CIM-6单元镍油脂氢化催化剂的研制

在用H2 冷等离子体处理常规Cu -Ni二元油脂加氢催化剂 ,发现一种新的、有用的催化剂表面结构和研制开发成功CIMCu -Ni二元油脂加氢催化剂及其相关技术的基础上 ,研制成了CIM - 6单元镍油脂加氢催化剂。实验结果表明 :1 CIM - 6催化剂用于豆油加氢制食用氢化油 ,其活性 (以催化剂的时空转化率计 )是SP - 7催化剂 (美国EngelhardCo.)的 4 5倍 ;用于菜油加氢制食用氢化油 ,其活性是SP - 7的 7 3倍。 2 CIM - 6的抗硫能力 (n(S) =3× 10 - 6 )是SP - 7的1 6倍。 3 CIM - 6的选择性比SP - 7略好     

离子膜电解工艺指标的制定

分析了离子膜电解工艺指标对运行过程的影响 ,制定出为确保离子膜长期稳定运行的各工艺指标的范围 :进槽盐水为pH >3.0 ,NaClO3<15g L ,Na2 SO4 <7g L ,Ca +Mg <2× 10 - 8,I <5× 10 - 7,SiO2 <1× 10 - 5,Mn <5× 10 - 8,TOC <1× 1- 5,SS <1× 10 - 6 ,Sr>2× 10 - 8,Ba <5× 10 - 8,Fe <1× 10 - 6 ,Al<1× 10 - 7,Ni<1× 10 - 8,F <1× 10 - 6 ;碱液质量分数为 ( 32 .5± 0 .5 ) % ;阳极液质量浓度为 2 2 0～ 2 30g L ;槽温在电流为 12 .5kA时为 ( 85± 2 .5 )℃。     

国内新型双功能加氢转化催化剂及其应用

新型双功能转化催化剂可应用于以炼厂气为原料的制氢和合成氨工艺。当炼厂气中烯烃含量 >8%时 ,应采用等温 -绝热流程和JT - 1G、JT - 4型催化剂 ;<8%时 ,应将JF - 1G与氧化锌脱硫剂串联使用 ,可使烯烃脱至 <0 5 % ,总硫含量脱至 <0 5× 10 -6,催化剂使用寿命可达 2年以上     

LY-9302型重整预加氢催化剂的开发应用

开发了LY - 930 2型重整预加氢催化剂 ,并在装置上使用 ,替代进口的S - 12含量催化剂。结果表明 :在反应温度 2 95～ 30 8℃、反应压力 2 8～ 2 9MPa、原料油中S含量≤ 346× 10 -6及N含量≤ 3 1× 10 -6、体积空速 4 4～ 7 0h-1、氢油体积比 88 7～ 117的条件下 ,预加氢精制油中S、N含量均小于 0 5× 10 -6,精制油液收率大于 97% ,完全能满足装置生产的要求 ;LY - 930 2型催化剂加氢脱硫、脱氮活性比原使用的S - 12型催化剂略高 ,选择性、寿命等均达到S - 12型的性能 ,完全能替代S - 12型催化剂     

合成氨生产的新进展

世界需求氮肥 (折氮量 )将从 2 0 0 1年 1 0 60× 10 8t增加到 2 0 0 3年 1 112× 10 8t,世界氮肥 (折氮量 )能力现为 1 3 2 7× 10 8t/a(合成氨能力 1 6× 10 8t/a)。2 0 0 5年前 ,全世界将有约 6 5× 10 6 t/a合成氨能力投产。沙特阿拉伯化肥公司 (SAFCO) (沙特基础工业公司子公司 )兴建的世界最大单系列合成氨装置将于 2 0 0 5年投产 ,该装置能力为 3 0 0 0t/d(约 1× 10 6 t/a) ,它比现有的最大装置要大5 0 %。另外 ,40 0 0t/d规模的装置也已完成初步设计。现在 ,世界最大单系列新建装置为阿根廷Profertil公司的 2 0 5 0t/d装置 ,采…     

动植物油脂低温低压氢化技术及助剂的研究

使用了一种镍催化剂低温、低压加氢技术 ,同时使用了具有较好吸附性的助剂 ,来提高加氢效率。氢化工艺能达到低温、低压、短氢化时间。使氢化过程更加完善。确定了反应的优惠条件 :氢化反应时间为 10 0～ 110min ,反应温度为 10 0℃ ,催化剂用量为 0 5 5kg(相对于 10kg猪油 ) ,反应压力为 0 .5 5MPa。在这一反应条件下猪油氢化可得到熔点为 5 6～5 8℃ ,碘值≤ 2的硬脂酸用氢化油。加入助剂能平均缩短反应时间约 15min。可以平均降低压力 0 0 5MPa。     

铈(Ⅳ)-吐温-40-间苯三酚化学发光体系的研究及其应用

基于在吐温 4 0存在下 ,间苯三酚与铈 (Ⅳ )在酸性介质中发生化学发光反应 ,建立了测定间苯三酚化学发光分析法 ,该法测定间苯三酚的线性范围为 5 0× 10 -8～ 5 0× 10 -5mol·L-1,检出限为 1 0×10 -8mol·L-1,相对标准偏差为 2 8% (5 0× 10 -6mol·L-1邻苯二酚 ,n =11)。该法应用于测定模拟水样的间苯三酚 ,结果令人满意。     

核黄素的循环伏安法分析

介绍了在 NH3 · H2 O- NH4 Cl( PH=1 0 )缓冲溶液中的核黄素 (维生素 B2 )循环伏安图 ;核黄素在 - 0 .545V( VS.Ag Cl/Ag)产生一个阴极峰 ;在 - 0 .50 6 V产生一个阳极峰。其波高与核黄素溶液的浓度分别在 6× 1 0 - 7～ 7× 1 0 - 6mol· l- 1和 4× 1 0 - 7～ 8× 1 0 - 6mol· l- 1范围内成线性关系 ,检测限分别为 4× 1 0 - 7mol· l- 1和 2× 1 0 - 7mol· l- 1。     

活性硅铝炭黑在胶管中的应用

为了降低成本 ,我公司对在胶管胶料中用活性硅铝炭黑替代半补强炭黑进行了应用试验 ,现将试用情况介绍如下。硅铝炭黑的主要成分为二氧化硅、氧化铝和炭。活性硅铝炭黑由普通硅铝炭黑活化而成。本工作选用彭州市龙新精细矿粉厂生产的活性硅铝炭黑 2进行试验。该活性硅铝炭黑的理化性能如表 1所示。表 1　活性硅铝炭黑 2的理化特性项　　目实测值 标准值1 )外观灰黑色灰黑色吸碘值 / (mg·g- 1 ) 13 .5 2 8～ 2 0DBP吸收值× 10 5/ (m3·kg- 1 ) 3 43 0～ 5 0pH值 7～ 10 7～ 10加热减量 ( 10 5℃× 1h) / % 1.2 1≤ 1.515 0 μm筛余物质量…     

催化动力学光度法测定痕量钒(Ⅴ)的研究

研究了在 p H=4及没食子酸存在下 ,微量钒 ( )催化溴酸钾氧化邻苯二胺的动力学条件 ,建立了催化动力学光度法测定痕量钒 ( )的新方法。方法的测定范围为 0～ 0 .0 2 5 μg· 2 5 m L- 1 ,检出限为 1.18× 10 - 6 g·L- 1 ,相对标准偏差为 4 .6 3% (n=10 ) ,线性回归方程为△ A=2 5 .6 6 c(μg· 2 5 m L- 1 ) - 0 .0 15 7(r=0 .9997) ,表观摩尔吸光系数ε4 6 0 nm=3.2 7× 10 7L· m ol- 1 · cm- 1 。该法灵敏度高 ,选择性好 ,直接应用于水样和食品样中痕量钒( )的测定 ,结果满意     

Production of biodiesel by esterification of natural fatty acids over modified organoclay catalysts

Biodiesel has been produced by esterification of natural fatty acids with methanol in the presence of a modified bentonite with 1-benzyl-1H-benzimidazole-based Brønsted acidic ionic liquids as catalysts. The effect of reaction temperature, type and amount of catalyst, molar ratio and reaction time was investigated. The results showed that MB3B (bentonite modified with 3,3′-(butane-1,6-diyl)bis(6-sulfo-1-(4-sulfobenzyl)-1H-benzimidazolium) hydrogensulfate) has the highest catalytic activity and best recyclability under the optimized reaction conditions. Thus, this modified bentonite is able to catalyze the esterification of oleic acid to its methyl ester in 6 h with yields of more than 92%. The catalytic activity of MB3B for the esterification of natural other fatty acids and alcohols has also been studied.     

聚乙二醇改性植物油的催化剂研究进展

综述了植物油改性合成聚乙二醇脂肪酸酯的催化剂研究进展。提出采用固体碱为催化剂进行脂肪酸酯类化合物与聚乙二醇酯交换反应来制备聚乙二醇脂肪酸酯基的方法。指出固体碱催化剂在此酯交换反应中的优良性能和应用前景。     

Unprecedented Reductive Esterification of Carboxylic Acids under Hydrogen by Reusable Heterogeneous Platinum Catalysts

Supported metal catalysts have been tested for an unprecedented reductive dimerization of carboxylic acids to esters under 8 bar hydrogen in solvent‐free conditions. Among various metal‐loaded tin oxide catalysts, platinum‐loaded tin dioxide (Pt/SnO₂) shows the highest ester yield for the reaction of dodecanoic acid. Among Pt catalysts on various supports, Lewis acidic oxides, especially SnO₂, show high activity. The most active catalyst, 5 wt% Pt/SnO₂ reduced at 100 °C, is effective for the reductive esterification of various carboxylic acids, and the catalyst is reusable for nine cycles, demonstrating the first successful example for the title reaction. Infrared (IR) studies of a model compound (formic acid) on some metal oxides indicate a strong Lewis acid‐base interaction between SnO₂ and the carbonyl oxygen. For Pt/SnO₂ catalysts with different Pt particle sizes, the activity increases with decreasing size of Pt metal. A cooperative catalysis of the Pt metal nanoparticles and the Sn⁴⁺ Lewis acid sites is proposed.

     

聚乙二醇改性菜籽油的碱催化合成及性能

在固体碱催化下,由菜籽油改性制得的菜籽油脂肪酸甲酯与聚乙二醇400(PEG400)进行酯交换反应,合成了绿色可降解的多功能非离子表面活性剂聚乙二醇脂肪酸酯。对酯交换反应的主要影响因素和产物性能进行了考察。结果表明,在m(菜籽油脂肪酸甲酯)∶m(PEG400)=2.0∶1.0,催化剂w(CaO/ZrO2)=0.8%(相对于反应物总质量),温度130℃,反应时间7.5h的条件下,聚乙二醇脂肪酸酯产率达91.56%;产物浊点53℃、表面张力35mN/m、乳化性361s、润湿力59s,说明具有很好的表面活性。     

杂多酸催化合成乳酸正丁酯

研究了以杂多酸催化乳酸和正丁醇合成乳酸正丁酯的反应，探讨了不同催化剂，催化剂用量，原料配比，反应时间，带水剂，催化剂的重复使用次数等对酯化率的影响。实验表明杂多酸为催化剂，具有反应条件温和，催化剂用量少，催化活性高等优点，而且，不腐蚀设备，反应后易处理，污染小。在适宜的工艺条件下，酯化率可达98．53％。催化剂重复使用表明杂多酸是合成乳酸正丁酯的适宜催化剂。     

Eco-friendly Pretreatment of Oil with High Free Fatty Acid Content Using a Sulfamic Acid/Ethanol System

In recent years, sulfamic acid (SA, NH₂SO₃H) has emerged as a novel green catalyst for organic synthesis because of several advantages, including its non‐volatility, non‐hygroscopicity, non‐corrosivity, and low cost. This work reports the use of sulfamic acid as a catalyst in the pretreatment of oil with a high content of free fatty acids (10 and 20 % FFA) in ethanol or methanol. The process (esterification reaction) used in the pretreatment of the oil was carried out under a variety of conditions, initial fatty acid content, temperature, type of alcohol, and % catalyst. The experiments using an NH₂SO₃H/ethanol system resulted in a high fatty acid ethyl ester conversion, 88.53 % (±0.95) from an initial acidity of 40 mg KOH/g (20 % FFA), using 8 % NH₂SO₃H as the catalyst. According to the results, the methodology using sulfamic acid and ethanol demonstrated elevated potential for a environmentally‐friendly means of biodiesel production.     

Combined Biocatalytic and Chemical Transformations of Oleic Acid to ω‐Hydroxynonanoic Acid and α,ω‐Nonanedioic Acid

A practical chemoenzymatic method for the synthesis of 9‐hydroxynonanoic acid and 1,9‐nonanedioic acid (i.e., azelaic acid) from oleic acid [(9Z)‐octadec‐9‐enoic acid] was investigated. Biotransformation of oleic acid into 9‐(nonanoyloxy)nonanoic acid via 10‐hydroxyoctadecanoic acid and 10‐keto‐octadecanoic acid was driven by a C‐9 double bond hydratase from Stenotrophomonas maltophilia, an alcohol dehydrogenase from Micrococcus luteus, and a Baeyer–Villiger monooxygenase (BVMO) from Pseudomonas putida KT2440, which was expressed in recombinant Escherichia coli. After production of the ester (i.e., the BVMO reaction product), the compound was chemically hydrolyzed to n‐nonanoic acid and 9‐hydroxynonanoic acid because n‐nonanoic acid is toxic to E. coli. The ester was also converted into 9‐hydroxynonanoic acid and the n‐nonanoic acid methyl ester, which can be oxygenated into the 9‐hydroxynonanoic acid methyl ester by the AlkBGT from P. putida GPo1. Finally, 9‐hydroxynonanoic acid was chemically oxidized to azelaic acid with a high yield under fairly mild reaction conditions. For example, whole‐cell biotransformation at a high cell density (i.e., 10 g dry cells/L) allowed the final ester product concentration and volumetric productivity to reach 25 mM and 2.8 mM h⁻¹, respectively. The overall molar yield of azelaic acid from oleic acid was 58%, based on the biotransformation and chemical transformation conversion yields of 84% and 68%, respectively.

     

Advantages of an Emulsion‐Produced Ziegler‐Natta Catalyst Over a Conventional Ziegler‐Natta Catalyst

Summary: Self‐supported and MgCl₂‐supported Ziegler‐Natta catalysts, produced by two catalyst synthesis methods are compared. Borealis Polymers OY (Finland), who supplied the catalysts, developed the catalyst synthesis methods. The first method (Method One) is based on an emulsion system and consists of an in situ single step preparation. The second method (Method Two) consists mainly of two steps: formation of the catalyst carrier particles, and their subsequent impregnation with the active material. The results showed that Method One produced catalysts of compact, spherical particles with good intra‐particle homogeneity and a narrow particle size distribution. On the other hand, Method Two produced catalyst particles whose properties depended directly on that of the catalyst carrier: they were spherical but very porous, with a broad particle size distribution. Polymer particles produced with the two catalyst systems are perfect replicas of the catalyst particles. Fines formed either during catalyst preparation or during polymerization were observed only with the catalyst prepared using Method Two. The particles of the catalysts produced using Methods One and Two had similar activities, independent of the initial particle size. Fragmentation of catalyst particles was very fast for both catalyst systems and was only observed to be 100% completed using the catalyst produced with Method One. Studies of the thermal properties showed that the catalyst prepared using Method One produced poly(propylene) of higher crystallinity and with a narrower melting peak.

SEM images of polymer particles produced by (A) Method One and (B) Method Two.     

合成苹果酯的催化剂研究

本文综述了铌酸、硫酸铝、无水AlCl3 、FeCl3 、CuCl2 、ZnCl2 、SnCl4/C、酸性树脂、固载型三氯化铁离子交换树脂、三氯化铁漆酚树脂的复合物、柠檬酸、1%饱和脂肪酸、固体超强酸SO2 -4/ZrO2 、SO2 -4/TiO2 、PO2 -4/TiO2 、SO2 -4/TiO2 /La3 + 和SO2 -4/Fe2 O3 、磷钼酸、固载杂多酸、TiSiW12 O40 /TiO2 以及WN - 1等二十余种不同催化剂催化合成苹果酯的实验结果。结果表明 :硫酸铝、酸性树脂、三氯化铁漆酚树酯、纳米级固体超强酸SO2 -4/TiO2 和活性炭固载的杂多酸 (HPA /C)五种催化剂对合成苹果酯的酯收率较高 ,具有实际应用价值。