Raffaele Cucciniello

A simplified early stage assessment of process intensification: glycidol as a value-added product from epichlorohydrin industry wastes

The present work deals with the production of glycidol through a new synthetic approach based on the conversion of 2-chloro-1,3-propanediol (β-MCH), a by-product in the epichlorohydrin production plant. β-MCH was converted with high yield (90%) and selectivity (99%) to glycidol using an alcoholic solution of KOH at room temperature in only 30 minutes. A simplified early stage assessment based on the use of the green metrics and a life cycle analysis were adopted in order to evaluate the environmental feasibility of this innovative route if compared with the traditional chain to epichlorohydrin. The waste recovery and the maximization of the overall process efficiency lead to sensible reductions per each indicator considered in the assessment, suggesting the possibility of developing on a full industrial scale. In addition, in order to verify the potentialities behind the substitution of the fossil-based glycidol with the product resulted from the recovery of the β-MCH, a cradle-to-gate analysis and the GREENMOTION® tool were adopted.

Glycidol, a Valuable Substrate for the Synthesis of Monoalkyl Glyceryl Ethers: A Simplified Life Cycle Approach

The disposal of any waste by recovering it within the production plant represents the ultimate goal of every biorefinery. In this scenario, the selective preparation of monoalkyl glyceryl ethers (MAGEs) starting from glycidol, obtained as byproduct in the epichlorohydrin production plant, represents a very promising strategy. Here, we report the synthesis of MAGEs through the reaction of glycidol with alcohols catalyzed by a green homogeneous Lewis acids catalyst, such as BiIII triflate, under very mild reaction conditions. To evaluate the green potential of the proposed alternative, a simplified life cycle assessment (LCA) approach was followed by comparing the environmental performance of the proposed innovative route to prepare MAGEs with that of the most investigated pathway from glycerol. A considerable reduction of all impact categories considered was observed in our experimental conditions, suggesting that the glycidol-to-MAGEs route can be a valuable integration to the glycerol-to-MAGEs chain. Thanks to the use of primary data within the LCA model, the results achieved are a very good approximation of the real case.

Synthesis of Monoalkyl Glyceryl Ethers by Ring Opening of Glycidol with Alcohols in the Presence of Lewis Acids

The present work deals with the production of monoalkyl glyceryl ethers (MAGEs) through a new reaction pathway based on the reaction of glycidol and alcohols catalyzed by Lewis acid-based catalysts. Glycidol is quantitatively converted with high selectivity (99 %) into MAGEs under very mild reaction conditions (80 °C and 0.01 mol % catalyst loading) in only 1 h using Al(OTf)3 or Bi(OTf)3 as catalyst. The proposed method enhances the choice of possible green synthetic approaches for the production of value-added products such as MAGEs.

An improved method for BTEX extraction from charcoal

In this paper we propose a simple procedure for the extraction of BTEX (benzene, toluene, ethylbenzene and xylenes) from activated charcoal. For this purpose synthetic samples were prepared in a laboratory and real samples were collected in a polluted environment using passive sampling. The proposed extraction procedure is based on the use of an appositely designed Soxhlet apparatus, dimensions of which are as small as the cartridge of the passive samplers, in order to accommodate this latter and permit us to use a small amount of solvent. The selection of the solvent was based on the strong desire to substitute carbon disulfide, which is by far the solvent of choice, with a less hazardous substance in order to enhance operator protection. Among the solvents tested the best results were obtained by using dichloromethane that, under optimized conditions, led to a complete recovery (>97%) of each analyte (BTEX), both in the synthetic and the real samples. The extraction procedure with CH2Cl2 in the Soxhlet lasted for about 20 minutes which also resulted in a reduced operating time.

First Attempt of Glycidol-to-Monoalkyl Glyceryl Ethers Conversion by Acid Heterogeneous Catalysis: Synthesis and Simplified Sustainability Assessment

The selective preparation of monoalkylglyceryl ethers (MAGEs) is a task for researchers owing to their broad range of applications. In this work, green feedstocks such as glycidol and alcohols were used to prepare MAGEs under mild reaction conditions (80 °C, 3 h, 0.5 mol % catalyst) in the presence of acid heterogeneous catalysts. Nafion shows the best performances in terms of conversion and selectivity to MAGES and also high stability. A comparison of the environmental performances with the most consolidated pathway from glycerol has shown that the usage of glycidol (recovered as a value-added product from Epicerol process) and Nafion leads to a lower impact on ecosystems. In addition, results achieved from a simplified socio-economic analysis show that the innovative route here proposed has potential (at the laboratory scale) of enhancing potential gains and of reducing the social implications resulting from externalities associated with environmental impacts (e.g., CO2 equivalents).

A study on the applicability of zinc acetate impregnated silica substrate in the collection of hydrogen sulfide by active sampling

A novel substrate for the hydrogen sulfide determination in air was developed based on zinc acetate impregnated silica in glass tubes. Collected H2S is quantified by ion chromatography after sulfide oxidation to sulfate in an alkaline solution of H2O2. Laboratory tests were conducted in controlled atmosphere to evaluate uptake rate, linearity, sample stability, influence of relative humidity and interfering gases. A pilot study was also conducted in the field in order to assess the applicability of the substrate and to understand the effect that gases such NO2 and CH4 can have on the efficiency of collection of H2S. The new substrate has shown to have several advantages with respect to the charcoal substrate, that is the one of choice as reported by National Institute of Occupational Safety and Health (NIOSH) method. In particular it does not suffer from sulfur background and it is not influenced by interfering gases such as NO2 and CH4.

A new sorbent tube for atmospheric NOx determination by active sampling

In this paper we used hydrated mayenite as reactive substrate for NOx active sampling in the air, which is novel. The performance of the mayenite-based sorbent for the NOx tubes was evaluated in two different monitoring surveys (autumn 2015 and winter 2016), characterized by different environmental conditions. Sorbent tubes filled with mayenite were exposed simultaneously to triethanolamine (TEA)-based sorbent tubes and to a chemiluminescence detector, as reference. The comparison of the NOx concentration levels measured by active sampling, using mayenite as NOx sorbent, showed a close relationship with the chemiluminescence analyzer. The effect of the environmental conditions on the performance of both mayenite and TEA-based sorbent tubes was evaluated and limitations connected to the use of TEA were discussed.

FTIR and NDIR spectroscopies as valuable alternatives to IRMS spectrometry for the δ(13)C analysis of food.

The (13)C/(12)C carbon isotope ratio is a chemical parameter with many important applications in several scientific area and the technique of choice currently used for the δ(13)C determination is the isotope ratio mass spectrometry (IRMS). This latter is highly accurate (0.1‰) and sensitive (up to 0.01‰), but at the same time expensive and complex. The objective of this work was to assess the reliability of FTIR and NDIRS techniques for the measurement of carbon stable isotope ratio of food sample, in comparison to IRMS. IRMS, NDIRS and FTIR were used to analyze samples of food, such as oil, durum, cocoa, pasta and sugar, in order to determine the natural abundance isotopic ratio of carbon in a parallel way. The results were comparable, showing a close relationship among the three techniques. The main advantage in using FTIR and NDIRS is related to their cheapness and easy-to-operate in comparison to IRMS.

Development of a new radial passive sampling device for atmospheric NOx determination

In this paper we used Na2CO3-impregnated silica as reactive substrate for the determination of atmospheric NOx (NO+NO2) by using a passive sampling device, with radial symmetry, which is unprecedented. We conducted laboratory and field tests at an urban setting, with co-located passive samplers and continuous measurements of NOx by a chemiluminescence detector, used as reference. The performance of the carbonate-based sorbent for the NOx sampler was evaluated in two different time frames (autumn 2016 and winter 2017), characterised by different environmental conditions. The comparison of the NOx concentration levels measured by passive sampling, using Na2CO3 as NOx sorbent, showed a close relationship with those obtained by the chemiluminescence analyzer. Validation experiments in the laboratory and in the field are reported together with the calculation of the diffusion-sampling rate of the samplers.

Environmental Application of Extra-Framework Oxygen Anions in the Nano-Cages of Mayenite

Trichloroethylene (TCE) is a chlorinated volatile organic compound (CVOC), used in the last years in dry-cleaning applications and as degreasing agent. In this study we report on the catalytic oxidation of gaseous trichloroethylene (TCE), in a fixed bed reactor, performed by using mayenite (Ca12Al14O33) synthetized by using the ceramic method. Results show that mayenite promoted the total oxidation of TCE to carbon dioxide and chlorine in the temperature range 300–500 °C. The catalyst is stable under the investigated reaction conditions showing high recyclability and could be used for several reaction cycles without any loss of activity and selectivity.