己内酰胺绿色生产技术

中国石化石油化工科学研究院历经20年,成功开发出己内酰胺绿色生产技术,建成3套20万t/a工业生产装置、多套工业装置正在建设中.己内酰胺绿色生产技术包括:钛硅分子筛与浆态床集成用于环己酮氨肟化合成环己酮肟;纯硅分子筛与移动床集成用于环己酮肟气相重排;非晶态合金催化剂与磁稳定床集成用于己内酰胺精制.工业实施后,装置投资下降70%、生产成本下降10%、原子利用率由60%提高到90%以上、三废排放是已有技术路线的1/200、无副产物硫酸铵.己内酰胺绿色生产技术产生了重大的经济效益和社会效益,践行了绿色化学的理念,是绿色化学的成功范例.     

绿色化学及其绿色系统工程技术与环境友好

绿色化学理念的基本内涵既有微观意义又有宏观意义与工程技术的意义。绿色化学及其绿色技术在社会生产与生活、传统化学工业改造与创新、资源合理充分利用与循环再生、绿色净化与监测、环境保护与开发等方面发挥重要作用。实施绿色化学及其绿色系统工程技术,使社会生产、生活绿色化,实现人类与环境友好对话,建设“环境友好”家园,营造“环境和谐”生活,是坚持可持续发展、科学发展核心战略的重要举措,是当今世界人类面临的重大挑战与机遇。     

绿色分析化学技术进展

绿色分析化学技术是国际分析化学的前沿,受到广泛关注.绿色分析化学是把绿色化学的原理使用在新的分析方法和技术方面.目前的研究主要集中在环境友好的样品前处理技术(如微波消解、微波萃取、固相萃取、固相微萃取、超临界流体萃取等)和绿色分析测试技术(如X射线荧光分析法、近红外技术、毛细管电泳、顶空气相色谱等).文章对上述内容进行了综述.     

绿色分子印迹技术简论

解析了绿色分子印迹技术(GMIT)的概念;结合水相和其他新型分子印迹技术、聚合物辅助设计及新型原材料的发展,简要阐述GMIT的发展动向.指出在绿色化学日益深入人心的今天,有必要深入探索和发展绿色分子印迹技术,从而拓展分子印迹技术研究领域、促进绿色化学的发展.     

绿色分析化学

绿色分析化学是把绿色化学的原理使用在新的分析方法和技术的设计方面,旨在减轻分析化学对环境的影响。无污染或少污染的绿色分析化学技术将是今后分析化学的一个发展方向。文中介绍了分析化学与环境的关系,绿色分析化学的特点及其方法的发展。     

绿色化学的进展

绿色化学是一门从源头上阻止污染的化学,近年来这方面的研究主要是围绕化学反应,原料,催化剂,溶剂和产品的绿色化开展的。根据这条主线,评述了绿色化学的一些主要研究进展。最后介绍了我国绿色化学的活动。     

制革工业中的绿色化学与技术

论述了中国制革工业研究和实施绿色化学与技术的重要性。概述了国内外在绿色皮革化学品的开发和应用, 清洁的制革生产以及制革废弃物利用方面的研究成果, 并提出了今后的发展方向。     

离子对色谱法测定生产己内酰胺中副产环己酸磺酸

建立了反相离子对色谱内标法测定甲苯法生产己内酰胺中副产环己烷羧酸磺酸含量.色谱条件为:色谱柱Agilent Hypersil ODS (4.0 mm×250 mm,5μm),内标物甲苯-4-磺酸,流动相为37.5%甲醇(V/V),10 mmol/L四丁基溴化铵,25 mmol/L KH2PO4,H3PO4调节pH 2.5～3.5,柱温30 ℃,流速1.2 mL/min,检测波长230 nm.结果表明:线性范围0.1006～3.0192 mg/mL,相关系数为0.9994,回收率99.51%～102.34%,RSD为0.4950%～0.5270% (n=6).     

绿色化学的进展

简介了绿色化学的任务、特点及当前应研究的几个中心问题。如寻找去除剧毒有害的化学原料、采用超临界流体作化学合成中的溶剂、计算机辅助绿色化学设计和用生物质作化工原料的研究等。     

绿色化学与绿色化学教育

本文介绍了绿色化学的定义和内涵,绿色化学的 12条原则,“原子经济”概念,绿色化学的研究动态以及实施绿色化学教育的意义和方法。     

Research and Practice in Green Chemical Technologies

Green chemistry is also called environment harmless or environment friendly chemistry.Green chemistry requires to use new synthetic methods, engineering technologies and processes to eliminate or reduce by-products, wastes or products that harmful to human health, community safety,and ecology environment. Green chemistry pursues to control the usage of the harmful and toxic materials, reduce waste emission, avoid necessity to treat the wastes; Green Chemistry advocates wastes management from the beginning, improving the efficiency of atoms, optimizing the use of resources and energy, lowering the cost of production. Green Chemistry technologies are the ultimate path to the clean chemical production in the future.Insight Co. takes "hospital of enterprises" and "bank of technologies" as our characteristics in business, and deems the development and spread of green chemistry as our mission. We developed an unique business model which combines education, research and production. In the past 8 years,we had applied and obtained more than 30 patents and received more than ten national and provincial awards in technology progress.We had made great progress in the manufacturing of organophosphorus pesticides, especially the production of omethoate, methamidophos, paraquat and glycyrrhizinic phosphor, etc., which made a stable foundation for INSIGHT's development. We had also achieved great success in the high efficiency low toxic pesticides, such as imidacloprid, etofenprox, metalaxyl and in the new synthetic methods in various amino acids as well as in the pharmaceutical intermediates. The new method of preparation indigo using N-phenylglycinonitrile is an advanced process in the world in terms of the clean production technology for Ferro cyanide and HCN's transformation rate improvement. We solved the pollution problem of the old route. The newly developed substituted product for indigo using a clean production technology which greatly reduced the material consumption and environmental pollution. Insight has facilities producing nearly 20 photo-initiators and developed the new technique for light-curing lubricity, water-born resin, the technique for water-bon coating and their associated applications. The successfully developed technology of new high performance emulsion will promote the technology advancement in the coating industry and the wide spread of new coating in China.Insight has developed a series of new technologies, including a novel reactor technology - using a newly designed patented blade, has been characterized as high efficiency & energy saving reactor.The novel technology research and development are widely applied in INSIGHT's ten-year practice.We studied and confirmed the non-thermal catalyzing effect of microwaves, proposed a "weak microwave" theory, and a chemical reaction rate equation. We proposed that in the existence of microwave magnesium ions and phosphate, amino acid can be activated to form peptide which maybe the path of the origin of life.A 3000mt/a pilot plant in Chongqing using carbon monoxide and hydrogen to produce dimethyl ether in a single step has been built via collaboration with the Dept. of Chemical Engineering at Tsinghua University. The large scale, low cost production of dimethyl ether may possible through comprehensive technology improvement. This technology will take full advantage of current ammonia production facilities, and try to solve the global fuel shortage problem.     

SINA法生产己内酰胺工艺中杂质分析

己内酰胺(CPL)工业生产方法有多种,由SINA公司开发的以甲苯为原料生产CPL中杂质种类多,与以苯为原料生产的己内酰胺产品中的杂质有很大的区别,并且杂质含量很低,且多数杂质物化性质与主成分相近,分离与检测都很困难。本文利用气相色谱-质谱联用仪对SINA法生产的己内酰胺进行了杂质的分析。     

Chemical Solutions to the Current Polycrisis

In the past 15 years, we've experienced an unprecedented series of crises, including financial (2008), health (2020), and most recently the supply chain disruptions and the energy emergency in Europe, caused by the war in Ukraine (2022). On top of that, climate change still poses a serious threat to our lives and our planet. These interconnected challenges create tremendous societal problems and compromise the viability of the chemical industry in an environment of price volatility and high inflation. Thus, the International Union of Pure and Applied Chemistry (IUPAC) has launched a series of actions to tackle this and raise awareness of the role of chemistry in solving our major threats. Since 2019, IUPAC has identified the “Top Ten Emerging Technologies in Chemistry” to connect chemical researchers with industry, bridging the gap between science and innovation, maintaining the current competitiveness of the chemical industry, as well as tackling our most pressing global challenges.     

Green synthesis and characterization of polymer-stabilized silver nanoparticles

Silver nanoparticles (Ag-NPs) were synthesized using a facile green chemistry synthetic route. The reaction occurred at ambient temperature with four reducing agents introduced to obtain nanoscale Ag-NPs. The variables of the green synthetic route, such as acidity, concentration of starting materials, and molar ratio of reactants were optimized. Dispersing agents were employed to prevent Ag-NPs from aggregating. Advanced instrumentation techniques, such as X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet–visible spectroscopy (UV–vis), and phase analysis light scattering technique (ZetaPALS) were applied to characterize the morphology, particle size distribution, elemental composition, and electrokinetic behavior of the Ag-NPs. UV–vis spectra detected the characteristic plasmon at approximately 395–410 nm; and XRD results were indicative of face-centered cubic phase structure of Ag. These particles were found to be monodispersed and highly crystalline, displaying near-spherical appearance, with average particle size of 10.2 nm using citrate or 13.7 nm using ascorbic acid as reductants from particle size analysis by ZetaPALS, respectively. The rapid electrokinetic behavior of the Ag was evaluated using zetapotential (from −40 to −42 mV), which was highly dependant on nanoparticle acidity and particle size. The current research opens a new avenue for the green fabrication of nanomaterials (including variables optimization and aggregation prevention), and functionalization in the field of nanocatalysis, disinfection, and electronics.     

六氢苯甲酸-环己酮肟联产己内酰胺组合工艺中酰胺液成分的气相色谱-质谱分析

石家庄化纤公司己内酰胺装置是以甲苯为原料,经氧化、加氢、酰胺化、中和、萃取及精制等工序的装置。其基本工艺技术从意大利引进。由于工艺本身的特点,副产物硫铵达3.8吨／吨己内酰胺。该装置设计年产硫氨19万吨,产量较大。由于市场的原因,冬天硫铵销售不畅,有时会危及己内酰胺的正常生产。六氢苯甲酸-环己酮肟联产己内酰胺工艺,就是结合了石家庄化纤公司现有工艺特点,开发的不增加硫铵产量的新工艺路线。了解产品组成,可以为实验优化操作条件、提高己内酰胺收率及避免副反应发生提供数据依据。同时,也为后期的精制工艺以及己内酰胺成品中的杂质定性定量分析提供了原始数据依据。利用气相色谱-质谱联用仪,对己内酰胺组合工艺以及甲苯工艺生产的酰胺液中的组成进行了测定,在选定的色谱操作条件下样品中各组分分离良好,并对其中所含的组分进行了定性分析。     

绝热法研究己内酰胺阴离子聚合尼龙动力学

采用己内酰胺钠盐、N-75缩二脲作为反应催化体系, 确定反应温度在145-160 ℃之间, 通过计算得到动力学参数: 反应级数为准一级、活化能在73.2-77.1 kJ·mol-1之间、指前因子在2.9×1011-3.6×1011 mol1-n·s-1范围内. 本实验条件下测定并计算的反应热为134.5-137.3 J·g-1, 与文献值(138.6 J·g-1)吻合. 并在前人基础上修正并建构了己内酰胺阴离子绝热反应动力学模型, 对反应过程的模拟结果与实验数据基本吻合, 从而证明了本模型的正确合理.     

Peroxodicarbonate as a Green Oxidizer for the Selective Degradation of Kraft Lignin into Vanillin

Lignin, the world's largest resource of renewable aromatics, with annually roughly 50 million tons of accruing technical lignin, mainly Kraft lignin, is highly underdeveloped regarding the production of monoaromatics. We demonstrate the oxidative depolymerization of Kraft lignin at 180 °C to produce vanillin 1 in yields up to 6.2 wt % and 92 % referred to the maximum yield gained from the quantification reaction utilizing nitrobenzene. Using peroxodicarbonate (C₂O₆²⁻) as “green” oxidizer for the degradation, toxic and/or harmful reagents are prevented. Also, the formed waste can serve as makeup chemical in the pulping process. Na₂C₂O₆ is synthesized in an ex-cell electrolysis of aqueous Na₂CO₃ at BDD anodes, achieving a yield of Na₂C₂O₆ with 41 %. At least, the oxidation and degradation of Kraft lignin is analysis via UV/Vis and NMR spectroscopy.     

Green chemistry and sustainability metrics in the pharmaceutical manufacturing sector

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Azide Ionic Liquids for Safe,Green, and Highly-Efficient Azidation Reactions to Produce Azide Polymers

Azide compounds are widely used and especially, polymers bearing pendant azide groups are highly desired in numerous fields. However, harsh reaction conditions are always mandatory to achieve full azidation, causing severe side reactions and degradation of the polymers. Herein, we report the design and preparation of two azide ionic liquids (AILs) with azide anion and triethylene glycol (E₃)-containing cation, [P_444E3][N₃] and [MIM_E3][N₃]. Compared with the traditional sodium azide (NaN₃) approach, both AILs showed much higher reaction rates and functional-group tolerance. More importantly, they could act as both reagents and solvents for the quantitative azidation of various polymeric precursors under mild conditions. Theoretical simulations suggested that the outstanding performance of AILs originated from the existence of ion pairs during the reaction, and the E₃ moieties played a crucial role. Lastly, after the reaction, the AILs could be easily regenerated, presenting a safer, greener, and highly efficient synthesis route for azide polymers.