Continuous Flow Upgrading of Selected C2-C6 Platform Chemicals Derived from Biomass.

The ever increasing industrial production of commodity and specialty chemicals inexorably depletes the finite primary fossil resources available on Earth. The forecast of population growth over the next 3 decades is a very strong incentive for the identification of alternative primary resources other than petro-based ones. In contrast with fossil resources, renewable biomass is a virtually inexhaustible reservoir of chemical building blocks. Shifting the current industrial paradigm from almost exclusively petro-based resources to alternative bio-based raw materials requires more than vibrant political messages; it requires a profound revision of the concepts and technologies on which industrial chemical processes rely. Only a small fraction of molecules extracted from biomass bears significant chemical and commercial potentials to be considered as ubiquitous chemical platforms upon which a new, bio-based industry can thrive. Owing to its inherent assets in terms of unique process experience, scalability, and reduced environmental footprint, flow chemistry arguably has a major role to play in this context. This review covers a selection of C2 to C6 bio-based chemical platforms with existing commercial markets including polyols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol, 1,4-butanediol, xylitol, and sorbitol), furanoids (furfural and 5-hydroxymethylfurfural) and carboxylic acids (lactic acid, succinic acid, fumaric acid, malic acid, itaconic acid, and levulinic acid). The aim of this review is to illustrate the various aspects of upgrading bio-based platform molecules toward commodity or specialty chemicals using new process concepts that fall under the umbrella of continuous flow technology and that could change the future perspectives of biorefineries.

Quantification and Variability Analysis of Lignin Optical Properties for Colour-Dependent Industrial Applications.

Lignin availability has increased significantly due to the commercialization of several processes for recovery and further development of alternatives for integration into Kraft pulp mills. Also, progress in lignin characterization, understanding of its chemistry as well as processing methods have resulted in the identification of novel lignin-based products and potential derivatives, which can serve as building block chemicals. However, all these have not led to the successful commercialization of lignin-based chemicals and materials. This is because most analyses and characterizations focus only on the technical suitability and quantify only the composition, functional groups present, size and morphology. Optical properties, such as the colour, which influences the uptake by users for diverse applications, are neither taken into consideration nor analysed. This paper investigates the quantification of lignin optical properties and how they can be influenced by process operating conditions. Lignin extraction conditions were also successfully correlated to the powder colour. About 120 lignin samples were collected and the variability of their colours quantified with the CIE L*a*b* colour space. In addition, a robust and reproducible colour measurement method was developed. This work lays the foundation for identifying chromophore molecules in lignin, as a step towards correlating the colour to the functional groups and the purity.

Components of sustainability considerations in management of petrochemical industries.

Sustainability comprises three pillars of social, environmental, and economic aspects. Petrochemical industry has a great inter-related complex impact on social and economic development of societies and adverse impact on almost all environmental aspects and resource depletion in many countries, which make sustainability a crucial issue for petrochemical industries. This study was conducted to propose components of sustainability considerations in management of petrochemical industries.A combination of exploratory study-to prepare a preliminary list of components of sustainable business in petrochemical industries based on review of literature and Delphi-to obtain experts' view on this preliminary list and provide a detailed list of components and sub-components that should be addressed to bring sustainability to petrochemical industries, were used.Two sets of components were provided. First general components, which include stakeholders (staffs, society, and environment) with four sub-components, financial resources with 11 sub-components, improvement of design and processes with nine sub-components, policy and strategy of cleaner production with seven sub-components and leadership with seven sub-components. The second operational components included raw material supply and preparation with five, synthesis with ten, product separation and refinement with nine, product handling and storage with five, emission abatement with eight, and improvement of technology and equipment with 16 sub-components.

[Evaluation of workplace air pollution with fluor compounds and their contents of biologic media in aluminium production workers].

The authors estimated fluorine compounds content of workplace air in electrolysis workshops of aluminium production, for various electrolysis technologies. The data cover results of physical and chemical analysis and material constitution of produced toxic dust complexes, urinary excretion levels of fluorine ion and fluorides accumulation in hair of aluminium production workers.

[Biologic monitoring of chlorine organic hydrocarbons in vinyl chloride and polyvinyl chloride production].

The authors presented data of chemical analytic control of chlorine compounds level in workplace air of vinyl chloride and polyvinyl chloride production, and biomonitoring results of vinyl chloride and 1.2-dichloroethane metabolite - thiodiacetic acid urinary level in workers of this production. Findings are exceeded hygienic norms on maximal concentrations of 1.2-dichloroethane in a workshop for vinyl chloride production from 1.0 to 2.85 MACs and of vinyl chloride in a workshop for polyvinyl chloride production from 2.06 to 5.52 MACs. Urinary levels of thiodiacetic acid were assessed in workers of vinyl chloride and polyvinyl chloride production in dependence on occupation, length of service and post-contact time.

[Changes in endocrine profile of workers in pulp and paper plant.]

Examination covered 245 individuals and included characteristics of endocrine state of pulp and paper plant workers over 2011-2012, in comparison with data from 1990, as well as comparison with reference groups of male workers with no contact with chemical'industry in Arkhangelsk. Findings are both in main and reference groups general decrease in levels of cortisol, thyroxin;progesterone, testosterone, insulin, somatotropin and increased serum level of estradiol. With that, inside both groups, reliable tendencies to increased levels of cortisol, thyroxin, insulin, SSH and lower concentration of progesterone in the pulp and paper plant workers vs. the reference group members. Positive tendency was absence of abnormal concentrations of insulin, SSH and lower frequency of high cortisol levels in the pulp and paper plant workers nowadays.

New technologies reduce greenhouse gas emissions from nitrogenous fertilizer in China.

Synthetic nitrogen (N) fertilizer has played a key role in enhancing food production and keeping half of the world's population adequately fed. However, decades of N fertilizer overuse in many parts of the world have contributed to soil, water, and air pollution; reducing excessive N losses and emissions is a central environmental challenge in the 21st century. China's participation is essential to global efforts in reducing N-related greenhouse gas (GHG) emissions because China is the largest producer and consumer of fertilizer N. To evaluate the impact of China's use of N fertilizer, we quantify the carbon footprint of China's N fertilizer production and consumption chain using life cycle analysis. For every ton of N fertilizer manufactured and used, 13.5 tons of CO2-equivalent (eq) (t CO2-eq) is emitted, compared with 9.7 t CO2-eq in Europe. Emissions in China tripled from 1980 [131 terrogram (Tg) of CO2-eq (Tg CO2-eq)] to 2010 (452 Tg CO2-eq). N fertilizer-related emissions constitute about 7% of GHG emissions from the entire Chinese economy and exceed soil carbon gain resulting from N fertilizer use by several-fold. We identified potential emission reductions by comparing prevailing technologies and management practices in China with more advanced options worldwide. Mitigation opportunities include improving methane recovery during coal mining, enhancing energy efficiency in fertilizer manufacture, and minimizing N overuse in field-level crop production. We find that use of advanced technologies could cut N fertilizer-related emissions by 20-63%, amounting to 102-357 Tg CO2-eq annually. Such reduction would decrease China's total GHG emissions by 2-6%, which is significant on a global scale.

Life cycle assessment of carbon capture and utilization from ammonia process in Mexico.

Post-combustion CO2 capture (PCC) of flue gas from an ammonia plant (AP) and the environmental performance of the carbon capture utilization (CCU) technology for greenhouse gas (GHG) emissions to an enhanced oil recovery (EOR) system in Mexico was performed as case study. The process simulations (PS) and life cycle assessment (LCA) were used as supporting tools to quantify the CO2 capture and their environmental impacts, respectively. Two scenarios were considered: 1) the AP with its shift and CO2 removal unit and 2) Scenario 1 plus PCC of the flue gas from the AP primary reformer (AP-2CO2) and the global warming (GW) impact. Also, the GW of the whole of a CO2-EOR project, from these two streams of captured CO2, was evaluated. Results show that 372,426 tCO2/year can be PCC from the flue gas of the primary reformer and 480,000 tons/y of capacity from the AP. The energy requirement for solvent regeneration is estimated to be 2.8 MJ/kgCO2 or a GW impact of 0.22 kgCO2e/kgCO2 captured. GW performances are 297.6 kgCO2e emitted/barrel (bbl) for scenario one, and 106.5 kgCO2e emitted/bbl for the second. The net emissions, in scenario one, were 0.52 tCO2e/bbl and 0.33 tCO2e/bbl in scenario two. Based on PS, this study could be used to evaluate the potential of CO2 capture of 4080 t/d of 4 ammonia plants. The integration of PS-LCA to a PCC study allows the applicability as methodological framework for the development of a cluster of projects in which of CO2 could be recycled back to fuel, chemical, petrochemical products or for enhanced oil recovery (EOR). With AP-2CO2, "CO2 emission free" ammonia production could be achieved.

Copper and cobalt recovery from pyrite ashes of a sulphuric acid plant.

The pyrite ashes formed as waste material during the calcination of concentrated pyrite ore used for producing sulphuric acid not only has a high iron content but also contains economically valuable metals. These wastes, which are currently landfilled or dumped into the sea, cause serious land and environmental pollution problems owing to the release of acids and toxic substances. In this study, physical (sulphation roasting) and hydrometallurgical methods were evaluated for their efficacy to recover non-iron metals with a high content in the pyrite ashes and to prevent pollution thereby. The preliminary enrichment tests performed via sulphation roasting were conducted at different roasting temperatures and with different acid amounts. The leaching tests investigated the impact of the variables, including different solvents, acid concentrations and leach temperatures on the copper and cobalt leaching efficiency. The experimental studies indicated that the pre-enrichment via sulphation roasting method has an effect on the leaching efficiencies of copper and cobalt, and that approximate recoveries of 80% copper and 70% cobalt were achieved in the H2O2-added H2SO4 leaching tests.

[Hygienic assessment of toxic dust factor at the aluminium smelter in Eastern Siberia].

There is presented the assessment of priority toxic matters in the air of working zone for basic occupations of aluminum smelting by electrolysis. There are presented results of different production technologies. There are presented the results of the physical-chemical analysis of the morphology and composition of produced toxic-dust complexes.

[The evaluation of immunoregulatory markers in the course of neurointoxication by mercury over the post-exposure period].

There was executed the examination of patients with occupational chronic mercury intoxication in the post-exposure period after the exposure to metallic mercury vapor. 47 persons with an established diagnosis of chronic mercury intoxication (HMI) passed the laboratory and immunological examination in the period of exposure to metallic mercury vapor in a production environment. The average age of men accounted for 49.2±1.2 years. The experience of work in hazardous working conditions amounted of 21.65±1.61 years (1 observation). All these same cases were observed in the institute clinic again after 5 years (2 observation) and 10 years (3 observation). A control group of healthy men consisted of 47 cases included persons of representative both age and general work experience, without a professional route of contact with hazardous substances. The level of such cytokines as IL-1ß, IL-2, IL-4, IL-6, TNF-a, INF-y and neurotropic IgG class antibodies directed to proteins of the nervous tissue (NF-200, GFAP, MBP, B-dependent Ca-channel, Glu-R, DA-R, R-GABA, Ser-R, R-Chol, DNA, B2GP) in serum were determined by enzyme linked immunosorbent assay. There was established the gain in the imbalance of inflammatory mediators and production ofneural antibodies in dynamics after the termination of the production in conditions of metallic mercury vapors. Revealed features of the regulatory relationship between the level of cytokines and the severity of the autoimmune process were shown to contribute to the maintenance and progression of neurodegenerative processes. There was recommended the identification of immunoregulatory markers (IL-1ß, IL-4, TNF-a, NF-AT to 200, GFAP, S-100) as an additional criteria for the diagnosis of health disorders in operating and monitoring the course of the progredient professional mercury intoxication.

[Clinical, biochemical and allergological indices characterizing occupational diseases of the bronchial and pulmonary system in employees at aluminium production].

There are many harmful factors that possess a damaging impact on the body of employees at aluminum production. It leads to the development of bronchial asthma (BA), chronic nonobstructive bronchitis (CNB) and chronic obstructive pulmonary disease (COPD). The pathogenesis of these disorders, as well as sensitizing effect offluorine in the aluminum production is not fully understood. The purpose of this work was to study the characteristics of laboratory indices in patients with occupational diseases of the respiratory system. In workers of aluminum production with the diagnosis of occupational diseases of respiratory system (15 patients with a diagnosis of asthma, 30 CNB cases, 20 COPD patients) we evaluated the content of total protein, total cholesterol, high density lipoprotein cholesterol (HDLC), total calcium, phosphorus, ceruloplasmin, hematological indices and performed emigration of leukocytes braking test (TTEEL). Clinical and biochemical profile ofpersons with occupational asthma was characterized by a low level of total calcium and ceruloplasmin, a high concentration of phosphorus in the blood serum and inhibition of leukocyte emigration in the test with sodium fluoride. For aluminum production CNB workers characteristic active proatherogenic process was pronounced by a decrease in the HDLC level and an increase in atherogenic index; higher hematocrit value and concentration of erythrocytes, and more than 50% of cases of sensitization to the presence of sodium fluoride. COPD cases had occupational lower average concentration of hemoglobin in the erythrocyte, total protein in serum, as well as polymorphic variant response to sodium fluoride in the form of a depression and activation of leucocytes emigration.

[The impact of the long-term exposure of industrial aerosols on clinical and functional indices of the broncho-pulmonary system in aluminum smelter workers].

It was found that the appearance of respiratory diseases among workers was established to be associated with the impact of aerosols with the complex chemical composition, exceeding corresponding MAC. Among respiratory diseases in workers there were detected predominantly chronic non-obstructive bronchitis - 59.15%, and chronic obstructive pulmonary disease (COPD) - in 35.2% of cases. In the analysis of spirometric indices of examined patients the vast majority (76.3%) of them showed disturbances of the bronchial patency of mild to moderate degree of the pronouncement. As a result of the implementation offlexible bronchoscopy there was established the presence of a diffuse lesion of bronchi with a predominance of subatrophic and atrophic processes in the mucosa. It was found that under the increase of the concentration of HF in the air of industrial premises the probability of bronchial obstruction and deterioration of the tracheobronchial patency in aluminum smelter workers was established to elevate.

[Peculiarities of air pollution in the production of continuous glass fiber].

With the use of a one-stage method we have carried out hygienic studies of the air of work area of the production of continuous glass fiber. There was revealed the emission of epichlorohydrin, formaldehyde, ethane acid, hydrochloride, spray of mineral petroleum oil, fine glass fiber dust in air of the work area. There was established the combined effect of hazardous substances of unidirectional action with the summation effect on the body. Hazardous substances containing in glass fiber sizers in combination with dust of glass fiber against the background of microtraumatization of the hand skin contribute to the development of occupational skin neoplasms. The studies became the basis of the development of preventive measures aimed at the reduction of risks of the impact of the chemical factor impact on workers.

A multi-scale, multi-disciplinary approach for assessing the technological, economic and environmental performance of bio-based chemicals.

In recent years, bio-based chemicals have gained interest as a renewable alternative to petrochemicals. However, there is a significant need to assess the technological, biological, economic and environmental feasibility of bio-based chemicals, particularly during the early research phase. Recently, the Multi-scale framework for Sustainable Industrial Chemicals (MuSIC) was introduced to address this issue by integrating modelling approaches at different scales ranging from cellular to ecological scales. This framework can be further extended by incorporating modelling of the petrochemical value chain and the de novo prediction of metabolic pathways connecting existing host metabolism to desirable chemical products. This multi-scale, multi-disciplinary framework for quantitative assessment of bio-based chemicals will play a vital role in supporting engineering, strategy and policy decisions as we progress towards a sustainable chemical industry.

Variation Trend and Driving Factors of Greenhouse Gas Emissions from Chinese Magnesium Production.

As the largest magnesium producer in the world, China is facing a great challenge of greenhouse gas (GHG) emissions reduction. In this paper, the variation trend and driving factors of GHG emissions from Chinese magnesium production were evaluated and the measures of technology and policy for effectively mitigating GHG emissions were provided. First, the energy-related and process-oriented GHG inventory is compiled for magnesium production in China. Then, the driving forces for the changes of the energy-related emission were analyzed by the method of Logarithmic Mean Divisia Index (LMDI) decomposition. Results demonstrated that Chinese magnesium output from 2003 to 2013 increased by 125%, whereas GHG emissions only increased by 16%. The emissions caused by the fuels consumption decline most significantly (from 28.4 to 6.6 t CO2eq/t Mg) among all the emission sources. The energy intensity and the energy structure were the main offsetting factors for the increase of GHG emissions, while the scale of production and the international market demand were the main contributors for the total increase. Considering the improvement of technology application and more stringent policy measures, the annual GHG emissions from Chinese primary magnesium production will be controlled within 22 million tons by 2020.

Separation of capsaicin from capsaicinoids by macroporous resin adsorption chromatography.

The aim of present study is to develop an efficient and low-cost method for capsaicin production isolated from capsaicinoids by macroporous resin adsorption chromatography. HZ816 resin has shown the best adsorption and desorption capacities for capsaicin among other resins. To optimize the operating parameters for separation, initial concentration, diameter-to-height ratio, mobile phase ratio, and crystallization method were investigated. When capsaicinoids solution (5 g/L) was loaded onto the column (diameter-to-height ratio = 1:12) with ethanol/1% w/w NaOH (4:6, v/v) as the mobile phase, capsaicin was purified most effectively. By using acid neutralization as the crystallization method, the purity of capsaicin improved from 90.3 to 99.5% with 82.3% yield. In conclusion, this study provides a simple and low-cost method for the industrial-scale production of high-purity capsaicin.

Manufacturing and shear response characterization of carbon nanofiber modified CFRP using the out-of-autoclave-vacuum-bag-only cure process.

The interlaminar shear response is studied for carbon nanofiber (CNF) modified out-of-autoclave-vacuum-bag-only (OOA-VBO) carbon fiber reinforced plastic (CFRP). Commercial OOA-VBO prepregs were coated with a CNF modified epoxy solution and a control epoxy solution without CNF to make CNF modified samples and control samples, respectively. Tensile testing was used to study the in-plane shear performance of [± 45°]4s composite laminates. Significant difference in failure modes between the control and CNF modified CFRPs was identified. The control samples experienced half-plane interlaminar delamination, whereas the CNF modified samples experienced a localized failure in the intralaminar region. Digital image correlation (DIC) surface strain results of the control sample showed no further surface strain increase along the delaminated section when the sample was further elongated prior to sample failure. On the other hand, the DIC results of the CNF modified sample showed that the surface strain increased relatively and uniformly across the CFRP as the sample was further elongated until sample failure. The failure mode evidence along with microscope pictures indicated that the CNF modification acted as a beneficial reinforcement inhibiting interlaminar delamination.

Electricity generation and wastewater treatment of oil refinery in microbial fuel cells using Pseudomonas putida.

Microbial fuel cells (MFCs) represent a novel platform for treating wastewater and at the same time generating electricity. Using Pseudomonas putida (BCRC 1059), a wild-type bacterium, we demonstrated that the refinery wastewater could be treated and also generate electric current in an air-cathode chamber over four-batch cycles for 63 cumulative days. Our study indicated that the oil refinery wastewater containing 2213 mg/L (ppm) chemical oxygen demand (COD) could be used as a substrate for electricity generation in the reactor of the MFC. A maximum voltage of 355 mV was obtained with the highest power density of 0.005 mW/cm² in the third cycle with a maximum current density of 0.015 mA/cm² in regard to the external resistor of 1000 Ω. A maximum coulombic efficiency of 6 × 10⁻²% was obtained in the fourth cycle. The removal efficiency of the COD reached 30% as a function of time. Electron transfer mechanism was studied using cyclic voltammetry, which indicated the presence of a soluble electron shuttle in the reactor. Our study demonstrated that oil refinery wastewater could be used as a substrate for electricity generation.

50 years of mass spectrometry at Firmenich: a continuing love story.

Mass spectrometry (MS) has been intensively used in the field of flavor and fragrance since its beginning in the 1950s, and it remains an essential technique for current and future research in this field. After a short historical section on the introduction and development of MS at Firmenich, this work reviews the main applications of MS-based techniques published by Firmenich researchers over the past 5 years. It exemplifies the use of gas chromatography (GC)-MS for the discovery of new odorant - hence volatile - molecules in a broad range of natural products, such as fruits, meats, and vegetables. Non-volatile compounds play a major role in taste attributes and are also possible precursors of odorant molecules. Their identification by liquid chromatography (LC)-MS in the context of malodor generation from sweat is a typical example of such a relationship. With their high selectivity and sensitivity, GC-MS and LC-MS instruments are used in the fields of flavor and fragrance not only for identification, but also as unique tools for the accurate quantitation of compounds in complex matrices. This is particularly important for regulatory analyses such as dosage of potential allergens in perfumes and for the development of delivery systems. Finally, because of the rapid response time of MS, the kinetics of processes such as the release of flavors in the mouth during food consumption can be monitored by direct sampling into the mass spectrometer.