基于TRIZ理论制取高纯氢氰酸的工艺改进研究

己二腈是一种重要的化工中间体，作为生产尼龙66的原料之一，其技术长期被国外垄断。丁二烯氰化法作为世界最先进的己二腈生产工艺，需要以高纯氢氰酸为原料，而氢氰酸是一种剧毒化学品，不能进行储运，因此研究高纯氢氰酸的就地生产是十分重要的。自主开发的甲醇氨氧化制取氢氰酸项目已完成实验室阶段开发，但遇到吸收效率低、氢氰酸易聚合的问题。巧妙运用了TRIZ理论提出整改方案，对甲醇氨氧化生产氢氰酸工艺进行改进，成功地解决了两大难题，为后续工业化开发提供重要基础。     

Glyclean TMAN型氢氰酸阻聚剂的工业试验

介绍了杜邦公司开发的Glyclean^TM型氢氰酸阻聚剂,代替醋酸用于齐鲁丙烯腈装置精制区域脱氰塔（T-106）的氢氰酸阻聚。实验证明：使用Glyclean^TMAN型氢氰酸阻聚剂后,T-106塔盘氢氰酸黑色聚合物基本消除,T-106塔再沸器（E-116A／S）运行周期延长,对氢氰酸的阻聚效果比使用醋酸更为显著。     

以副产氢氰酸生产亚氨基二乙酸的技术经济评价

1　前言大庆石油化工总厂和大庆油田化工总厂各有一套 50ｋｔ/ａ丙烯氨氧化法丙烯腈装置 ,这二套装置每年副产的氢氰酸总量在 1 4ｋｔ以上 ,综合利用途径都以生产丙酮氰醇为主。近几年来 ,由于市场供求形势发生变化 ,丙酮氰醇装置开工率较低 ,大部分氢氰酸得不到利用 ,只能在焚烧炉中白白烧掉 ,造成了资源的极大浪费。在当前国有大企业也普遍面对扭亏增盈课题的形势下 ,迫切需要面向市场开发新的适销对路的高附加值氢氰酸深加工产品 ,以实现更大的经济效益和环境效益。亚氨基二乙酸就是一种新的高附加值氢氰酸深加工产品。该产品在国外的主…     

草甘膦生产技术研究进展

本文综述了世界上已经实现工业化的草甘膦生产路线,重点介绍了氯乙酸-甘氨酸法、氢氰酸-甘氨酸法、二乙醇胺-IDA法、氢氰酸-IDA法优缺点及应用情况。通过对比分析,得出随着以活性炭催化氧化双甘膦制备草甘膦为重要步骤的氢氰酸-IDA法技术的突破以及所用活性炭催化剂再生技术的开发,该工艺势必成为草甘膦生产行业的主流技术。     

叔丁胺

叔丁胺是生产安全促进剂NS的中间体,其用量正在增加。根据我国现有情况,建议可在氢氰酸产地采用氢氰酸法就近生产叔丁胺。同时,应继续研究开发异丁烯氨化法工艺技术,并尽快投入工业化生产。     

国外合成氢氰酸技术发展概况

安氏法仍是比较经济合理的氢氰酸生产方法;丙烯腈副产氢氰酸的合理利用必将大大提高经济效益。目前已显示具有潜在生命力的新方法仍不断被开发,如甲醇氨氧化法、乙腈氨氧化法等,这些方法的产率高、成本低,有希望与丙烯腈副产的氢氰酸相竞争。     

氰化氢生产装置精馏塔的模拟与优化

在甲醇氨氧化制取氢氰酸工艺的基础上,用Aspen Plus软件对氢氰酸的分离与提纯进行模拟,同时考虑塔板数、进料位置、回流比和塔压等因素对氢氰酸分离效果的影响,以及对整个工艺流程能耗等因素的比较与分析,选出最优流程,得到最佳工艺参数;在此条件下获得质量分数为99.90%的氢氰酸,计算结果与实验结果基本相符,可为该工艺开发提供理论依据。     

泰国将使丙烷制丙烯腈技术推向工业化

丙烯腈主要生产路线是在多组分催化剂（含钒、锑）作用下丙烯经流化床氨氧化反应生成丙烯腈，同时副产氢氰酸，氢氰酸可用作甲基丙烯酸甲酯的原料。反应速率受丙烯限制。由于现有技术以丙烯为原料，来源具有相当的不确定性，而采用丙烷为替代原料，可降低原材料费用。由丙烷氨氧化直接生产丙烯腈的关键在于开发使丙烷活化的催化剂（钒／锑氯化物）。至少已有3家以上公司开发此工艺。     

亚氨基二乙酸性质,用途和生产

作为生产草甘膦的中间体、用途广泛的螯合剂或螯合型离子交换树脂的原料,亚氨基二乙酸是一种亟待开发的氢氰酸深加工产品。立足丙烯腈副产氢氰酸资源建设万吨级亚氨基二乙酸装置,对于有关石化企业和草甘膦行业均具有重要意义。本文详尽叙述了亚氨基二乙酸的性质、用途和生产技术。     

氢氰酸后续产品的开发利用

氢氰酸是丙烯腈的副产品,综合利用氢氰酸将会提高丙烯腈装置的经济效益。介绍了几种利用氢氰酸合成其他化学品的工业生产方法,旨在使企业更多地了解氢氰酸的综合利用。     

我国脂肪酸的生产和应用

简要介绍脂肪酸的分类、原料来源、生产工艺、品种以及用途。并对我国脂肪酸的生产现状进行了分析。重点介绍了脂肪酸在我国橡胶工业中、塑料助剂等领域的应用,脂肪酸甲酯作为表面活性剂在不同领域的广泛应用,最后还简述了癸二酸和改性醇酸树脂应用。     

酸液体系的研究现状分析和现场应用

酸化解堵与压裂改造相比,它具有施工相对简单和成本相对较低等特点,所以酸化解堵是一项各油田广泛使用的油气田增产技术。酸化解堵技术已有将近100历史,现已研制出具有不同特点的酸液体系,如乳化酸、泡沫酸、固体酸、多氢酸等,基本能满足复杂地质条件对酸液的要求。     

油酸的精制研究

油酸酰胺是一种很好的塑料添加剂 ,可用作塑料加工成型时的脱膜剂、润滑剂。油酸的原料来源很广 ,牛油、羊油、猪油等动物油油脂以及大豆油、花生油、棕榈油等植物油脂中都含有大量的油酸。由于油酸的来源和生产方法多种多样 ,因此其所含的脂肪酸种类及含量都不尽相同。除油酸外 ,还有亚油酸、亚麻酸等高不饱和脂肪酸。针对油酸中因含有大量的多不饱和组分如亚油酸、亚麻酸而容易产生氧化泛黄的问题 ,采取了尿素络合法对原料油酸进行精制 ,以减少原料中亚油酸、亚麻酸组分的含量。经气相色谱验证 ,产品达到了应用指标 ,提高了产品的抗氧性。     

磷钼杂多酸的合成研究

介绍了磷钼杂多酸的合成。通过正交试验探讨了反应物料量比、三氧化钼浓度、反应温度和反应时间对产物产率的影响。结果表明,最适宜的反应条件为:反应物量比n(三氧化钼)∶n(磷酸)=12∶1.0、反应温度t=70℃、反应时间7 h、三氧化钼与水的质量比1∶8。经红外光谱分析及熔点测定确定所得产品为磷钼杂多酸化合物。并以磷钼杂多酸取代硫酸作催化剂制备乙酸乙醋来研究其催化活性,并与硫酸做催化剂进行对比实验收率为70.75%,超过硫酸催化剂水平。     

The Growth‐Inhibiting Effects of Beef Fatty Acids on MCF‐7 Cells Are Influenced Mostly by the Depot Location and Inconsistently by the Biohydrogenation Intermediate Content

Biohydrogenation intermediates (BHI) including conjugated linoleic acid (CLA) isomers are formed during ruminal biohydrogenation of polyunsaturated fatty acids (PUFA) in ruminants. Although many studies have examined the anticarcinogenic effects of CLA, few studies have reported the anticarcinogenic properties of BHI in their natural form found in dairy and beef fats. The present study compared the growth‐inhibitory effects of fatty acids from beef perirenal fat (PRF) or subcutaneous fat (SCF) with low or high levels of BHI in MCF‐7 human breast cancer cells. Cells were exposed for 72 h to media containing increasing doses (50 to 400 μM) of different beef fat treatments. Fatty‐acid analysis showed that BHI were readily incorporated into cell phospholipids (PL) in a treatment‐dependent manner, but higher BHI in PL did not consistently inhibit growth. Culturing with low‐BHI PRF or high‐BHI PRF did not lead to growth inhibition, but low‐BHI SCF inhibited growth, and inhibition was further increased by high‐BHI SCF. Other classes of fatty acids may, therefore, be interacting with BHI resulting in differential effects on growth inhibition in human breast cancer cells.     

Fatty Acid Profiles in Sunflower Grains During Storage in Different Environments

This study aimed to evaluate the fatty acid profiles of sunflower oil extracted from hybrid grains produced and stored in different environments. The trials were conducted in Teresina (Piauí), Vilhena (Rondônia), and Jaguariúna (São Paulo) in randomized complete block design with 4 replicates. After harvesting, grains from 1 high oleic and 3 traditional hybrids were packed in kraft paper bags and stored in a covered shed and in a cold chamber up to 12 months. The fatty acid profiles were determined by gas chromatography after 0, 4, 8, and 12 months of storage. Analyses of variance were conducted in a split‐plot design, with hybrids being considered as whole plots and storage times as subplots. Tukey's test was performed to compare hybrids and regression analyses for storage times. The initial fatty acid profile of the grains of the same hybrid varied depending on the production location. The grain storage of high oleic and traditional sunflower hybrids during 12 months in covered shed and in cold chamber resulted in little changes in oil fatty acid profiles, regardless of the initial contents. These changes occurred only for linoleic and palmitic acids.     

Fatty Acid Profiles of Oil Obtained from Mid-Oleic Sunflowers Grown in Tropical Region

This study aimed to verify whether the fatty acid profiles of mid-oleic genotypes grown in the tropical region of Brazil fit the Codex Alimentarius and to examine the possibility of using traditional inbred lines to produce high-oleic hybrids. For this purpose, we assessed the fatty acid profile of six mid-oleic hybrids grown in environments with different minimum temperatures during oil formation in the achenes. The tests were conducted between 2015 and 2017 in an experimentally randomized complete block design with four replications. The oleic, linoleic, palmitic, and stearic acid contents were determined using gas chromatography. The mid-oleic hybrids presented varying levels of fatty acids, with oleic acid ranging between 43.6% and 84.6%, linoleic acid between 8.5% and 45.6%, palmitic acid between 3.9% and 5.7%, and stearic acid between 2.2% and 6.2%. Some of the fatty acid values were outside the ranges established by the CODEX STAN 210-1999 and were characteristic of high-oleic type sunflowers. This finding shows that we can take advantage of the potential of combining traditional inbred lines to produce high-oleic hybrids for faster and more economical breeding programs in these environments.     

Quality of Sunflower Oil Obtained in the Main Producing Region of Brazil: Adherence to the Codex Alimentarius

The objective of this work was to evaluate the quality of the oil extracted from sunflower achenes grown in Campo Novo de Parecis, the main producing region of Brazil, to optimize its use by the processing and food industries. In addition, the fatty acid profiles of the oil were checked for their adherence to the CODEX STAN 210–1999. Traditional and high-oleic genotypes were grown between 2014 and 2017 during trials with a randomized complete block experimental design with four replications. The contents of oleic, linoleic, palmitic, and stearic acids were determined using gas chromatography. The fatty acid profiles of traditional genotypes were observed to be outside the ranges established by the CODEX, with an oleic acid content above 39.4% and linoleic, palmitic, and stearic acid values lower than 48.3%, 2.7%, and 5.0%, respectively, as well as high-oleic sunflower oil with a stearic acid content of less than 2.6%. The availability of this information can, on the one hand, positively impact industries and encourage the use of better quality raw materials that are more technologically and nutritionally adequate. On the other hand, the commercialization of sunflower oil with a fatty acid profile outside the ranges established by CODEX can be difficult, because the contents are out of specification due to the climatic conditions in the cropping region.     

质子酸催化合成α-氯代十二酸工艺研究

采用廉价的浓硫酸为催化剂,氧气为自由基捕集剂,以十二酸为原料,经氯化合成α-氯代十二酸。系统考察了反应温度、催化剂用量、氯气流量、氧氯比、反应时间等因素的影响,得到最佳工艺条件:十二酸20 g,在反应温度135℃、催化剂10%、氯气流量50 mL·min-1、vO2/vCl2=1∶2、反应时间3 h,可实现十二酸基本完全转化,目标产物α-氯代十二酸选择性达到94.5%。     

热盐酸缓蚀抑雾剂

在实验室合成的一种咪唑啉类化合物与其它物质复配得到了一种适合于碳钢在高温盐酸中酸洗浸蚀的复合缓蚀抑雾剂。采用失重法和中和滴定法对其性能进行评定 ,实验结果表明 :该缓蚀抑雾剂在 2 0 %盐酸中 ,酸洗温度在常温至 85℃范围内缓蚀率达 90 %左右 ,抑雾率达 85%左右 ,并具有较好的综合性能