双极膜技术在无机盐工业中的应用

介绍了近十年来双极膜技术的最新研究成果及其在无机盐产酸、产碱工艺中的应用。将双极膜技术应用于氯碱工业中,在阳极上,以析氧反应替代传统的析氯反应。将双极膜电解槽与现行的氯氢离子膜电解槽连用,可构建出新的氯氢平衡的体系,以实现氯碱厂中析氯量的有效控制。在钾盐生产的工艺中联产硫酸和烧碱。     

离子交换膜法—步制高纯碱的国外动态

目前氯碱工业正大规模地从水银法向隔膜法转化,但随着隔膜槽的大量应用又随之而产生了新的矛盾:(1)隔膜碱的质量低劣,含盐量高达1.0～1.5％,不能适应化纤厂等对高纯烧碱的要求。(2)隔膜法制碱需消耗大量蒸汽,用于浓缩和脱盐。(3)金属阳极的普遍采用大大提高了电流密度,但在高电流密度下电解,氯中含氢量提高到1.5～2.0％,给氯气的应用造成困难,且有造成爆炸的危险。(4)石棉隔膜寿命短,消耗量大。各国较大的制碱公司为克服上述缺点自六十年代相继对离子交换膜法一步制取高纯烧碱     

己内酰胺绿色生产技术

绿色化学的理想是实现反应的＂原子经济＂性,生产环境友好的绿色产品,这就要求原料中的每一个原子进入产品,不产生废物和副产品,并采用无毒无害的原料、催化剂和溶剂。根据绿色化学的理念,中国石化石油化工科学研究院历经20年,开发成功己内酰胺绿色生产技术,建成20万t/a工业生产装置。这项技术包括：单釜连续淤浆床与钛硅分子筛集成...     

四川化工总厂情况简介

四川化工总厂座落在成都市青白江区,是我国特大型化工骨干企业之一,隶属四川省化工厅。四川化工总厂创建于一九五六年九月,一九五九年建成投产。当时是我国自行设计、施工、投产的中型氮肥厂,设计能力和产品方案为7.2万吨/年,硫酸8万吨/年,硫酸铵10万吨/年,硝酸铵124万吨/年。一九六四年至一九七五年,该厂对合成氨装置在关键设备     

1953—2005年中国燃煤大气铅排放量估算

采用随时间变化的铅排放因子估算了中国1953—2005年燃煤大气铅排放量。在52年间,中国燃煤累计向大气排放19.1万t铅,平均每年以4.02%的速度增加,其中2001—2005年排铅38 688 t,平均增速达9.55%;工业用煤的铅排量占总量的87%,生活用煤铅排量占8%;2006年的燃煤铅排量超过了10 000 t。这表明,燃煤造成的铅污染已成为当前中国面临的重要环境问题。     

2001—2005中国各省(市)燃煤大气铅排放量估算

首次估算了中国各省(市)燃煤大气铅排放量和铅排放强度。结果表明,在2001—2005年,山西、湖北、山东、河北、河南的燃煤铅排量均超过3 000 t,各省(市)共向大气排铅5.9万t,年平均增长速度达14.5%。燃煤大气铅排放强度与儿童铅中毒率之间存在复杂的相关关系,在人口铅排强度低于0.5 t/万人的省(市),两者呈显著负相关关系;而在人口铅排强度超过0.6 t/万人的省(市),两者呈极显著正相关关系。     

“走出去”对企业产能利用率的影响—来自“一带一路”倡议准自然实验的证据

通过使用2010—2018年中国上市企业数据,基于“一带一路”倡议准自然实验,运用单时点和多时点双重差分法,考察了“走出去”对企业产能利用率的影响。基准估计和稳健性检验的结果表明,“一带一路”倡议作为中国新时期“走出去”的重要战略,显著地提升了企业的产能利用率,对外直接投资和海外工程建设都是有效的途径。异质性分析显示,“一带一路”倡议提升产能利用率的效应,在国有企业、高生产率企业、资本密集度低的企业和非出口企业中表现得更为突出。为了揭示传导机制,通过进一步理论建模分析,结果显示,“一带一路”通过降低调整成本、缓解信息不对称,以及削弱政府的规模偏好,提升了企业的产能利用率。     

高活性聚异丁烯的合成与结构表征

根据我国关于推广乙醇汽油的新政,国内原有1800万吨左右甲基叔丁基醚(MTBE)产能正面临生死抉择,作为其下游产品的大量异丁烯资源需另谋出路。因此开发高活性聚异丁烯高新技术,可缓解异丁烯利用率低以及油品质量升级带来的双重压力,促进炼化企业碳四产业链的可持续发展。本论文以水(H₂O)/二氯乙基铝(EADC)/2,2-二氯二乙基醚(CEE)作为引发体系,考察相关正离子聚合的聚合特征和规律,探究出具有高转化率、高α-外烯烃含量的高活性聚异丁烯(HRPIB)的制备方法。     

Mathematical Simulation and Design of Three-Phase Bubble Column Reactor for Direct Synthesis of Dimethyl Ether from Syngas

A three-phase reactor mathematical model was set up to simulate and design a three-phase bubble column reactor for direct synthesis of dimethyl ether (DME) from syngas, considering both the influence of part inert carrier backmixing on transfer and the influence of catalyst grain sedimentation on reaction. On the basis of this model, the influences of the size and reaction conditions of a 100000 t/a DME reactor on capacity were investigated. The optimized size of the 10000 t/a DME synthesis reactor was proposed as follows: diameter 3.2 m, height 20 m, built-in 400 tube heat exchanger (φ38×2 mm), and inert heat carrier paraffin oil 68 t and catalyst 34.46 t. Reaction temperature and pressure were important factors influencing the reaction conversion for different size reactors. Under the condition of uniform catalyst concentration distribution, higher pressure and temperature were proposed to achieve a higher production capacity of DME. The best ratio of fresh syngas for DME synthesis was 2.04.     

我国的高分子生产技术引进

本文对我国自建国以后通过引进国外技术发展起来的高分子生产状况进行了综合评述。对其在各阶段的特点以及在我国经济建设与技术发展上的作用进行了总结与分析,指出:截止到1988年底我国共引进(指已投产者)25个合成高分子品种及298.52万吨/年生产能力。     

离子交换膜法合成2,2′-二氯氢化偶氮苯

应用离子交换膜法电解邻氯硝基苯合成2,2′-二氯氢化偶氮苯.讨论了电极活化条件、电流密度、电解液温度等因素对电解还原反应的影响.结果表明:在反应温度t=80℃,阴极、阳极电解液分别为10%和30%(by m ass)的NaOH溶液,电流密度4.2A/dm2条件下电解,电流效率最高,可达73%,收率为83%.     

A Study of Concentration Polarization on Ion Exchange Membrane Electrodialysis

The concentration polarization phenomena in ion exchange membrane electrodialysis have been studied with single exchange membrane cell. The limiting current densities of Asahi ion-permselective membranes CK-1 and CK-2, Selemion ion-exchange membranes CMV, AMV, DMV and ASV have been measured with Ag-AgCl reversible electrode in various electrolyte solutions under 25°C and constant flow rate. In sodium chloride solution, the cation exchange membrane is easier to occur concentration polarization than the anion exchange membrane. The limiting current density increases as the concentration of solution increases for the same kind of ion exchange membrane. The experimental limiting current densities of Selemion CMV and AMV in NaCl, KCl, MgCl₂, CaCl₂, BaCl₂, Na₂SO₄, NaOH and HCl aqueous solutions are measured. The results show that the limiting current density increases as the ion mobility and diffusivity increase, and is affected by the transference number of ion. For the mixture of electrolyte solution, there are linear relationship between limiting current density and equivalent fraction of electrolytes.     

生物膜电极法降解水中2-萘酚的影响因素

以2-萘酚为目标污染物,在对比电化学法和微生物法降解效果的基础上,研究了隔膜式电解体系中基体材料性质、电解池隔膜种类、温度和电流密度对生物膜电极法降解2-萘酚作用效率的影响.结果表明,生物膜电极法相比传统的电化学法和微生物法对2-萘酚类污染物的去除有一定优势,其作用效果与微生物生长状态有直接关系.以碳毡为基体的生物膜电极降解效果起始阶段优于钛网基生物膜电极,但一段时间后钛网基生物膜电极降解性能更稳定.阴离子交换隔膜电解池体系对2-萘酚的降解效果优于阳离子交换隔膜电解池体系,35℃条件下0.5 mA/cm²电流密度是最佳作用条件.     

用交流阻抗法研究某些离子选择电极的响应特性

用交流阻抗法研究了两种液膜胆R汁酸电极和两种聚氯乙烯(PVC)膜钙离子选择电极. 从体电阻R_b和电荷传递电阻R_(ct)得到膜内离子迁移活化能E_a, 及电极的表观标准交换电流密度i°_0等信息. 结果表明: E_a比R_b更能反映离子在膜内迁移的情况, 离子在PVC膜中的迁移比在液膜中困难得多; i°_0能在一定程度上反映电极性能的优劣等。     

Electrosynthesis and biological properties of persulfate–chloride solutions

A method for electrochemical synthesis of medical solutions for oxidation of toxic substances in the human organism has been developed. The method is based on electrooxidation of sodium sulfate in the presence of chloride and NaOH microadditions (in amounts that provide рН 13) in a filter-press membrane electrolyzer. A diagram is presented for choosing the optimum ratio between the current density and the flow rate of electrolyte during the electrosynthesis of a medical solution. The use of an electrolyte of the suggested composition under the optimum electrosynthesis conditions leads to solutions with physiological рН values (7.2–7.4) and high oxidative ability with respect to Micrococcus sp. and Staphylococcus coag (–), but there was no injuring effect on blood cells.     

Nickel based electrocatalysts for oxygen evolution in high current density, alkaline water electrolysers

A number of nickel based materials are investigated as potential oxygen evolution catalysts under conditions close to those met in modern, high current density alkaline water electrolysers. Microelectrodes are used to avoid distortion of voltammetric data by IR drop even at the high current densities employed in such water electrolysers. High surface area nickel metal oxides prepared by cathodic deposition and mixed oxides prepared by thermal methods are considered. A mixed Ni/Fe oxide is the preferred electrocatalyst. The influence of hydroxide ion concentration and temperature on the voltammetry is defined. Preliminary stability tests in a zero gap cell with an OH(-) conducting membrane show no significant increase in overpotential during 10 days operation in 4 M NaOH electrolyte at a current density of 1 A cm(-2) at 333 K.     

用于二氧化碳电催化还原的电解器研究进展

The electrocatalytic CO₂ reduction reaction (CO₂RR) driven by renewable energy is an efficient approach to achieve the conversion and utilization of CO₂. In this context, CO₂RR has become an emerging research focus in the field of electrocatalysis over the past decade. While a large number of nanostructured catalysts have been developed to accelerate CO₂RR, the tradeoff between activity and selectivity usually renders the overall electrocatalytic performance very poor. Beyond catalyst design, rationally designing electrolyzers is also of substantial importance for improving the CO₂RR performance and achieving its scale-up for practical applications. To a large extent, the electrolyzer configuration determines the local reaction environment near an electrode by affecting the process conditions, thereby resulting in remarkably different electrocatalytic performances. To be techno-economically viable, the performance of CO₂ electrolyzers is expected to be at least comparable to that of the current state-of-the-art proton exchange membrane (PEM) water electrolyzers, with regard to their activity, selectivity, and stability. Researchers have made great progress in the development of CO₂ electrolyzers over the past few years, but they are also facing many issues and challenges. This review aims to provide an in-depth analysis of the research progress and status of current CO₂ electrolyzers including H-cell, flow-cell, and membrane electrode assembly cell (MEA-cell) electrolyzers. Herein, operation at industrial current densities (> 200 mA∙cm⁻²) is set as a basis when these electrolyzers are discussed and compared in terms of the four main figures of merit (current density, Faradic efficiency, energy efficiency and stability) that describe the CO₂RR performance of an electrolyzer. The advantages and drawbacks of each electrolyzer are discussed and highlighted with emphasis on the key achievements reported to date. Compared to conventional H-cell electrolyzers that work well in mechanistic studies, the newly developed electrolyzers using gas diffusion electrodes, both flow-cell and MEA-cell electrolyzers, are able to break the limitation of CO₂ solubility in water and acquire industrial current densities. Although flow-cell electrolyzers have achieved current densities exceeding 1 A∙cm⁻², they suffer from low energy efficiencies because of the significant iR drop and poor stability owing to the use of alkaline electrolytes. These issues can be overcome in the case of zero-gap MEA-cell electrolyzers with ion exchange membranes being as solid electrolytes. The anion exchange membrane (AEM)-based CO₂ electrolyzers are at the center of the current research, as they demonstrate promising activity and selectivity toward specific CO₂RR products and exhibit excellent stability for over thousands of hours in few cases. Meanwhile, the crossover of CO₂ and liquid products from the cathode to the anode through the membrane tends to lower the utilization efficiency of the CO₂ supplied to the AEM electrolyzers. MEA-cell electrolyzers using cation exchange membranes and bipolar membranes have also been explored; however, neither of them have shown satisfactory CO₂RR performance. The development of new polymer electrolyte membranes and ionomers would help address these problems. While issues and challenges still exist, MEA-cell electrolyzers hold the greatest promise for practical applications. As concluding remarks, research strategies and opportunities for the future have been proposed to accelerate the development of CO₂RR technology for practical applications and to deepen the mechanistic understanding behind improved performance. This review provides new insights into rational electrolyzer design and guidelines for researchers in this field.     

Studies on the influence of various experimental conditions on electrochemical generation of ferrate(VI) in NaOH-KOH mixed electrolyte

Ferrate(VI) was prepared by electrooxidation in diaphragm electrolyzer with iron wire gauze as anode and NaOH-KOH mixed solution as electrolyte. The influences of various experimental conditions, such as the volume ratio of NaOH-KOH mixed electrolyte, temperature, current density, passivation of iron anode were investigated on ferrate current efficiency. Due to the low solubility of K₂FeO₄ in concentrated alkaline solution and the passivation of iron wire gauze anode, a highest current efficiency over 90% was obtained at 45°C and at a current density of 5 mA cm⁻² in mixed electrolyte with the volume ratio of NaOH: KOH equal to 6: 4. The result is superior to using NaOH and KOH as electrolyte respectively. In addition, polarization curves, scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) were employed to further study the effects of synthesis conditions on ferrate(VI) in theory. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 7, pp. 853–857. The article is published in the original.     

Electrochemically induced Favorsky rearrangement of alkyl benzyl ketones

Electrolysis of alkyl benzyl ketones in MeOH in an undivided electrolyzer in the presence of the NaI—NaOH mediator system induces the process similar to the Favorsky rearrangement to produce arylalkanecarboxylates in 80—90% yield (per substance) and with the 50—55% current efficiency.     

In operando synchrotron X-ray radiography studies of polymer electrolyte membrane water electrolyzers

Polymer electrolyte membrane water electrolysis (PEL) cells are studied in-operando by synchrotron X-ray radiography. Two-phase flow phenomena associated with the evolution of oxygen and hydrogen in the surrounding water are investigated on a running electrolyzer cell. We examine the gas bubble discharge from the porous transport layer (PTL) into the flow channel and discuss the transport of bubbles in the flow channel. The transport of gas inside the PTL and the number of gas bubble discharge sites is examined and correlated with current density.