Improved synthesis and characterization of saturated branched‐chain fatty acid isomers

The development of viable technologies for producing green products from renewable fats and oils is highly desirable since such materials can serve as replacements for non‐renewable and poorly biodegradable petroleum‐based products. Mixtures of saturated branched‐chain fatty acid isomers (sbc‐FAs), commonly referred to as isostearic acid, are important intermediates for the production of biodegradable lubricants, cosmetics, emollients, and hydraulic fluids. Present methods for producing sbc‐FAs, however, often give low yields of sbc‐FAs or sbc‐FA preparations with a high content of dimer acid fatty acid co‐products. This study reports an improved route to synthesizing sbc‐FAs from monounsaturated fatty acids using a modified H‐Ferrierite zeolite catalyst in conjunction with small amounts of triphenylphosphine additive. The yields of sbc‐FAs (up to 80 wt%) and co‐products (up to15 wt%) were determined using a modification of a previously reported GC method. A more detailed analysis of the distribution of sbc‐FA isomers in the products was made by the combined use of GC × GC‐TOF‐MS. Additionally, it was found that the H‐Ferrierite zeolite catalyst was recyclable and reusable up to 10 times without significant loss of activity and selectivity for sbc‐FAs.     

Synthesis and physical properties of isostearic acids and their esters

Saturated branched‐chain fatty acids (sbc‐FAs) are found as minor constituents in several natural fats and oils. Sbc‐FAs are of interest since they have lower melting points than their linear counterparts and exhibit good oxidative stability; properties that make them ideally suited in a number of applications. We (and others) have previously synthesized sbc‐FAs by clay‐ or zeolite‐catalyzed isomerization of unsaturated linear‐chain fatty acids (ulc‐FAs) to unsaturated branched‐chain fatty acids (ubc‐FAs) that were subsequently hydrogenated to the desired sbc‐FAs. These acid‐catalyzed isomerization reactions, however, proceed in moderate conversion and selectivity. Recently, our group found that H‐Ferrierite zeolite catalyst isomerized ulc‐FAs to their branched‐chain counterparts in high conversion (>95%) and selectivity (85%). This paper reports the use of this type of catalyst for the preparation of a series of sbc‐FAs and their ester derivatives. Selected physical properties of these branched acids and esters such as cloud point (CP) and pour point (PP), cold filter plugging point (CFPP), viscosity index (VI), thermo‐oxidation stability, iodine value, and lubricity are also reported.     

Linear Hydrocarbons Adsorbed in the Acid Zeolite Gmelinite at 700 K ab Initio Molecular Dynamics Simulation of Hexane and Hexene

First-principles molecular dynamics simulations are performed to sample the behavior of linear hydrocarbons within the acid zeolite gmelinite at high temperature. The analysis of the trajectories, the time-development of the bond lengths, and simulated IR spectra are presented for both neutral and protonated molecules. The acid proton shows no affinity toward paraffin and slightly increased affinity toward the double bond of the olefin. No spontaneous protonation of the olefin is observed. The simulation of the protonated linear C6H13+ molecule shows that the protonated species is stabilized within the zeolite framework, and no collapse to the neutral molecule occurs. No cracking or isomerization event is observed. The protonated molecule shows rather high mobility accompanied by a series of hydride transfers along the chain of the molecule. The transfer of the H atom leads to a relocation of the positive charge. The relocation is correlated to the position of the Al site in the zeolite framework. In the simulated IR spectra we observe no distinctive feature evidencing the existence of the protonated species.     

Effect of Ni in palladium <Emphasis Type="Italic">β</Emphasis>-zeolite on hydroisomerization of <Emphasis Type="Italic">n</Emphasis>-decane

Bifunctional catalysts containing (0.1–0.5 wt%) Nickel and 0.1 wt% of Pd supported on H-β zeolite were synthesized by incipient wetness impregnation method and characterized by XRD, TEM, XPS, TPD and TPR techniques. The catalytic activity of Ni containing and Ni free Pd/H-β Catalysts was studied, and it was found that Ni up to a threshold value (0.3 wt% on β) produced increased the n-decane conversion and isomerization selectivity. When Ni content exceeds the threshold value, the conversion increases but isomerized products decrease. Moreover, Ni containing Pd/H-β showed increased sustainability and favored the protonated cyclopropane (PCP) intermediate mechanism in n-decane isomerization. The catalyst containing 0.3 wt% Ni 0.1 wt% Pd is adjudged as one performing better than other catalysts studied because of the isomerized mixture from it shows better octane number.     

Isomerization of n-hexane over nickel-loaded zeolite catalysts

The isomerization of n-hexane to branched-chain isomers was studied over various zeolite supports containing nickel between 1 to 5 wt%. NaA, NaY, CaY and Zeolon 900H were loaded with nickel by an impregnation technique. It was observed that at a nickel content of about 2.5 wt%, all the catalysts showed maximum activity for isomerization. A catalyst containing 1 wt% Ni/CaY gave the maximum selectivity among all the catalysts studied. Increasing the nickel loading beyond 2.5 wt% Ni with CaY and Zeolon 900H led to more hydrocracking. No major change in the activity and selectivity of Ni/NaA catalysts was observed beyond 2.5 wt% Ni, whereas the activity of Ni/NaY catalysts remained almost constant over the range of nickel content studied. A catalyst containing 2.5 wt% Ni on Zeolon 900H gave the maximum yield of isomers at 643°K. The apparent activation energy of the reaction was found to be 48.6 kJ/mol for 1 wt% Ni on Zeolon 900H catalyst.     

Pt-loaded zeolites for reducing exhaust gas emissions at low temperatures and in lean conditions

In this study, pure and platinum-loaded zeolites, ZSM-5, Beta, zeolite Y and Ferrierite, were examined for the reduction of NO with propene in lean conditions and at low temperatures. The studies were carried out by utilising the FT-IR technique both in determination of surface species as well as concentrations in the gas flow at reactor outlet. The maximum in the intermediate formation can be observed at the light-off temperatures over all studied catalyst materials. The maximum conversions of NO were reached with 1 wt% Pt-loaded Beta and Y zeolites in excess oxygen. The lowest light-off temperatures of NO as well as propene can be detected also with Beta and Y zeolite catalysts.     

MCM-22/REHY催化剂上的FCC汽油改质

采用USY、REY和REHY分子筛为催化剂，在固定流化床上进行了催化裂化(FCC)汽油改性试验。结果表明，REHY催化剂表现出较好的芳构化和异构化性能。在反应温度400 ℃、液态汽油空速2 h^－1和反应时间15 min条件下，质量分数为5%的MCM-22对REHY催化剂起到很好的助催作用，液体收率达94.4%，而添加相同量的ZSM-5时，液体收率仅为90.46%；两者的异构化产物选择性和芳烃收率差别不大。考察了反应条件对5%MCM-22/REHY上反应的影响。     

FCC工艺中提升增产丙烯助剂性能研究进展

流化催化裂化（FCC）是炼厂最重要的二次加工工艺,也是石油化工应用中丙烯的第二大来源。随着丙烯需求消费的不断增长,在FCC催化剂中添加增产丙烯助剂是一种灵活、高效提高丙烯收率的途径,其助剂主要由活性组分ZSM-5分子筛和基质组成。本文主要从活性组分ZSM-5分子筛和基质两方面分别介绍目前阶段增产丙烯助剂的研究现状,通过对ZSM-5分子筛的改性来提升活性组分的性能,重点综述了调变分子筛的酸度、改善孔结构及粒度和提高水热稳定性;分析了基质孔结构和酸性的梯度分布对助剂在FCC工艺中提高原料的转化、减少生焦和增产丙烯的重要作用。最后指出在合成分子筛过程中引入改性元素,减少元素流失,提高改性元素的利用率,同时在助剂基质方面的研究仍有不足,开发低成本、大孔径和适宜酸度的高性能基质也是增产丙烯助剂未来的研究方向。     

Deactivation of ZSM-5 additives in laboratory for realistic testing

ZSM-5 deactivates differently from Y zeolite. Dealumination of Y zeolite during deactivation causes UCS shrinkage and thereby decline in activity and changes in selectivity. For ZSM-5 instead deactivation removes alumina from the zeolite structure, but in spite of that the zeolite structure does not collapse. Therefore, deactivation causes activity decline due to loss of active alumina sites, but no significant changes in the strength and separation between acid sites. Unlike with FCC catalyst, physical properties of ZSM-5 additive do not change significantly with deactivation and surface area and pore volume measurements cannot be used as indications of additive performance. Yet, since both Y and ZSM-5 are used simultaneously in practice, the information on the relative rates of deactivation between the two zeolites is very important. Therefore, the question remains, what is the best way to deactivate and test ZSM-5 additives in the laboratory to obtain realistic performance, e.g. propylene yield and to obtain proper ranking of various additives. This paper discusses the effect of deactivation conditions as well as performance testing aspects of ZSM-5 additives. It is shown that choice of deactivation conditions has an effect on additive ranking and performance. By choosing the deactivation conditions properly ranking can be made clearer and more realistic additive performance is obtained.     

Utilization of ZSM-5/MCM-41 composite as FCC catalyst additive for enhancing propylene yield from VGO cracking

A micro-mesoporous ZSM-5/MCM-41 composite molecular sieve (ZM13) was synthesized and tested as an FCC catalyst additive to enhance the yield of propylene from catalytic cracking of vacuum gas oil (VGO). The catalytic performance of the additive was assessed using a commercial equilibrium USY FCC catalyst (E-Cat) in a fixed-bed micro-activity test unit (MAT) at 520?°C and various catalyst/oil ratios. MCM-41, ZSM-5 and two ZSM-5/MCM-41 composites were systematically characterized by complementary techniques such as XRD, BET, FTIR and SEM. The characterization results showed that the composites contained secondary building unit with different textural properties compared to pure ZSM-5 and MCM-41. MAT results showed that the VGO cracking activity of E-Cat did not decrease by using these additives. The highest propylene yield of 12.2 wt% was achieved over steamed ZSM-5/MCM-41 composite additive (ZM13) compared with 8.6 wt% over conventional ZSM-5 additive at similar gasoline yield penalty. The enhanced production of propylene over composite additive was attributed to its mesopores that suppressed secondary and hydrogen transfer reactions and offered easier transport and accessibility to active sites. Gasoline quality was improved by the use of all additives except MCM-41, as octane rating increased by 6?C12 numbers.     

由直链不饱和脂肪酸异构制备支链脂肪酸的研究进展

介绍了直链不饱和脂肪酸制备支链脂肪酸的研究现状,综述了脂肪酸异构机理,异构催化剂如白土催化剂、沸石催化剂,催化剂的筛选原则,着重讨论了各种常用沸石对于脂肪酸异构反应不同的影响以及现有的合成工艺。分析了脂肪酸的分离技术,包括精馏分离法、溶剂结晶法、尿素包结法、超临界流体萃取法的优缺点,指出沸石催化生产支链饱和脂肪酸的关键问题是需要解决混合脂肪酸作为原料反应的选择性问题,其相关的基础性工作,如更明确的反应机理和催化剂结构参数对反应的影响,仍是将来的研究方向。     

Characterization of Modified Nanoscale ZSM-5 Zeolite and Its Application in the Olefins Reduction in FCC Gasoline

Nanoscale HZSM-5 zeolite was hydrothermally treated with steam containing 0.8 wt% NH₃ at 773 K and then loaded with La₂O₃ and NiO. Both the parent nanoscale HZSM-5 and the modified nanoscale HZSM-5 zeolites catalysts were characterized by TEM, XRD, IR, NH₃-TPD and XRF, and then the performance of olefins reduction in fluidized catalytic cracking (FCC) gasoline over the modified nanoscale HZSM-5 zeolite catalyst was investigated. The IR and NH₃-TPD results showed that the amount of acids of the parent nanoscale HZSM-5 zeolite decreased after the combined modification, so did the strong acid sites deactivating catalysts. The stability of the catalyst was still satisfactory, though the initial activity decreased a little after the combined modification. The modification reduced the ability of aromatization of nanoscale HZSM-5 zeolite catalyst and increased its isomerization ability. After 300 h onstream, the average olefins content in the gasoline was reduced from 56.3 vol% to about 20 vol%, the aromatics (C₇–C₉ aromatics mainly) and paraffins contents in the product were increased from 11.6 vol% and 32.1 vol% to about 20 vol% and 60 vol% respectively. The ratio of i-paraffins/n-paraffins also increased from 3.2 to 6.6. The yield of gasoline was obtained at 97 wt%, while the Research Octane Number (RON) remained about 90.     

铁镍复合助剂对煤热解过程中氮迁移规律的影响

为了减少煤炭燃烧过程中NO_x的排放,在管式炉中进行了煤与金属助剂（FeCl₃、NiCl₂）的热解实验,研究了助剂负载量、热解温度、助剂添加方式对氮迁移及N₂产率的影响并且对复合助剂作用机理进行了探讨。结果表明：随着助剂负载量的增加,氮脱除率及N₂产率呈现先增加后趋于稳定的趋势,且负载量以0.8%Fe复合1.0%Ni为最佳。在700~1000℃的热解温度范围内氮脱除率及N₂产率随热解温度的增加而增加。对煤进行溶胀处理添加复合助剂后,氮脱除率及N₂产率要优于未经处理的煤样。铁基助剂与镍基助剂在催化煤热解氮迁移过程中形成互补,铁基助剂的添加增加了镍基助剂的活性,弥补了单助剂的劣势,且复合助剂相比于单助剂有更强的氮脱除效果并且N₂产率达到最高39%。铁镍复合助剂对煤中N-5转化为N₂的催化效果更加明显,因为复合助剂对吡咯的内氢转移和开环有更强的催化作用。本研究能够为煤炭洁净化利用提供理论和实验依据。     

Nickel impregnated Pt/H-β and Pt/H-mordenite catalysts for hydroisomerization of n-hexane

Nickel impregnated Pt/H-β and Pt/H-MOR catalysts with different Ni content were prepared and subjected to hydroisomerization of n-hexane in the presence of flowing H₂ gas. The states of Pt and Ni were identified by ESCA. The particle size measured by TEM shows that average particle size increases with increasing Ni loading. The acidity of the catalysts was measured by TPD of ammonia. The catalytic activity of Ni containing and Ni free Pt/H-β and Pt/H-MOR catalysts was compared and found that addition of Ni up to a threshold value (0.3 wt% for β and 0.1 wt% for MOR) increases the n-hexane conversion and dimethyl butanes selectivity due to better metal-acid synergism and decreases the amount of cracked products. When the Ni amount exceeds the threshold values the conversion decreases and cracked products increase. Further the Ni impregnation of Pt containing acidic supports increases the sustainability of the catalysts and was found to favor the protonated cyclopropane (PCP) intermediate mechanism in n-hexane isomerization. β zeolite was found to be a better potential support than mordenite and the isomerized product mixture shows better octane number.     

Preparation and characterization of ceramic foam supported nanocrystalline zeolite catalysts

The influence of the viscosity of the ceramic slip on the manufacture of ceramic foams by the polymer sponge method was studied. The foams were coated with silicalite (100 nm) and HZSM-5 (650 nm) crystals by dipping them in a zeolite suspension without binder additives. The amount of zeolite loaded can be controlled through the zeolite content of the dipping suspension. Uniform coatings are achieved starting with about 1 g zeolite/m² foam.     

Enhancing propylene production from catalytic cracking of Arabian Light VGO over novel zeolites as FCC catalyst additives

The catalytic cracking of vacuum gas oil over fluid catalytic cracking (FCC) catalyst containing novel additives was investigated to enhance propylene yield. A conventional ZSM-5, mesoporous ZSM-5 (Meso-Z), TNU-9 and SSZ-33 zeolite were tested as additives to a commercial equilibrium USY FCC catalyst (E-Cat). Their catalytic performance was assessed in a fixed-bed micro-activity test unit (MAT) at 520 °C and various catalyst/oil ratios. The cracking activity of all E-Cat/additives did not decrease by using these additives. The highest propylene yield of 12.2 wt.% was achieved over E-Cat/Meso-Z compared with 9.0 wt.% each over E-Cat/ZSM-5 and E-Cat/TNU-9, at similar gasoline yield penalty. The enhanced production of propylene over Meso-Z is attributed to its mesopores that suppressed secondary and hydrogen transfer reactions and offered easier transport and accessibility to active sites. The lower enhancement of propylene over the large-pore SSZ-33 additive was due to its high-hydrogen transfer activity. Gasoline quality was improved by the use of all additives, as octane rating increased by 7-12 numbers for all E-Cat/additives.     

Zeolite‐catalyzed isomerization of oleic acid to branched‐chain isomers

Branched‐chain (bc) saturated fatty acids (SFA) have potential as oleochemical intermediates since they have better oxidative stability than linear unsaturated fatty acids (UFA) and have better low‐temperature properties than linear SFA. Previous studies in converting UFA to bc‐FA using clay catalysts have resulted in only modest yields and conversions. Recent reports, however, have suggested that certain zeolites can be effective catalysts for converting UFA to bc‐FA in higher yields and conversions. In this work, we examined the scope and potential of the zeolite‐catalyzed synthesis of bc‐FA starting from readily available monounsaturated linear FA. Our results show that common UFA such as oleic acid can be converted to bc‐isomers using modified Ferrierite zeolite catalysts with high conversions (98%) and high selectivity (85%) and that the zeolite catalysts are reusable for at least three cycles. The positions of branching (methyl) on the FA chain were determined from the GC‐MS spectra of the picolinyl esters of the bc‐FA.     

Isomerization of n-butene over ferrierite zeolite modified by silicon tetrachloride treatment

Ferrierite zeolite modified by the deposition of SiCl₄, was prepared and investigated as a catalyst for the skeletal isomerization of 1-butene. The prepared catalysts were characterized by XRD, atomic absorption spectroscopy, ammonia TPD, FT-IR, BET/pore size distribution and pyridine chemisorption. The deposition of SiCl₄ preserved zeolite crystallinity although XRD and FT-IR analysis suggested a little framework de-alumination not evidenced by chemical analysis. This treatment narrowed pore size and diminished the strong/weak and Brönsted/Lewis acid sites ratio. As the SiCl₄ amount increased, the conversion of 1-butene decreased and selectivity to isobutene increased. This may be attributed to the higher spatial constraints inside the pores which restrict undesired reactions, such as 1-butene dimerization followed by cracking.

Abstract

The effect of temperature, weight hour space velocity and partial pressure of 1-butene was studied over modified and parent catalyst, indicating that a unimolecular mechanism prevails on modified samples while bimolecular processes are present on fresh ferrierite specially at short times on stream.     

植物油基润滑油应用研究现状

植物油具有生物可降解性、低挥发性、优良的润滑性和良好的黏温性,但植物油存在热氧化安定性差、低温性能差等缺陷,不能直接作润滑油和润滑添加剂应用,需要对其进行改性。常用化学改性方法有选择性氢化、酯交换和环氧化等,其中环氧化-开环反应引入活性基团和双键上的自由基加成反应是合成植物基润滑油添加剂的两种有效的改性方法。最后,就改性植物油用作可降解润滑油基础油和添加剂提出了研究方向并做了展望。     

Solid acid (superacid) catalyzed regioselective adamantylation of substituted benzenes

Adamantylation of substituted benzenes with 1-bromo-adamantane was catalyzed by solid acids including acidic ion exchange and ionomer resins, HY zeolite, sulfated zirconia and supported superacids on HY zeolite and SiO₂. Adamantylation generally takes place in excellent yield giving predominantly para products without formation of byproducts. The reactions did not require the usual workup of Friedel-Crafts reactions as catalysts were simply filtered of. Cross-linked polystyrene resin sulfonic acid (Amberlyst) was found particularly suitable as besides its high catalytic activity, high regioselectivity was observed with almost exclusive formation ofp-adamantylated benzenes. AMI, PM3 and MNDO semiempirical calculations of heats of formation showed that of all regioisomers, the para isomer is the most stable. The temperature dependence of adamantylation was also investigated allowing the optimization ofp-substituted product in high yield and excellent selectivity. Lack of isomerization of 1-p-tolyla-damantane using solid (Amberlyst, Nafion-H) and liquid acids (neat and modified trifluoromethanesulfonic acid) indicates absence of product isomerization, while the intramolecular rearrangement of the intermediate arenium complex is still possible.Catalysis by solid superacids, Part 30. For part 29, see ref.[1A].