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.     

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.     

Lewis Base Additives Improve the Zeolite Ferrierite‐Catalyzed Synthesis of Isostearic Acids

Isostearic acids (IA) are highly utilized for industrial purposes especially in the area of biolubricants, such as cosmetics and slip additives for polyolefin and related copolymer films. This study was designed to develop a zeolitic catalysis process for efficient IA production through isomerization of fatty acids. The process utilized zeolite protonated Ferrierite with a small amount of base additive to neutralize (i.e., poison) the acidic sites on the external surfaces of the zeolite particles to prevent side reactions. Of the six base additives examined, the proton sponge combined with the zeolite protonated Ferrierite was found to be the most effective for this isomerization. With only 0.5 wt% proton sponge additive to 5.0 wt% Ferrierite, the dimers were successfully suppressed from 20.6 wt% yield to 2.42 wt% with an IA yield of 83.4 wt% and a 98 % conversion.     

Selective Microbial Degradation of Saturated Methyl Branched-Chain Fatty Acid Isomers

Three strains of Pseudomonas (P.) bacteria were screened for their capabilities of degrading chemically synthesized saturated branched-chain fatty acids (sbc–FA). Mixtures of sbc–FA with the methyl-branch located at various locales along the fatty acid were used as a carbon feedstock in shake-flask culture. Utilization (and hence degradability) of the sbc–FA was monitored based on positive bacterial growth, fatty acid recovery rates and chromatographic (gas chromatography (GC) and GC-mass spectroscopy (MS)) analysis of the recovered carbon source. P. putida KT2442 and P. oleovorans NRRL B-14683 were both able to grow on sbc–FA utilizing 35 wt% and 27 wt% of the carbon source, respectively after 144 h. In contrast, P. resinovorans NRRL B-2649 exhibited the most efficient use of the carbon source by utilizing 89 % of the starting material after 96 h resulting in a cell dry weight (CDW) of 3.1 g/L. GC and GC–MS analysis of the recovered carbon source revealed that the bacterial strains selectively utilized the isostearic acid in the sbc–FA mixture, and a new group of C₁₀, C₁₂, C₁₄ and C₁₆-linear and/or branched-chain fatty acids (approximately 4–29 wt%) were formed during degradation.     

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.     

Production of olefins from ethanol by Fe and/or P‐modified H‐ZSM‐5 zeolite catalysts

BACKGROUND: Much attention has been paid to the catalytic conversion of ethanol to olefins, since biomass resources such as ethanol are carbon‐neutral and renewable, and olefins are useful as both fuels and chemicals. It has been reported that zeolite H‐ZSM‐5 is effective for converting ethanol to hydrocarbons, with the chief products being aromatic compounds. RESULTS: Successive addition of Fe and P to the H‐ZSM‐5 improved the initial selectivity for propylene, while the sole addition of Fe or P and co‐addition of Fe and P showed medium initial selectivity. In general, catalysts showing higher initial selectivity for propylene exhibited a steeper decrease in propylene selectivity with time on‐stream. The cause of the change in product selectivity may be carbon deposition during reaction. Addition of Fe and P can improve catalytic stability when processing both neat and aqueous ethanol. The catalytic performance was regenerated by calcination in flowing air. CONCLUSION: Fe‐ and/or P‐modified H‐ZSM‐5 zeolite catalysts efficiently produced olefins (especially propylene) from ethanol. Effective catalyst regeneration was achieved by calcination in flowing air. Copyright © 2010 Society of Chemical Industry     

Synthesis of alkyl‐branched fatty acids

Alkyl‐branched fatty compounds are of interest for industrial products in the cosmetics and lubricant areas. In this review, clay‐ and zeolite‐catalyzed isomerizations of unsaturated fatty compounds, especially of oleic acid, are discussed. While clay‐catalyzed reactions give most complex mixtures of dimeric fatty acids and of monomeric so‐called “isostearic acid”, the zeolite‐catalyzed process yields preferentially an isomeric mixture of isostearic acids having the methyl branch on the 8–14 positions of the alkyl chain. Synthetically useful additions of alkyl radicals can only be performed on ω‐unsaturated fatty compounds, whereas perfluoroalkyl iodides were added to fatty compounds with terminal as well as internal double bonds using electron transfer‐initiated radical addition reactions. Electrophilic additions of alkyl carbenium ions generated by decomposition of alkyl chloroformates by ethylaluminum sesquichloride give well‐defined alkyl‐branched oleochemicals with good yields.     

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.     

Combining Results of Two GC Separations Partly Achieves Determination of All <Emphasis Type="Italic">cis</Emphasis> and <Emphasis Type="Italic">trans</Emphasis> 16:1, 18:1, 18:2 and 18:3 Except CLA Isomers of Milk Fat as Demonstrated Using Ag-Ion SPE Fractionation

Milk fat is a complex mixture of geometric and positional isomers of monounsaturated and polyunsaturated, including short-, long- and branch-chain fatty acids (FAs). There has been partial success to resolve this mixture of FAs using different GC temperature programs, or a combination of GC isothermal and temperature programs. To overcome the problem associated with overlapping isomers prior silver-ion separation was recommended. However, this procedure is time consuming and not practical for routine analysis. In addition, previous methods focused mainly on the trans and cis isomers of 18:1. The present method takes advantage of differences in the relative elution times between different types of FAs. The method involved analyzing each milk fat using the same highly polar 100-m capillary column and GC instrument, and conducting two separations using temperature programs that plateau at 175 and 150 °C. The relative shift among the geometric and positional isomers at these two temperature settings was enough to permit identification of most of the trans and cis 16:1, 18:1 and 20:1, the c/t-18:2 and the c/c/t-18:3 isomers found in milk fat. The identity of these FAs was confirmed by prior separation of the total fatty acid methyl esters (FAMEs) of milk fat using Ag⁺-SPE columns, and comparing the fractions to the total milk fat. The Ag⁺-SPE technique was modified to obtain pure saturated, trans- and cis-monounsaturated and diunsaturated FAMEs. By combining the results from these two separate GC analyses, knowing the elution order, it was possible to determine most of the geometric and positional isomers of 16:1, 18:1, 20:1, 18:2 and 18:3 without a prior silver-ion separation. Only few minor FAs could not be resolved, notable the conjugated linoleic acid isomers that still required the complimentary Ag⁺-HPLC separation. The two GC temperature programs have been successfully used to routinely analyze most FA isomers in total milk and beef fats in about 200 min without the use of prior silver-ion separations.     

Biotechnological synthesis of long‐chain dicarboxylic acids as building blocks for polymers

An important field in sustainable industrial chemistry is the development of new applications for fats and oils. One of the promising applications is the use of fatty acid derivatives, e.g. dicarboxylic acid (DCA), as polymer building blocks. In contrast to conventional plastics, bioplastics are polymers derived from renewable biomass sources. In addition to their contribution to the conservation of fossil resources and reduction in CO₂ emissions by waste incineration, many bioplastics are biodegradable. The majority of industrial DCA production for polyamide (PA) and polyester (PE) synthesis is still done via chemical synthesis. While short‐chain DCA can be synthesized in high yields, costs of long‐chain DCA production rise significantly due to the generation of various by‐products and are connected mostly to a costly purification. Thus biotechnology provides novel biochemical approaches for long‐chain DCA synthesis that can provide an eco‐efficient process alternative. In the present article, strategies for the development of high‐level production strains for long‐chain DCA are illustrated. Basic strategies for strain development, in order to achieve an effective enrichment of DCA, require the knowledge of the respective biochemical pathways. These are discussed in detail. Furthermore an overview of fermentation strategies and characteristics of corresponding polymers is given.     

C18‐unsaturated branched‐chain fatty acid isomers: Characterization and physical properties

Iso‐oleic acid is a mixture of C₁₈‐unsaturated branched‐chain fatty acid isomers with a methyl group on various positions of the alkyl chain, which is the product of the skeletal isomerization reaction of oleic acid and is the intermediate used to make isostearic acid (C₁₈‐saturated branched‐chain fatty acid isomers). Methyl iso‐oleate, a mixture of C₁₈‐unsaturated branched‐chain fatty acid methyl ester isomers, is obtained via acid catalyzed esterification of iso‐oleic acid with methanol. The branched‐chain materials are liquid at room temperature and their “oiliness” property makes them an attractive candidate for the lubricant industry. In this paper, we report characterization of these branched‐chain materials using comprehensive two‐dimensional GC with time‐of‐flight mass spectrometry (GC × GC/TOF‐MS) and their physical and lubricity properties using tribology measurements.     

Catalytic Activity of Copper Oxide Impregnated HZSM‐5 in Methanol Conversion to Liquid Hydrocarbons

A number of CuO/HZSM‐5 catalysts have been studied in a small scale fixed bed reactor for the conversion of methanol to gasoline range hydrocarbons at 673 K and at one atmospheric pressure. All the catalysts were prepared by wet impregnation technique. The copper oxide loading over HZSM‐5 (Si/Al=45) catalyst was studied in the range of 0 to 9 wt%. XRD, surface area analyzer, metal trace analyzer, SEM techniques and TGA were used to characterize the catalysts. Incorporation of CuO onto HZSM‐5 zeolite significantly increased conversion and liquid hydrocarbon product yields. The major liquid products of the reactions were ethyl benzene, toluene, xylene, isopropyl benzene, ethyl toluene, trimethyl benzene and tetramethyl benzene. The maximum methanol conversion and hydrocarbon product yield was obtained at a copper oxide loading of 7 wt%. Effect of run time on conversion and product distribution was also investigated to compare the performance of these catalysts and coke on the catalyst was determined. Effect of space‐time and temperature on methanol conversion and products yield with 7 wt% CuO/HZSM‐5 has also been investigated and analyzed qualitatively.     

Extraction of a Homogeneous Rhodium Catalyst from Saturated Branched Fatty Derivatives

Saturated branched fatty derivatives are of great interest for the lubricants and cosmetics industry due to their improved temperature and viscosity behavior compared to the corresponding linear homologues. One way to produce saturated branched derivatives is the homogeneous rhodium‐catalyzed conjugation and co‐oligomerization of linoleic compounds based on renewable resources, e.g., sunflower oil, with ethene. The catalyst extraction behavior of the homogeneous rhodium catalyst RhCl₃·3H₂O from saturated branched fatty derivatives for catalyst recycling was studied. Investigation of the extraction parameters was performed using the model substance isostearic acid. Additionally, extraction of rhodium from co‐oligomer mixtures with different grade of saturation was carried out successfully. Also, the influence of solvent residues from prior reaction steps was evaluated.     

Catalytic para‐xylene maximization: III. Hydroisomerization of meta‐xylene on H‐ZSM‐5 catalysts containing different platinum contents

Hydroisomerization of meta‐xylene was carried out using catalysts containing 0.15–0.60 wt% Pt on H‐ZSM‐5 zeolite, in a pulsed microreactor system connected to a gas chromatograph at a flow of hydrogen of 20 cm³ min⁻¹ and temperatures of 275–500 °C. Increasing temperature, increased isomerization with low rates. Increasing Pt content of the catalyst, decreased hydrodealkylation considerably via masking strong acid sites as revealed by temperature programmed desorption of ammonia measurements. Formation of trimethylbenzenes was inhibited by Pt incorporation in the H‐ZSM‐5 zeolite. The activation energies obtained for meta‐xylene hydroisomerization were relatively low (24.4–61.6 kJ mol⁻¹) on all catalysts under study. Para‐xylene yields in the xylenes mixture of product relative to the corresponding thermodynamic equilibrium values amount to about 0.8–0.9 at temperatures of 400–500 °C but were lower at lower temperatures. © 1999 Society of Chemical Industry     

Effective biosynthesis of poly(3‐hydoxy‐ butyrate‐co‐4‐hydroxybutyrate) with high 4‐hydroxybutyrate fractions by Wautersia eutropha in the presence of α‐amino acids

BACKGROUND: Biopolymers produced by microbes are in demand as their biodegradable and biocompatible properties make them suitable for disposable products and for potential use as biomaterials for medical applications. The effective microbial production of copolyesters of 3‐hydroxybutyrate (3HB) and 4‐hydroxybutyrate(4HB) with high molar fractions of 4HB unit by a wild‐type Wautersia eutropha H16 was investigated in culture media containing 4‐hydroxybutyric acid (4HBA) and different carbon substrates in the presence of various α‐amino acids. RESULTS: The addition of carbon sources such as glucose, fructose and acetic acid to the culture medium containing 4HBA in the presence of α‐amino acids resulted in the production of random poly(3HB‐co‐4HB) with compositions of up to 77 mol% 4HB unit, but the yields of copolyesters with 60–77 mol% 4HB units were less than 15 wt% of dried cell weights. In contrast, when carbon sources such as propionic acid and butyric acid were used as the co‐substrates of 4HBA in the presence of α‐amino acids, poly(3HB‐co‐4HB) copolyesters with compositions of 72–86 mol% 4HB were produced at maximally 47.2 wt% of dried cell weight (11.3 g L^?1) and the molar conversion yield of 4HBA to 4HB fraction in copolyesters was as high as 31.4 mol%. Further, poly(3HB‐co‐4HB) copolyesters with compositions of 93–96 mol% 4HB were isolated at up to 35.2 wt% of dried cell weights by fractionation of the above copolymers with chloroform/n‐hexane. CONCLUSION: The productivity of copolyesters with over 80 mol% 4HB fractions was as high as 0.146 g L^?1 h^?1 (3.51 g L^?1 for 24 h) by flask batch cultivation. Copyright © 2007 Society of Chemical Industry     

Synthesis of Fatty Acetoacetates Under Microwave Irradiation Catalysed by Sulfamic Acid in a Solvent-Free System

The 1,3‐dicarbonyl compounds are important building blocks to obtain products with various biological activities and technological applications. In this work, we used a simple transesterification method to develop fatty acetoacetates in a solvent‐free medium using a green catalyst, sulfamic acid (NH₂SO₃H), under microwave irradiation. The experimental results demonstrate good yields in a short reaction time (13 min), which makes this method an efficient approach to synthesize fatty acetoacetates from a wide range of saturated, unsaturated, and polyunsaturated long chain fatty alcohols, and ricinoleic derivatives. Experiments of recycling of the catalyst were performed and no decrease in catalytic activity of sulfamic acid was observed.     

Selective Synthesis of Polyoxyethylene–Polyoxypropylene Block Copolymer (Poloxamer) Fatty Acid Monoesters Over Homogeneous Organotin Catalyst

The synthesis of selected polyoxyethylene–polyoxypropylene block copolymer (poloxamer) fatty acid monoesters is presented. Organotin homogeneous catalyst Sn bis(2‐ethylhexanoate) effectively catalyzed the esterification reaction of (EO)–(PO)–(EO) block copolymer (poloxamer) with fatty acids. The reaction proceeded in high yield and high selectivity to monoesters. Content of diesters in final products was below 1 wt%. The new protocol opened up a high yield and high selective method for the synthesis of poloxamer fatty acid monoesters. These products are potentially interesting for industrial applications, e.g. in lubricants, cosmetics and, in particular, as potential emulsifying agents compatible with hydrocarbon bases, such as paraffin.     

Liquid Phase Selective Catalytic Oxidation of Oleic Acid to Azelaic Acid Using Air and Transition Metal Acetate Bromide Complex

Industrially important di‐carboxylic acids are synthesized from mono‐carboxylic unsaturated and unsaturated fatty acids. In this study, the aim is to perform the simultaneous catalytic oxidative C=C cleavage of oleic acid (OA) to azelaic acid and pelargonic acid, and oxidation of the terminal methyl group in pelargonic acid to azelaic acid using cobalt‐ and manganese‐acetate as catalyst, hydrogen bromide as co‐catalyst and air in acetic acid at elevated pressure (2.8–5.8 barg) and temperature (353–383 K). Oxygen solubility is determined under varying pressure, temperature and OA loading. The effect of OA loading, pressure and temperature on OA conversion and azelaic acid selectivity is studied by varying one variable at a time; however, the presence of the synergistic effect of the catalyst and co‐catalyst is investigated by central composite design assisted response surface methodology. Oxidation of terminal methyl group in saturated fatty acid is also confirmed by the oxidation of stearic acid to octadecanedioic acid using identical oxidation conditions of OA. Oxidation products of fatty acids are quantified by gas chromatographic analysis. The innovation of the work is thus the ability of the catalytic system to perform a total oxidation of a terminal methyl group of the hydrocarbon chain. OA oxidation kinetics relating to catalyst and co‐catalyst concentration along with oxygen solubility at elevated temperature and pressure is established. The frequency factor and activation energy for OA oxidation is determined using the Arrhenius equation.     

Use of BPX‐70 60‐m GC columns for screening the fatty acid composition of industrial cookies

The fatty acid (FA) composition of food is requested for labelling purposes and food composition tables. Suitable analytical methods for labelling purposes must be able to efficiently identify and accurately quantify FA as swiftly and cheaply as possible. This study evaluated a middle‐length highly polar column, the BPX‐70 60‐m column, to balance analysis efficiency and duration. The use of a 60‐m column led to the loss of data on minor FA but a gain in analysis time. The column was evaluated by analysing the FA composition of ten cookies made with different kinds of fats, including milk fat, and pure and/or partially hydrogenated vegetable oils. The FA elution order in this GC phase has been poorly documented in the literature compared to equivalent highly polar CPSil‐88 and SP‐2460 GC phases. Co‐elutions and overlaps on the BPX‐70 column were studied and commented upon. Overall, the BPX‐70 60‐m column could be used for rapid screening of the FA composition of simple foods. Analysis of the FA composition of a complex matrix, such as a dairy product, and specific analysis of trans‐FA required a longer highly polar column, possibly after fractionation by silver‐ion liquid chromatography. Compared to other GC phases, the BPX‐70 enabled effective isolation of 18:3 isomers although these isomers co‐eluted with 20:1 isomers on other highly polar GC phases. However, some CLA isomers co‐eluted with other FA on this column, and a specific analysis of these special FA would require another phase and/or different chromatographic conditions.     

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。