长链烯烃的应用

概述了长链烯烃的生产工艺,石蜡裂解和低碳烯烃齐聚。详述了长链烯烃的应用,可生产烯烃共聚体、润滑油、表面活性剂、油田化学品等。通过对它们需求量和生产能力数据进行分析,得出国内外对长链烯烃需求量日益增大,开发生产长链烯烃具有重要意义。     

FCC粗汽回炼生产低烯烃汽油

车用汽油烯烃含量高将带来严重环保问题.FCC装置在正常使用重油提升管时,可设计汽油提升管,用来回炼粗汽油,在降烯烃催化剂作用下,汽油中的C5～C8烯烃可进一步裂化为小分子烯烃,成为液化气组分;另外烯烃参与氢转移反应,得氢饱和为烷烃;同时烯烃环化可生成芳烃,最终使改质汽油的烯烃体积含量降至35%以下.由于芳烃辛烷值较高,从而使汽油保持稳定的高辛烷值.在有效解决芳烃缩合生焦的问题后,该工艺对汽油降烯烃效果理想.     

Organocatalytic asymmetric epoxidation of olefins by chiral ketones

Chiral ketones have been shown to be effective organocatalysts for asymmetric epoxidation of olefins with broad substrate scope. High enantioselectivity has been obtained for a wide variety of trans and trisubstituted olefins, as well as a number of cis olefins, with encouragingly high ee's for some terminal olefins. The stereochemical outcome of the reaction can be rationalized by a spiro transition state model.     

NMR study on sulfonation of internal olefins

Terminal olefins can be converted into the corresponding sulfonates by sulfonation with SO₃ followed by hydrolysis, the products are used as detergent ingredients. Although internal olefins were also expected to be good feed stocks, it was difficult to convert them into the corresponding sulfonates with as good of a yield as that of terminal olefins under the same synthesis conditions. Our studies have been carried out in order to clarify the reason for poorer conversion of the internal olefins. It was found by a nuclear magnetic resonance spectroscopic study that the major components of the sulfonated intermediate of internal olefins wereβ-sultones, the amounts of which were usually very small in sulfonated terminal olefins. A portion of theseβ-sultones was desulfonated, depending on temperature, to the original olefins and the corresponding sulfate salts during alkaline hydrolysis. The prevention of desulfonation of theβ-sultones in the hydrolysis process was one of the most important aspects for the production of internal olefin sulfonates. Finally, by keeping the hydrolysis temperature below 35°C, the conversion of internal olefins into sulfonates was achieved with the same yield as that of conventional terminal olefins.     

流化催化裂化汽油改质和增产低碳烯烃的研究

采用GL型催化剂,在小型固定流化床实验装置上考察了反应温度、剂油比、空速和水油比等操作条件对流化催化裂化(FCC)汽油催化改质汽油的产品分布、低碳烯烃(丁烯、丙烯和乙烯)产率和族组成的影响。实验结果表明,在一定反应条件下,FCC汽油通过催化改质可以降低烯烃含量,提高芳烃含量和辛烷值,在满足新汽油标准的同时提高了低碳烯烃的产率。此外,较高的反应温度、剂油比和水油比以及较低的空速有利于FCC汽油催化改质和增产低碳烯烃。     

甲醇制烯烃技术(MTO)工艺技术进展

甲醇制烯烃技术(MTO)是一种生产低碳烯烃的途径,可有效缓解低碳烯烃供应紧张的现状,使烯烃来源多样化。文章着重介绍了MTO工艺的反应机理、反应热力学、反应动力学以及催化剂研究进展和几种典型甲醇制烯烃技术的发展近况,并分析了我国进一步发展该技术需要解决的问题。     

丁烯齐聚催化剂研究进展

烯烃催化齐聚是C_４烯烃综合利用的一个重要途径。本文论述了近年来低碳烯烃,特别是C_４烯烃齐聚催化剂的研究进展,介绍了不同催化剂体系的反应特点及工艺状况。     

煤或天然气经甲醇制低碳烯烃工艺研究新进展

由煤或天然气经甲醇制低碳烯烃工艺是解决石油资源紧张、低碳烯烃需求量越来越大等问题的有效路线。介绍了几种有代表性的经甲醇制低碳烯烃工艺,包括美国UOP/Hydro甲醇制烯烃工艺,中国科学院大连化学物理研究所的合成气经由二甲醚制低碳烯烃(SDTO)工艺,德国Lurgi公司的甲醇制丙烯工艺,以及甲醇制烯烃与AtoFina/UOP烯烃裂解的集成工艺;分析了各工艺目前达到的技术指标及最近的技术改进,关注了各工艺近几年的工业化进程。除了SDTO工艺外,其他几种工艺有望在未来几年内实现工业化。国内甲醇制低碳烯烃工艺的开发应借助于流化催化裂化成熟的工程设计经验,同时加大甲醇制烯烃工艺流化床催化剂的开发力度。     

煤制烯烃与油制烯烃市场分析

随着世界首套煤制烯烃项目神华包头煤化工项目的成功商业化运行，近年来国内陆续有多家煤制烯烃工厂投产运行。煤制烯烃的大量兴起给聚烯烃市场带来了新的活力，同时中国塑料市场的飞速发展使我国的聚烯烃供给逐渐形成了中国石油天然气集团公司、中国石化集团公司和煤制烯烃的三足鼎立的局面。本文指出从产品利润来看，虽然油制烯烃的市场价格普遍较高，但受成本因素的制约，特别是近些年来国际油价居高不下的影响下，油制烯烃整体利润比煤制烯烃低。随着煤制烯烃的逐步成长，其已慢慢占领通用料市场，再加上进口料对高端市场的冲击，国内聚烯烃市场在不久的将来终会呈现过剩的局面。成本、环保、高端产品技术研究和能源供应等问题也是油制烯烃和煤制烯烃角逐的主战场，产品的经济效益，煤制烯烃的突破瓶颈将是赢得市场的关键。     

Reactivity of several olefins in the HDS of full boiling range FCC gasoline over PtPd/USY

Reactivity of C₄–C₆ olefins during the selective HDS of a full boiling range FCC gasoline over PtPd/USY catalyst was studied under various process conditions. Effect of the structure and carbon number of olefins on their conversion is discussed. It was found that the rate of hydrogenation decreases with the carbon number of linear olefins. Terminal olefins are readily converted to internal ones by double bond shift to approach the equilibrium composition of olefin isomers.     

甲醇制低碳烯烃工艺的新技术及其进展

用甲醇替代石油资源,通过MTO、MTP来生产乙烯和丙烯是减少对石油的依存度,持续健康发展化工产业的重要途径。我国已开始进入甲醇制低碳烯烃工业化装置建设阶段。重点介绍了具有代表性的几种甲醇制烯烃工艺,对各工艺技术及其新进展进行了阐述。甲醇生产乙烯和丙烯工艺工业化的难点是MTO催化剂的开发和MTO反应器的放大,建立MTO/MTP的联合装置是未来利用煤或天然气生产低碳烯烃的一个方向。     

官能团化烯烃的氢甲酰化反应研究及应用进展

氢甲酰化反应已发展成为重要的工业均相催化反应之一,通过官能团化烯烃氢甲酰化反应可以得到官能团化的醛类化合物,该类化合物大多是精细化学品或合成中间体,官能团化烯烃显示出很多不一样的特性。综述近年来官能团化烯烃氢甲酰化反应研究进展,介绍乙烯基芳烃、α-官能团化烯烃以及β-官能团化烯烃的氢甲酰化反应及应用,并对官能团化烯烃氢甲酰化反应进行展望。     

Palladium‐Catalyzed,Chelation‐Assisted Stereo‐ and Regioselective Synthesis of Tetrasubstituted Olefins by Oxidative Heck Arylation

An efficient synthesis of tetrasubstituted olefins was achieved via a palladium‐catalyzed, chelation‐assisted oxidative Heck arylation protocol from trisubstituted olefins bearing a tether with a directing group in a completely stereo‐ and regioselective manner. The stereo‐ and regioselectivity as well as excellent yields of tetrasubstituted olefins originated from the stabilization of a palladium intermediate by chelation between the palladium center and a directing group.     

甲醇制烯烃技术进展及与石油烃裂解制烯烃对比

介绍了甲醇制烯烃技术的反应机理和主要的技术问题,并将甲醇制烯烃技术与传统的石油烃裂解制烯烃技术在分离工艺和对环境的影响方面进行了对比。通过对比,表明甲醇制烯烃工艺在能耗、环保等方面与石油路线相比具有一定的竞争力。     

Cross-metathesis of biomass to olefins: Molecular catalysis bridging the gap between fossil and bio-energy

Terminal olefins are important building blocks for the industry of biofuels, oligomers, and lubricants production. The industrial processes for production of olefins involving oligomerizationofethylene or cracking of petrochemical waxes have several flaws including low yield and high cost in product separation. Cross-metathesis of bio-derived unsaturated fatty esters and olefins with ethylene (ethenolysis), allows the conversion of sustainable waste biomass to various renewable olefins with much safer, less toxic, sustainable, and zero-CO₂ emission processes. To our best knowledge, however, a comprehensive summary of key advances in this field (since 2017) is yet to be available, particularly on molecular features of homogeneous and heterogeneous catalysts. This paper presents a critical review on molecular structures of metal complex and oxide catalysts for ethenolysis of olefins and oleochemicals. The influence of cationic centers, coordination conditions, nature of ligands, operating conditions on catalyst performances will be systematically discussed along with relevant reaction mechanism. The key challenges for rational design of coordinated cationic hybrids have been summarized, which will provide insights to technological advancement of large-scale production of oleochemical-derived olefins.     

Study on reformulation of fluid catalytic cracking gasoline and increasing production of light olefins

The effects of reaction temperature, mass ratio of catalyst to oil, space velocity, and mass ratio of water to oil on the product distribution, the yields of light olefins (light olefins including ethylene, propylene and butylene) and the composition of the fluid catalytic cracking (FCC) gasoline upgraded over the self-made catalyst GL in a confined fluidized bed reactor were investigated. The experimental results showed that FCC gasoline was obviously reformulated under appropriate reaction conditions. The olefins (olefins with C atom number above 4) content of FCC gasoline was markedly reduced, and the aromatics content and octane number were increased. The upgraded gasoline met the new standard of gasoline, and meanwhile, higher yields of light olefins were obtained. Furthermore, higher reaction temperature, higher mass ratio of catalyst to oil, higher mass ratio of water to oil, and lower space velocity were found to be beneficial to FCC gasoline reformulation and light olefins production.     

窄馏分切割技术在清洁汽油生产工艺中的应用

采用旋转带蒸馏仪对国内某炼油厂预加氢后催化汽油进行窄馏分切割,分析各窄馏分硫和烯烃分布规律,为全馏分催化汽油分馏提供精确的切割方案。实验结果表明,通过将切割轻汽油总硫含量控制在指标要求上限,最大量将烯烃切入轻汽油中,降低重汽油烯烃含量,可减少在加氢脱硫过程中由于烯烃饱和导致的辛烷值损失。     

天然气制低碳烯烃技术及其工艺进展

天然气是一种高效、优质、清洁能源,也是一种重要的化工资源,利用天然气制取低碳烯烃是C1化学研究的重要课题之一。介绍了以天然气为原料制取低碳烯烃的3种研究方向及相关的工艺进展,并分析了天然气制烯烃的经济性。     

重整生成油C_8馏分中芳烯烃的分析

采用毛细管气相色谱-氢火焰离子化检测器(CGC-FID)和气相色谱-质谱法(CGC/MS)分析了重整生成油C8馏分中的芳烯烃。实验使用HP-FFAP毛细管色谱柱(50m×0.32mm×0.50μm)和ATTM-WAX毛细管色谱柱(50m×0.32mm×0.30μm),根据烃类化合物在这两种色谱柱上的保留规律,用CGC/MS联用技术和UOP方法744-06以及标准样品相结合的方法对重整生成油C8馏分中的芳烯烃进行了定性定量分析,从12O多种组分中鉴定出18种烯烃,对其中的15种烯烃组分进行了定量分析,对其它3种烯烃组分进行了半定量分析。本法操作简单、重复性好,适用于重整生成油C8馏分和二甲苯塔塔顶液的烯烃检测,也可用于芳烃厂同类产品质量控制分析。     

烯烃与环烷烃在催化裂化中反应的异同点

烯烃和环烷烃是催化裂化原料中常见的两种分子类型,对这两类分子反应特点和反应规律的研究对于深入认识催化裂化反应具有重要意义。采用计算化学工具,详细研究烯烃和环烷烃裂化过程中的热力学和动力学。结果表明,在B酸中心作用下,烯烃主要发生裂化反应;在L酸中心作用下,烯烃容易发生环化反应生成环烷基正碳离子,并进一步发生反应生成环烷烃和环烯烃;环烷烃的裂化反应受到热力学限制,反应发生较为困难;烯烃环化反应和环烷烃裂化反应互为逆反应,在催化裂化过程中烯烃环化反应占据优势。