Identification of potential technologies for 1,4-Butanediol production using prospecting methodology

1,4-Butanediol (1,4-BDO) is a four-carbon diol used for industrial applications such as organic solvents, and the production of adhesives, fibers and polyurethanes. 1,4-BDO currently is produced through several petrochemical routes: hydrogenation of maleic anhydride, isomerization of propylene oxide, acetoxylation of butadiene, and the reaction between formaldehyde and acetylene. The current trends in 1,4-BDO production involve the utilization of renewable sources such as biomass. In this context, the present study aimed to identify promising technologies of 1,4-BDO production through prospecting methodology based on the analyses of patents and scientific article, describing the most relevant aspects of those emerging technologies. An increasing amount of 1,4-BDO production focused on biotechnological routes has been reported, with the US heavily involved in the development of new technologies. This study tracked three promising technologies which have potential for application in a biorefinery context because those processes involve (i) production of 1,4-BDO from sugars, classified herein as the biotechnological route; (ii) production of intermediates from sugar fermentation followed by catalytic conversion into 1,4-BDO, classified herein as the hybrid route, and (iii) furan/furfural conversion into 1,4-BDO. © 2020 Society of Chemical Industry     

Synthesis and evaluation of the thermal properties of biosourced poly(ether)ureas and copoly(ether)ureas from 1,4:3,6‐dianhydrohexitols

A new series of poly(ether)ureas were prepared by solution polyaddition of three diamines based on 1,4:3,6‐dianhydrohexitols with three types of diisocyanate. The corresponding poly(ether)ureas were obtained with high yields. They were characterized by various analytical techniques (NMR, TGA and differential thermal analysis, DSC). NMR spectroscopy allowed us to confirm structure type and to optimize reaction conditions and DSC proved the high thermal properties of the products obtained (T_g and T_m in the range 126 ? 158 °C and 235 ? 330 °C respectively). Then, copoly(ether)ureas partially based on commercial diamines were synthesized in order to reduce polymer cost and tune their thermal behaviour. The reactivity of both diamines was evaluated by their incorporation in the polymer by means of NMR spectra. Then their thermal properties were compared with fully commercial diamine based polyureas by DSC studies. © 2014 Society of Chemical Industry     

Selective Hydrogenation of Biomass-Derived Succinic Acid: Reaction Network and Kinetics

The conversion of bio-based succinic acid (SA) to the value-added chemicals 1,4-butanediol (BDO), γ-butyrolactone (GBL), and tetrahydrofuran (THF) can replace the corresponding petrochemical production routes to achieve a sustainable process. The reaction network for aqueous-phase catalytic hydrogenation of succinic acid over a supported Re-Pd catalyst was identified and the reaction kinetics was determined. With the developed kinetic model, the composition of the product mixture regarding the desired products (BDO, GBL, THF) can be described as a function of educt concentration, temperature, and pressure. The maximum BDO yield was achieved at high pressure and low temperature, while low pressure and high temperature favored GBL and THF production.     

Three-dimensional layered porous graphene aerogel hydrogen getters

Organic getters are often introduced into sealed systems to remove the excessive reactive hydrogen gas. In this work, the formable graphene aerogel hydrogen getters are prepared by integrating the alkyne-containing molecules (e.g., DEB) into the palladium-loaded three-dimensional layered porous graphene aerogel (Pd-GA). The performance of Pd-GA/DEB composite materials in reducing reactive hydrogen gas is examined at pressures of 0.1–1 bar at a temperature of 25 °C, and the hydrogen consumption is measured as a function of time. Results suggest that the hydrogen uptake capability of Pd-GA/DEB getters increases with the loading of Pd particles on the GA and the content of Pd⁰. The highest hydrogen absorption capacity is up to 215.5 cm³/g, and the hydrogenation rate of DEB molecules is 89.3%. This study promotes the fundamental understanding of solid-phase catalytic hydrogenation and the applications of 3D layered porous graphene aerogel in hydrogen absorption.     

Investigation on sulphonated zinc oxide nanorod incorporated sulphonated poly (1,4-phenylene ether ether sulfone) nanocomposite membranes for improved performance of microbial fuel cell

Hydrothermally prepared zinc oxide nanorods are sulphonated (S–ZnO NR) and incorporated into 15% Sulphonated Poly (1,4-Phenylene Ether Ether Sulfone) (SPEES) to improve the hydrophilicity, water uptake and ion transfer capacity. Water uptake and ion transfer capacity increased to 34.6 ± 0.6% and 2.0 ± 0.05 meq g^?1 from 29.8 ± 0.3% and 1.4 ± 0.04 meq g^?1 by adding 7.5 wt% S–ZnO NR to SPEES. Morphological studies show the prepared S–ZnO NR is well dispersed in the polymer matrix. SPEES +7.5 wt% S–ZnO NR membrane exhibits optimum performance after three-weeks of continual operation in a fabricated microbial fuel cell (MFC) to produce a maximum power density of 142 ± 1.2 mW m^?2 with a reduced biofilm compared to plain SPEES (59 ± 0.8 mW m^?2), unsulphonated filler incorporated SPEES (SPEES + 7.5 wt% ZnO, 68 ± 1.1 mW m^?2) and Nafion (130 ± 1.5 mW m^?2) thereby suggesting its suitability as a sustainable and improved cation exchange membrane (CEM) for MFCs.     

A study on the relationship between biodegradability enhancement and oxidation of 1,4-dioxane using ozone and hydrogen peroxide

Advanced oxidation involving O₃/H₂O₂ was used to eliminate 1,4-dioxane and to enhance the biodegradability of dioxane-contaminated water. Oxidation experiments were carried out in a bubble column reactor operating in fed-batch. The rate of dioxane removal and enhancement in biodegradability was investigated at hydrogen peroxide to ozone ratios between 0 and 0.6 mol:mol and pH between 5 and 11. A theoretical model was also applied to predict the experimental data and to investigate the effects of dioxane concentration, pH, and H₂O₂ concentration. The model predictions fit the experimental data well and there was a linear correlation between dioxane oxidation and BOD enhancement. At low dioxane concentrations, the oxidation rate was first order and it gradually approached zero order with increasing dioxane concentration. Also, the biodegradability of the solution increased with pH up to about 9 and it stayed constant with further pH increase. Hydrogen peroxide initially enhanced dioxane removal and biodegradability enhancement of the solution. However, at H₂O₂:O₃ ratios greater than about 0.4-0.45 mol:mol, i.e. about 2.90 mM for H₂O₂ concentration, H₂O₂ had negative impacts and resulted in reduced dioxane removal and biodegradability increase.     

2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯的合成、晶形控制及其与HTPB推进剂组份的相容性

以2-羟甲基-2-硝基-1,3-丙二醇为起始原料,通过缩酮反应、氧化偶联反应、水解反应、硝化反应四步反应合成出了2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯(SMX),并采用红外光谱、元素分析及核磁共振谱进行了结构表征。采用Materials Studio Modeling软件中的Growth Morphology方法模拟了SMX晶体的生长形态和结晶习性,分析了重要构晶晶面的表面结构特征,研究了溶剂效应对晶体形貌的影响。采用乙酸乙酯/石油醚混合液对SMX进行重结晶实验。通过DSC法研究了SMX与端羟基聚丁二烯(HTPB)推进剂组份:HTPB、高氯酸铵(AP)、铝(Al)粉、奥克托今(HMX)、黑索今(RDX)和甲苯二异氰酸酯(TDI)的相容性。结果表明,乙酸乙酯/石油醚结晶体系可改善产品的晶体形貌,理论预测与实验结果相符。SMX与HMX、RDX、Al粉相容性较好,与AP轻微敏感,与HTPB和TDI不相容。     

Synthesis, Thermal Stability and Sensitivity of 2, 4-Dinitroimidazole

Pursuing new insensitive high explosive (IHE) is the main research hot-point in explosive field. Nitroimidazole compounds were mainly studied in the medicine chemistry in the past[1-2], seldom seen as the components of explosives and propellants. But now, several nitroimidazole compounds, such as 2, 4-dinitroimidazole (2, 4-DNI), 2, 4, 5-trinitroimidazole (2, 4, 5-TNI) and 1-methyl-2, 4, 5-trinitroimidazole (MTNI) etc are found to be the important intermediates of synthesizing new high explosives or itself possessing excellent explosive performances[3-5]. This paper introduces the synthesis, especially the experimental thermal stability, sensitivity and security of 2, 4-dinitroimidazole (2, 4-DNI).