 mol/L、固液比为1∶4、反应温度为100℃和反应时间为5 h条件下,二氧化硅浸出率为61.8%,白炭黑产品中二氧化硅含量超过90%,主含量达到行业标准。     

黄磷炉渣精制白炭黑的实验研究

以黄磷炉渣为原料,经硝酸浸出,钙元素以硝酸钙的形式分离,浸出渣经洗涤、干燥、煅烧可得到优质的白炭黑产品.白炭黑SiO2含量达到98.80%,Fe含量11 mg/kg,比表面积201 cm2/g.研究表明,浸出的最佳工艺条件为:搅拌速度360 r/min,反应时间4 h,反应温度80 ℃,液固比为10∶ 1,硝酸浓度20%,浸出渣洗涤终点pH=6.0.     

热酸浸出回收黄钾铁矾渣中有价元素

实验研究了硫酸和盐酸对黄钾铁矾渣中Fe,Si,Zn,Pb的浸出工艺.结果表明,硫酸浸出黄钾铁矾渣的最佳工艺条件是反应温度95℃、反应时间2 h、搅拌速率300 r/min、硫酸浓度1.2 mol/L、液固质量比100:5,该条件下Fe,Zn的浸出率达80%.盐酸浸出黄钾铁矾渣的最佳工艺条件是反应温度95℃、盐酸浓度2.8 mol/L、搅拌速率400 r/min、反应时间1.5 h、液固质量比100:5,该条件下Fe,Zn,Pb的浸出率分别达83%,89%和99%.采用黄钾铁矾法可将浸出液中的Fe元素沉淀,所得黄钾铁矾渣进行无害化固定处理,得富含Zn元素的溶液.     

Methylation of methyltrichlorosilane with methyl chloride over active metals and activated carbon

Gas phase methylation of methyltrichlorosilane with methyl chloride to high-valued dimethyldichlorosilane was carried out by using metallic aluminum as a chlorine acceptor in the co-presence of activated carbon, tin, and zinc. The addition of activated carbon in metallic aluminum significantly enhanced the methylation of methyltrichlorosilane, and dimethyldichlorosilane was dominantly produced. Activated carbon played a catalyst role in the methylation reaction. When active metals, such as tin and zinc, were added in the mixture of aluminum and activated carbon, the active metals and activated carbon synergistically catalyzed the methylation of methyltrichlorosilane with methyl chloride toward the formation of dimethyldichlorosilane.     

硅胶负载四氯化锡催化合成N,N-二乙氨基乙醇己酸酯

以硅胶为载体,用浸渍法制备了不同负载量的SnCl4催化剂,用于催化合成DA-6(N,N-二乙氨基乙醇己酸酯),通过BET法对SnCl4/SiO2催化剂的表面结构进行了分析。考察了SnCl4负载量、催化剂用量、原料摩尔配比、反应温度对N,N-二乙氨基乙醇己酸酯收率的影响,实验结果表明:当n(N,N-二乙氨基乙醇):n(己酸)=1:1.2、54.1%SnCl4/SiO2催化剂用量为反应原料的2(m/m)%、溶剂为甲苯、反应时间6h时,DA-6收率达94.4%。     

实验室合成无水四氯化锡的改进

实验室传统的合成无水四氯化锡的方法属于间歇操作，当制备量较大时，需中途停止反应，一次次地将液态产物取出或压气排出，再补充锡粒，才能通入氯气进行反应。且原料（主要是Cl2）利用率较低。本实验从反应器及工艺流程两方面作了改进，使无水四氯化锡的合成能连续进行。并使原料利用率得以提高。     

新型杀生剂DDSC的合成研究

以锡、氯化苄和二甲基十二烷基叔胺为原料,经过两步反应,合成了新型杀生剂二苄基二(二甲基十二烷基胺基)氯化锡(简称DDSC)。通过单因子和正交实验,考察了单体摩尔配比、催化剂用量、反应时间、反应温度等因素对反应的影响。结果表明,适宜的合成条件为:反应时间4~5 h,原料摩尔配比为1∶1∶1,溶剂比为8∶2,催化剂用量为单体质量的2%,低温滴加温度为60℃,高温反应温度为80℃。在此条件下,DDSC的合成总收率可达85%以上。     

Some aspects of the behaviour of tin(II) chloride during coal hydrogenation in the absence of a solvent

In this application of optical and electron microscopy to the study of catalytic hydrogenation of coal, the coal is regarded as a stationary phase and the catalyst and hydrogen as mobile entities. Sampling was carried out at various stages, in the 320–474 °C temperature range, of the catalytic hydrogenation of a high-volatile bituminous coal (Bayswater seam, New South Wales, Australia) with tin(II) chloride in the absence of a solvent. The behaviour of coal macerals during hydrogenation, the mode of occurrence, morphology and composition of the catalyst, and the distribution of the elements of interest (Sn, CI, Fe, S) in hydrogenated vitrinite are described. The study has shown that both tin and chlorine can enter the coal at the very earliest stages of hydrogenation. Deep penetration of the coal by tin and chlorine takes place with progressive hydrogenation; the extent of the catalyst penetration coincides with the optically-defined hydrogenation zone. Discrete catalyst grains are confined to the hydrogenated zone; these grains do not occur at the active front of hydrogenation. Tin(II) sulphide is the product of the scavenging of sulphur by tin and is the predominant form of the catalyst after the onset of mesophase formation.     

The mechanism of stabilization of poly(vinyl chloride). II. Cleavage of organotin sulfur compounds by anhydrous hydrogen chloride

A number of organotin compounds of the type R_nSn Y_4–n, where R = alkyl or aryl; Y = alkylthio, arylthio or carbothiolate; and n = 1, 2, 3 have been prepared and treated with hydrogen chloride at 180°C in o-dichlorobenzene solution. The organotin compounds were also tested at 190°C as thermal stabilizers for PVC. Cleavage of tin–carbon bonds by hydrogen chloride was demonstrated in some cases by analysis of the organotin–hydrogen chloride reaction products. The formation of monoalkyl(aryl)tin chlorides or stannic chloride, or both, in the model system was shown to correspond to a catastrophic mode of degradation in the polymer. The use of stabilizers with fewer than two alkyl or aryl groups on tin also gave this mode of degradation.     

过渡金属氧化物修饰的金纳米催化剂苯甲醇氧化性能

采用一步法合成介孔二氧化硅负载的金纳米催化剂,以氯化锡为前驱体,通过浸渍法向金纳米催化剂中引入助剂氧化锡,得到过渡金属氧化物修饰的金纳米催化剂。通过N2吸附-脱附、X射线衍射、透射电镜和固体紫外漫反射光谱等对催化剂结构进行表征。将所合成的催化剂用于苯甲醇选择性氧化反应,考察助剂组分对催化剂性能的影响,结果表明,氧化锡的引入改变了金纳米颗粒的表面电子结构,增加了催化剂活性与选择性;但随着氧化锡含量继续增加,催化剂活性降低,这主要是因为金纳米颗粒表面过渡金属氧化物覆盖度增加,减少了催化剂活性组分与苯甲醇的接触。当氧化锡质量分数0.2%时,催化剂效果最佳,在100℃和氧气压力0.2 MPa下反应3 h,苯甲醇转化率25.7%,苯甲醛选择性75.9%,苯甲酸选择性15.8%,苯甲酸苄酯选择性6.3%。     

Transformations of sodium during gasification of low-rank coal

Specially prepared forms of a high-sulphur South Australian lignite containing sodium in two forms; as a carboxylate, forming a part of the coal organic matter or as soluble salt (NaCl) were investigated. The influence of gasification environment (gas type, temperature and time) on the transformations of sodium and the extent of vaporisation were studied. Contrary to theoretical equilibrium calculations for the high levels of sulphur present in the coal, no sodium sulphide formation was found upon the transformation of carboxylate sodium. Experiments confirmed rather the formation of sodium carbonate during gasification or pyrolysis of the sulphur-rich coal. Sodium was found to evaporate, with sodium release higher during gasification in steam or carbon dioxide than for pyrolysis in nitrogen. The release of sodium and chlorine from coal containing sodium chloride was disproportionate. Almost all of the chlorine was measured to have been released during gasification and pyrolysis by 850 °C. The release of sodium was nearly half of that of chlorine and inferred to be in the form of sodium chloride vapour. Identification of sodium carbonate in the residual pyrolysed char confirms the reaction of sodium chloride with hydrogen from coal carboxylic acid groups. Neither sodium sulphide nor sodium hydroxide was identified in char for coal containing sodium chloride.     

我国合成邻苯二甲酸二丁酯用催化剂研究现状

评述了对甲苯磺酸、氨基磺酸、强酸性阳离子交换树脂、一水硫酸氢钠、五水四氯化锡、氧化锡、稀土化合物、杂多酸和相转移催化剂等催化剂催化合成邻苯二甲酸二丁酯的方法。     

西氯化锡催化合成草酸二丁酯的研究

以草酸和正丁醇为原料,采用四氯化锡作催化剂合成草酸二丁酯,考察了影响反应的因素。实验结果表明,酯化反应的优化条件：草酸、正丁醇、四氯化锡的摩尔比为1：3．5：0．038,反应时间50min,产率可达92．16％。