Production Of Polyols Research Articles

Business Roundup

Business Roundup ShareShare onFacebookTwitterWechatLinked InRedditEmail C&EN, 2016, 94 (13), p 15March 28, 2016Cite this:C&EN 94, 13, 15AbstractNexeo Solutions, which calls itself the largest U.S. plastics distributor, is being sold by TPG to an affiliate of the private equity firm WL Ross & Co. for $1.6 billion. TPG, also a private equity firm, acquired Nexeo from Ashland in 2011 for $979 million. IHS is merging with the financial information provider Markit in a transaction worth about $13 billion. IHS, based in Englewood, Colo., is the largest supplier of market research for the chemical industry. In 2011, it purchased Chemical Market Associates Inc. (CMAI), which was renamed IHS Chemical. Novacap, a French chemical maker, is in the process of being sold by its majority owner, the investment company Ardian, to Eurazeo and Mérieux Développement, two European investment firms. Novacap is a former Rhodia business that employs about 1,600 people. Invista is set to expand the production of aromatic polyester polyols at its site in Vlissingen, the Netherlands.View: PDF | Full Text HTML

Sustainable Polyurethane Adhesives Derived from Carbon Dioxide

The demand for fuels as raw materials is increasing disproportionally, thus producing huge environmental impacts, as is the case of carbon dioxide emissions into the atmosphere. Nowadays, society is facing several challenges, including the implementation of new technologies that are able to meet energy needs and promote sustainable development. Therefore, one of the most commonly produced and used polymers worldwide, polyurethane, which is currently completely dependent on fossil fuels, could be developed in an environmentally sustainable way. In this regard, CO2 may be used for the synthesis of new materials, such as for the production of polyols, essential components in the manufacture of polyurethane. This work focused on the synthesis of polyurethane adhesives containing polyols from CO2. They were synthesised with 4,4'-diphenylmethane diisocyanate (MDI) and 1,4-butanediol as a chain extender. The sustainable polyurethane adhesives derived from carbon dioxide were characterised by Fourier Transform Infrared Spectroscopy (FTIR) and thermogravimetric tests (TGA). Finally, the adhesion properties were measured from a T-peel test on leather/polyurethane adhesive/ SBR rubber joints, in order to establish the amount of CO2-based polyol that could be added to polyurethane adhesives satisfactorily to meet the quality requirements of footwear joints.

【総説：応用糖質科学シンポジウム】 担子菌系酵母<i>Moniliella megachiliensis</i>の浸透圧ストレス応答とポリオール生成による適応戦略

担子菌系酵母Moniliella megachiliensisのポリオール生成につき，浸透圧ストレス応答と環境適応の観点から，その代謝制御系の解析を行った．エリスリトールは対数増殖期以降，erythrose reductase (ER) の遺伝子発現の増大に同調して大量に生成した．また，本遺伝子を強制発現した出芽酵母ではエリスリトールの生成が見られなかったことから，ERは本菌に特異的な酵素であると考えられた．浸透圧ストレスのシグナル伝達に関わるMAPK Hog1は，出芽酵母のそれと高い相同性を有するもののC 末端領域がやや長く，このことがポリオール生成能の差に反映していると推定された．一方，エリスリトール生成を担うペントースリン酸経路 (PPP) には，2，3個の相同遺伝子をもつことが判明した．特に，解糖系とPPPとの共役部位に位置し，エリスリトール生成に重要な役割を果たすtransketolase遺伝子とtransaldolase遺伝子にはER遺伝子と同様，複数の相同遺伝子が存在し，ストレス応答転写因子結合領域であるSTRE 配列を有していた．それら相同遺伝子の発現動態は浸透圧 (NaCl) や酸化 (menadione) などのストレスによって異なるが，エリスリトール生成量とは相関性を示した．また，浸透圧剤 (NaCl，グルコース，ソルビトール) の種類により，細胞内ポリオールの生成比が変化することがわかった．

Viscosimetric Study of Andiroba Oil-based Polyols (Carapa Guianensis Aubl)

Natural bases and alternative easy degradability have been employed in the petrochemical industry for polymer formulation, paints, foams, detergents, lubricating oils and especially, due to its viscous characteristics. The great advantage of renewable raw materials to replace fossil products prompted the study of viscosity of andiroba oil ( Carapa guianensis Aubl.) after chemical modifications. The oil was characterized by the acid number, kinematic viscosity, saponification value, moisture content, iodine index, peroxide index, oxidative stability, hydroxyl number and density, and then subjected to chemical modifications (alkaline ethyl transesterification and hydroxylation in situ). The production of andiroba polyols was optimized using factorial design, based on the reduction in the degree of unsaturation, monitored mainly by the increase in kinematic viscosity. The study of the conversion process was effective for the synthesis of polyols in different viscosity ranges, indicating the best conditions for obtaining polyols having flow characteristics compatible with commercial lubricants. DOI: 10.5935/1984-6835.20160067

A Study on Environmental Assessment of Residue from Gasification of Polyurethane Waste in E-Waste Recycling Process

With expanding economic growth, the consumption and changing period of electronics products have increased rapidly in last couple of decades in Korea. A refrigerator generally contains 10% of polyurethane. Since the amount of used refrigerators collected at recycling facilities of E-wastes (electronic waste) has increased since 2007, the generation of polyurethane waste has also increased. Polyurethane recycling technologies have been investigated for polyol production and sound-absorbing materials, which are not commercialized yet due to high cost of the technology. However many kinds of plastic wastes are being used as SRF (solid refuse fuel) like RDF (refuse derived fuel), so polyurethane in E-waste could be utilized as valuable fuels, since it has high calorific values and contains low sulfur, low chlorine, and less hazardous substances[Park, C. S. (2013).]. Using a fixed bed reactor, gasification experiment was conducted onpellet type SRF made of polyurethane at 1,000 °C temperature for study purpose. Environmental assessment on gasification residue was also performed byleaching test and the loss on ignition[Kim, C. S., 2008]. The main objective of this experiment was to assess whether polyurethane gasification residue is hazardous for environment or not and also to find out it is recyclable or not.

Selectivity-Switchable Conversion of Cellulose to Glycols over Ni–Sn Catalysts

The direct hydrogenolysis of cellulose represents an attractive and promising route for green polyol production. Designing a catalyst system that could control the selectivity of polyols of this process is highly desirable. In this work, we realized the selectivity-switchable production of ethylene glycol (EG) and 1,2-propylene glycol (1,2-PG) by using Sn species with different valences in combination with Ni catalysts. The combination of Ni/AC and metallic Sn powders exhibited a superior activity toward EG (57.6%) with up to 86.6% total polyol yield, while the combination of Ni/AC and SnO favored the formation of 1,2-PG (32.2%) with a 22.9% yield of EG. The Sn species in NiSn alloy in situ formed from metallic Ni and Sn powders was found to be the active sites for the high selectivity of EG as evidenced by control experiments and characterizations including X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy dispersive X-ray mapping, and 119Sn Mos...

Kinetic insight into the effect of the catalytic functions on selective conversion of cellulose to polyols on carbon-supported WO3 and Ru catalysts

Efficient conversion of cellulose, the most abundant biomass on Earth, to chemicals in high yields remains a formidable challenge. Here, we report the marked change in the distribution of polyol products in the cellulose reaction on Ru/C and WO3/C, strongly depending on the competitive reactions of the glucose intermediate. WO3 crystallites not only promote, as a solid acid, the efficient hydrolysis of cellulose to glucose, but also catalyze the selective cleavage of the C–C bonds in glucose and other C6 sugar intermediates, leading to the formation of ethylene glycol and propylene glycol, in competition with the sugar hydrogenation to the corresponding C6 polyols (e.g. sorbitol) on Ru/C. The basic C support, behaving similar to other solid bases (i.e. MgO), catalyzes the isomerization of glucose into fructose, leading to the favored formation of propylene glycol instead of ethylene glycol. Such strong dependence of the product distribution on the catalytic functions is clarified by the kinetic analysis of the three competitive reactions of glucose, including its hydrogenation, isomerization and C–C bond cleavage. Importantly, such kinetic analysis can predict the maximum selectivity ratio of propylene glycol to ethylene glycol, which is 2.5, for example, at 478K under the reaction conditions in this work, corresponding to a maximum yield of propylene glycol of ∼71%. These understandings shed new insights into the selective conversion of cellulose, which provides guidance for the rational design of catalyst functions and tuning of reaction parameters towards the controllable synthesis of specific products from cellulose.

Study on a Fixed Bed Gasification of Polyurethane SRF from Electronic Waste

With expanding economic growth, the consumption and changing period of electronics products have increased rapidly last a couple of decades in Korea. A refrigerator generally contains 10% of polyurethane. Since the amount of used refrigerators collected at recycling facilities of E-wastes has increased since 2007, the generation of polyurethane waste has also increased. Polyurethane recycling technologies have been investigated such as polyol production and sound-absorbing materials, which are not commercialized yet due to high cost of the technology. However many kinds of plastic wastes are being used as solid refuse fuel (SRF) like RDF, so polyurethane in E-waste could be utilized as valuable fuels, since it has higher heating values and contains low sulfur, low chlorine, and less hazardous substances. In this study an attempt to fabricate pellet type of SRF from polyurethane waste was conducted to use them as fuels even though it was not easy to make pellet, because characteristics of polyurethane were high volume and low density. Recently, Korean Association of Electronics Environment (KAEE) is producing pelletized SRF. The basic characteristics of polyurethane such as elemental composition, thermal properties and proximate analysis were carried out to assess whether they could be used as fuels or not. Using a fixed bed test reactor, gasification experiments were also conducted at the temperature of 1,000 ℃ by measuring exhaust gas compositions and gas pollutants.

폐 우레탄 재생 폴리올과 신재 폴리올의 전과정 환경영향 비교에 관한 연구

A life cycle assessment (LCA) methodology was employed to evaluate environmental impact of recycled polyol from polyurethane in an R&D stage and to suggest future direction for improvement of environmental performance of the recycling technology. The comparison result shows between recycled polyol in the developing stage and in the anticipated mass production with virgin polyol production that environmental impact of recycled polyol of the developing stage and the anticipated mass production level correspond to 93%, 60% of that of virgin polyol, respectively. The LCA result identifies improvement areas of reducing environmental impact in recycling polyols, that is, use of alkylene oxide and steam. In the future research, this must be taken into consideration for better performance of recycling technology.

Design and analysis of a second and third generation biorefinery: The case of castorbean and microalgae

In this work, a biorefinery system including castor bean seeds and microalgae is used as a case study to evaluate the integration of second and third generation biorefineries. A biorefinery concept was applied for the combined production of polyol, ethylene-glycol, omega-3 acid, biodiesel, methanol and heat and power from castor bean and microalgae. Castor bean cake and microalgae paste were used to feed a biomass-fired system (BIGCC), where part of CO2 produced in flue gas is captured and employed as substrate for microalgae growth. To evaluate the performance of this biorefinery concept three scenarios based on different levels of mass and energy integration were modeled and assessed from techno-economic and environmental points of view. The scenario with the best economic and environmental performances was the one including full mass integration, full heat integration, and cogeneration scheme.

Identification of molecular species of polyol oils produced from soybean oil by Pseudomonas aeruginosa E03-12 NRRL B-59991

Abstract The objective of this study is to identify the chemical species of the polyol oil products produced from soybean oil by Pseudomonas aeruginosa E03-12 NRRL B-59991. We reported earlier the polyol products produced from soybean oil by Acinetobacter haemolyticus A01-35 (NRRL B-59985) ( Hou and Lin, 2013 ). The polyol oil produced by strain A01-35 were a mixture of 57 molecular species of DAG containing tri-, di-, mono-hydroxy FA and normal FA. In this study, tricaprylin was selected as internal standard for HPLC quantitative estimation of products. A CombiFlash chromatographic method was established for separation of the polyol oil products. The molecular species of the polyol oils produced from soybean oil by strain E03-12 were identified with HPLC/MS. We identified 41 derivatives of DAG, among them 32 molecular species containing one hydroxy FA and one normal FA, 8 molecular species containing two hydroxy FA without normal FA, and one molecular specie containing two normal FA without hydroxylated FA. The hydroxy FA included mono-, di- and tri-hydroxy FA. Eight molecular species of DAG containing one trihydroxy FA and 14 molecular species of DAG containing one dihydroxy FA. We have also identified 64 molecular species of TAG, among them 13 molecular species containing two hydroxy FA, 42 molecular species containing one hydroxy FA and 9 molecular species containing no hydroxylated FA. This is different from our previous findings with A. haemolyticus A01-35 which produced only DAG polyol oils. E03-12 is a better strain for developing into an industrial bioprocess.

Production of C2 and C3 polyols from d-sorbitol over hydrotalcite-like compounds mediated bi-functional Ni–Mg–Al–Ox catalysts

Production of C2 and C3 polyols from d-sorbitol over Ni/MgxAlyOx+1.5y catalysts with different Mg/Al molar ratio were performed under mild conditions. It was found that this reaction proceeded effectively over these bi-functional catalysts prepared via thermal decomposition and reduction of Ni–Mg–Al hydrotalcite-like compounds. The detected conversion of d-sorbitol over Ni/Mg1.29Al0.06O1.38 reached 80.7% at 453K and further increased to 97.0% at 473K. Characterizations indicate that the performance of these catalysts depended mainly on its surface basicity.

Bio-based foam for thermal insulation. Valorisation of CNSL (cashew nut shell liquid)

Everyone now knows that the building industry accounts for 43% of energy consumption and 25% of greenhouse gas emissions. It thus constitutes one of the key objectives in the pursuit of the Factor 4 issues in 2050. The thermal insulation defects of buildings and mistreatment of airtightness problems are the main causes low energy performance of the built French park. The fight against energy waste therefore passes deals with the thermal insulation of heated buildings. The thermal insulation performances are firstly determined by their thermal conductivity and the physical quantity characterizing the behaviour of materials during the heat transfer by conduction. With an average thermal conductivity of 0.023 W/m.K, polyurethane foam remains very good for building insulation. The advantage of this material therefore results in a gain of living space. Indeed for a given heat resistance, the thickness of material required is lower than for the homologous. However, PU foams are generally expensive especially because of the presence of fossil compounds as well as adverse effects on the environment and health (discharge of volatile organic compounds VOCs). In 2007, the French chemical industry is committed to use by 2017, 15% of bio based raw materials and diversify its industrial resources used (agricultural resources, especially non-food processes, and lignocellulosic waste and coproducts). However, only 8% of raw materials of the French chemical industry are renewable. Polyurethane foams are generally composed of two main compounds: Polyols, and isocyanate, the both from fossils resources. There is today part of a solution dealing with bio polyols from rape seed oils, but in most of case too much expensive for this industry. CNSL (Cashew Nut Shell Liquid) is a co-product of cashew nut exploitation. It is a kind of vegetal oil mainly composed of anacardic Acid and cardanol. This oil may be a very performant and low coast raw material ($ 300/ton) for polyol production to substitute fossil polyols in Polyurethane composition. CoDEM is today developing new bio based expanded foam with CNSL to reach a target thermal conductivity near 0,025 W/m.K This communication may explains the first part of our works substituting polyols and first results measured in our laboratory.

One-pot catalytic production of polyols from cellulose

Because of decreasing crude-oil reserves, and increasing concerns regarding global climate change and higher energy demands, focus has recently turned to the exploration of new renewable alternatives to fossil feedstocks for the production of energy fuels and chemicals. Recently, biomass has attracted much attention and been rapidly developed because it is readily available, cheap, and carbon neutral. In particular, the catalytic production of polyols from biomass and its derived compounds has become the subject of global research. Polyols, which are important industrial raw materials, are widely used for the production of hydrogen, liquid fuels, and chemicals. Cellulose, the most abundant source of biomass in nature, can be catalytically converted to polyols. This review summarizes and comments on recent advances in cellulose upgrading for the production of polyols (sorbitol, isosorbide, ethylene glycol, and 1,2-propylene glycol); it also outlines the challenges in this field, and our research work.

English

An investigation on a batch production of palm kernel oil polyol (PKO-p) was conducted via esterification and condensation. The process design was thoroughly studied as a preliminary step for future upscaling. The process variables included necessity of vacuum pump, controlling of heating rate, recording the production time, nitrogen gas flow and agitator speed. About 250 mL PKO-p was successfully synthesized within 3 h. Vacuum pressure was applied to haul out moisture from the system. The control of heating rate and production time are vital to avoid sudden oxidation.

Dow successfully starts up a key facility for production of polyether polyols in Thailand

Methods have been developed and compared for the analysis of a glycerol-based polyether polyol using a low-field, medium-resolution NMR spectrometer, with an operating frequency of 29 MHz for 1H. Signal areas in the time and frequency domains were used to calculate the ethylene oxide (EO) content of individual samples. The time domain signals (free induction decay) were analysed using a new version of the direct exponential curve resolution algorithm (FID-DECRA). Direct analysis of the 1H NMR FT spectra gave percentage EO concentrations of reasonable accuracy (average percentage error of 1.3%) and precision (average RSD of 1.8%) when compared with results derived from high-field 13C NMR spectrometry. The direct FID-DECRA method showed a negative bias (−0.8±0.12% w/w) in the estimation of percentage EO concentration, but the precision (average RSD of 0.9%) was twice as good as that of direct spectral analysis. When the 13C NMR analysis was used as a reference method for univariate calibration of the 1H NMR procedures, the best accuracy (average percentage error of 0.5%) and precision (average RSD of 0.6%) were obtained using FID-DECRA, for EO concentrations in the range 14.8–15.5% w/w. An additional advantage of FID-DECRA is that the analytical procedure could be automated, which is particularly desirable for process analysis.

Genetic and Environmental Effects on Fatty Acid Composition in Soybeans with Potential Use in the Automotive Industry

ABSTRACTEnvironmental effects on quantitative traits such as seed oil fatty acid composition in soybean [Glycine max (L.) Merrill] can significantly affect the performance of a given genotype when exposed to varying growing conditions. High linoleic acid oils have the potential to be used as raw materials for the production of polyols and polyurethane that can be used in the automotive industry. The objectives of this study were (i) to determine the sources of variation affecting seed oil fatty acids profiles and (ii) to evaluate stability of soybean genotypes with different fatty acids across different environments. Fifty‐six soybean genotypes with altered fatty acid composition selected from two recombinant inbred line populations segregating for saturated and linoleic acids were used along with commercial high yielding cultivars. All genotypes were evaluated in southwestern Ontario, Canada, at three locations in 2008 and two locations in 2009, and data was collected for fatty acid composition as well as other seed and agronomic traits. Combined analysis of variances showed significant location and genotype × location effects for stearic and oleic acids. Genotype × environment effect was significant for unsaturated fatty acids plus seed oil and protein concentrations. The effect of genotype × year was significant for unsaturated fatty acids. Stability analyses using Francis and Kannenberg's mean coefficient of variation stability, Shukla's stability variance statistic (σ2), and Lin and Binns cultivar superiority measure identified genotypes E‐49 and E‐14 as being superior for high linoleic and low saturated fatty acids oil production for potential use in the automotive industry.

Adding Value to Power Station Captured CO2: Tolerant Zn and Mg Homogeneous Catalysts for Polycarbonate Polyol Production

Using captured waste carbon dioxide (CCU) as a chemical reagent is an attractive means to add value to carbon capture and storage (CCS) and is a high-priority target for manufacturing. One promising route is to copolymerize carbon dioxide and epoxides, to prepare aliphatic polycarbonates. In this study, three homogeneous dinuclear Zn and Mg catalysts, previously reported by our group (see Kember, M. R.; Knight, P. D.; Reung, P. T. R.; Williams, C. K Angew. Chem., Int. Ed. 2009, 48, 931–933 and Kember, M. R.; Williams, C. K. J. Am. Chem. Soc. 2012, 134, 15676–15679) have been investigated using captured and contaminated carbon dioxide, with cyclohexene oxide, to produce polymers. Carbon dioxide captured from the carbon capture demonstrator plant at Ferrybridge Power Station, U.K., is applied for the efficient production of poly(cyclohexylene carbonate). Remarkably, the dinuclear Zn and Mg catalysts display nearly equivalent turnover numbers (TON) and turnover frequencies (TOF) using captured CO2 versus tho...

Structure, Activity, and Deactivation Mechanisms in Double Metal Cyanide Catalysts for the Production of Polyols

AbstractPolyether polyols are used widely in the plastic and coating industries in the form of polyurethanes. The polymerization of epoxides can be catalyzed by double metal cyanides (DMCs), Zn3[Co(CN)6]2. These catalysts were first reported in the 1960s by General Tire Inc. and provide products with excellent technical features, which are better than those that result from traditional alkaline polymerization as side reactions are alleviated. However, DMC‐catalyzed polymerization is not free of drawbacks as high‐molecular‐weight side products (1–3 wt %) can form in the propylene process. These tails are detrimental to the subsequent use of these polymers, in particular to foam stability. Despite the wide industrial interest in DMCs, there are only a few experimental studies and a complete lack of theoretical research of their structure, activity, and performance. The present work is thus the first attempt to describe the nature of the active site, the main polymerization mechanism, and two potential origins for the high‐weight tails from a theoretical standpoint by analyzing three crucial steps in the polymerization process.

ChemInform Abstract: Recent Advances in the Production of Polyols from Lignocellulosic Biomass and Biomass‐Derived Compounds

AbstractReview: 136 refs.