Neutral Methanol Research Articles

Study on the stability and properties of carbon neutral methanol in blends with diesel fuel

As the simplest liquid fuel, methanol can be sustainably produced from carbon dioxide and renewable energy sources. It is one of the most competitive green fuels. However, there are difficulties in being miscible with conventional fuels when it is used as a blended fuel. In this paper, the furan from biomass is used as the co-solvent of methanol blended fuel, which is expected to address the issue. In this study, not only surface tension, electrical conductivity, and particle size were used to characterize the macroscopic and microscopic structures of carbon neutral methanol blended fuels, and fuel properties including the density, lower calorific value and corrosivity of the mixed fuel have also been discussed. Results indicate that biomass furan reduces the surface tension and keeps the mixed fuel in a microemulsion state for more than 45 days. It increases the fuel density, reduces the unit calorific value cost, and slightly aggravates the corrosion. Carbon neutral methanol fuel, with the help of biomass furan, can be used together with traditional fossil fuels, providing a potential effective path for the efficient and convenient application of new carbon neutral fuels and biomass fuels.

On the fate of protonated chloroformates in the gas phase: a competition between forming HCl and chloroformic acid.

Chloroformates are prevalent in the atmosphere due to their utilization as fuel additives and industrial solvents. These species may undergo interactions with atmospheric water resulting in protonated chloroformates. This study delves into the gas-phase dissociation of these protonated species. Tandem mass spectrometry was employed to scrutinize the unimolecular dissociation of protonated methyl (1), ethyl (2), neopentyl (3), and phenyl chloroformate (4). Notably, 1 and 4 exhibited HCl loss, yielding CH3OCO+ and C6H5OCO+, respectively, with 1 additionally generating neutral methanol and ClCO+. 4 additionally loses CO and CO2. In contrast, 2 and 3 each only exhibit a single fragmentation channel, with 2 losing C2H4 to generate protonated chloroformic acid and 3 generating protonated 2-methylbutene by losing neutral chloroformic acid. Density functional theory at the B3LYP/6-311+G(d,p) level of theory was employed to explore minimum energy reaction pathways for each ion, and CBS-QB3 single-point energy calculations were added to provide reliable energetics. The Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the rate constants for selected competing processes were carried out to link theory and experiment. One common unimolecular process observed was the 1,3-H shift of the proton from the carbonyl oxygen to the ester oxygen before dissociation.

Ignition characteristics of ammonia-methanol blended fuel in a rapid compression machine

Ammonia has attracted wide attention in recent years as a carbon-free fuel. However, the low reactivity and combustion inertness of ammonia pose challenges to its applications in engines. Adding highly reactive fuels, such as renewable carbon–neutral methanol, offers a potential solution. To investigate the ignition characteristics of ammonia-methanol blended fuel, ignition delay time measurement and fast gas sampling under stoichiometric conditions with four ammonia blending ratios (20 % ammonia, A20; 40 % ammonia, A40; 80 % ammonia, A80; 95 % ammonia, A95) were carried out on a rapid compression machine under engine-relevant conditions. The effective thermodynamic conditions were 15–25 bar and 810–970 K. The concentrations of fuels NH3, CH3OH, and intermediate species N2O, CO, as well as products N2, CO2 were detected using gas chromatography. Chemical analysis was performed based on simulations using five ammonia-methanol reaction mechanisms. The ignition delay time results showed that the addition of methanol shortened the ignition delay time, with only a little change in ignition delay time beyond 20 % methanol content. Methanol significantly promoted the production of OH radical, leading to the enhancement of the overall mixture reactivity. The sampling results showed different consumption patterns of ammonia and methanol during the ignition process at different mixing ratios. For A80, methanol was consumed from the early stage of the ignition process, while ammonia consumption was negligible in the early stage. Conversely, for A95, ammonia consumption began in the early stage. This suggests that methanol and its intermediate species inhibited the consumption of ammonia, however, ammonia promoted the consumption of methanol. Chemical analysis further revealed that the inhibitory effect of methanol on ammonia consumption was weakened with the decrease of methanol proportion.

Enhancing the methanol yield of industrial-scale fixed bed reactors using computational fluid dynamics models

Achieving our decarbonisation goals for the maritime transport sector requires the bulk production of liquid hydrocarbon fuels, suitable for the existing infrastructure, such as methanol (MeOH). For this, optimisation of fixed bed chemical reactors is vital. Unlike demonstration-scale setups, optimising the design of such reactors using Computational Fluid Dynamics (CFD) models is both cheaper and faster. In this study, using a 2D pseudo-homogeneous CFD model, a single tube from a multi-tubular industrial-scale MeOH reactor is simulated. Using available experimental data, the CFD model was validated yielding excellent accuracy, with an average error of 2.6 %. The model identified a temperature hot-spot near the bed entrance, while the predicted pressure drop was 11 % of the operating pressure. Both effects could considerably reduce the efficiency of the reactor, either by catalyst deactivation or by increasing the compressor requirements, respectively. Through a parametric study where the tube’s length and diameter were varied within the ±50 % range, 53 total cases are produced and solved, creating an extensive pareto set of data for the key output parameters, such as methanol production, pressure, and temperature. A response surface was also generated, revealing the interconnection between the tube’s design and the operating parameters. This enabled a performance optimisation of the reactor design for two industrially relevant scenarios, with the optimised reactor achieving a 6.9 % higher MeOH yield and a 75 % reduced pressure drop. Through industrial involvement, the reactor can be further optimised, and would act as a critical foundation for more extensive techno-economic and socio-economic evaluations for sustainable carbon–neutral methanol production.

Integrated capture and solar-driven utilization of CO2 from flue gas and air

Integrated capture and solar-driven utilization of CO2 from flue gas and air

Impact of extraction method on alkaloid content and antioxidant activity of Matricaria pubescens

Matricaria pubescens is a medicinal plant much appreciated by the people of the Saharan regions and widely used to treat many diseases. The present study was devoted to evaluate the effect of extraction technique, pH and nature of solvent on alkaloid content and antioxidant activity of M. pubescens. Alkaloid extraction was carried out by applying two techniques, maceration extraction and Soxhlet extraction, using several solvents at different pH (alkaline chloroform, acid methanol, neutral methanol and neutral ethanol). In the present study, the antioxidant activity of the alkaloid extracts of M. pubescens was evaluated using ferric reducing power, molybdate reducing power, DPPH radical scavenging activity, ABTS radical scavenging activity, β-carotene bleaching assay, hydroxyl radical scavenging activity (assessed by deoxyribose assay and HOSC assay) and oxygen radical absorbance capacity (ORAC). The obtained results show that the extraction rates obtained and the antioxidant activities of alkaloid extracts were affected by the extraction technique, pH and the solvent used. The highest extraction rates were obtained with the ethanolic neutral (Soxhlet) and methanolic acidified (maceration) extracts. The alkaloid extracts of M. pubescens exerted a reducing activity of ferric and molybdate ions. They also showed significant radical scavenger activity against DPPH, ABTS, hydroxyl, and peroxyl radicals. This significant wealth of alkaloids and these various antioxidant activities could justify the traditional use of M. pubescens.

Hydrolytic Stability of Unsubstituted Hydrazones of Aromatic Carbonyl Compounds in Reversed-Phase HPLC

Unsubstituted hydrazones RR′C=NNH2 are unstable during gas chromatographic separation. Testing of their resistance to hydrolysis under reversed-phase HPLC showed that aromatic ketone hydrazones are stable. In contrast, aldehyde hydrazones are only stable in neutral methanol–water systems (in the absence of acidic modifiers). In acetonitrile–water systems containing 0.1% of formic acid, only aromatic ketone hydrazones are stable, while aldehyde derivatives are completely hydrolyzed. This difference in stability must be taken into account in determining other compounds of these classes. To detect the hydrolysis of analytes, we compared the retention indices of the initial carbonyl compounds and hydrazones at different volume ratios of organic modifiers and aqueous phases and different pH values of the eluent, the relative absorbance values of the characterized components A(254/220) = A(254)/A(220), and the chromatography–mass spectrometric data.

Methanol Negative Ion Fragmentation Probed in Electron Transfer Experiments.

In this contribution, we report a novel comprehensive investigation on negative ion formation from electron transfer processes mediated by neutral potassium atom collisions with neutral methanol molecules employing experimental and theoretical methodologies. Methanol collision-induced fragmentation yielding anion formation has been obtained by time-of-flight mass spectrometry in the wide energy range of 19 to 275 eV in the lab frame. The negative ions formed in such a collision process have been assigned to CH3O-, OH-, and O-, with a strong energy dependence especially at lower collision energies. The most intense fragment anions in the whole energy range investigated have been assigned to OH- and CH3O-. Additionally, the potassium cation energy loss spectrum in the forward scattering direction at 205 eV impact energy has revealed several features, where the two main electronic states accessible during the collision events have vertical electron affinities of -8.26 ± 0.20 and -10.36 ± 0.2 eV. Quantum chemical calculations have been performed for the lowest-lying unoccupied molecular orbitals of methanol in the presence of a potassium atom, lending strong support to the experimental findings.

Carbon neutral methanol from pulp mills towards full energy decarbonization: an inside perspective and critical review

A neutral and potentially negative carbon cycle for methanol production and use.

Electrodeposited palladium as efficient electrocatalyst for hydrazine and methanol electro-oxidation and detection

Electrodeposited palladium was used as an electrocatalyst for electrochemical oxidation of hydrazine and methanol and the development of a sensitive platform for their detection. The electrochemical behavior of the electrode was evaluated by cyclic voltammetry (CV) while electroanalytical properties were determined by means of differential pulse voltammetry (DPV). The electrodeposited Pd catalyst exhibited good electrocatalytic activity towards the oxidation of hydrazine in neutral solution and methanol oxidation in alkaline solution. Under optimized DPV conditions, the electrodeposited Pd electrode shows good sensing capability in hydrazine and methanol detection.

Improving hygroscopic stability of palmatine chloride by forming a pharmaceutical salt cocrystal of palmatine chloride-gallic acid with neutral molecule

In order to ameliorate the hygroscopicity of palmatine chloride (PMTCl), an unreported salt cocrystal (2(C21H22O4NCl)·C7H6O5·2CH3OH, PMTCl-GA) of palmatine chloride with gallic acid (GA) has been designed and synthesized by a solvent evaporation method. Structure analysis shows that the asymmetric unit of PMTCl-GA includes two PMT cations, two chloride anions, a GA neutral molecule and two methanol molecules. Simultaneously, two PMT cations, two chloride anions, two GA neutral molecule are alternately linked by O–H⋯Cl, C–H⋯Cl and C–H⋯O hydrogen bonds to form synthon R46 (30). On this basis, the 2D layered structure is formed by C–H⋯O hydrogen bond connection, and then adjacent 2D layered structures are connected by C–H⋯O hydrogen bond to form a 3D supramolecular structure. The hygroscopic stability of PMTCl-GA is significantly higher than that of PMTCl, thus it is conjectured that in PMTCl-GA, GA neutral molecule and methanol participate in the self-assembly process of a salt cocrystal, occupying the binding sites between chloride anions with strong hydration ability and external water molecules, which reduces the binding ability of PMTCl-GA with external water molecules. This work has suggested that the physicochemical properties of ionic active pharmaceutical ingredients can be improved by introducing neutral components to form a salt cocrystal. Although the hygroscopic stability of PMTCl-GA was markedly improved compared to that of PMTCl, unfortunately, the solubility of PMTCl-GA was reduced compared to PMTCl, which still needs to be discussed in the subsequent research. In addition, the antibacterial activity of PMTCl-GA against S. aureus, S. albus and E. coli compared with the PMTCl was improved in vitro at different concentrations.

Production of Carbon Neutral Methanol Using Co-Electrolysis of CO2 and Steam in Solid Oxide Electrolysis Cell in Tandem with Direct Air Capture

The increasing concentration of carbon dioxide (CO2) in the atmosphere since the industrial revolution is a major contributor to climate change. Among the several options to tackle this issue, the removal of CO2 from the atmosphere and its subsequent use is becoming increasingly attractive. This paper presents a techno-economic feasibility study and quantification of the environmental benefits of combining direct air capture (i.e. capturing CO2 from the atmosphere) with co-electrolysis of water and the captured CO2 in a solid oxide electrolyser cell (SOEC). Using Aspen Plus, a direct air carbon capture process is modelled in tandem with SOEC to generate carbon monoxide and hydrogen, which are subsequently converted to fuels. The carbon capture model uses regenerative loops of sodium hydroxide and sodium carbonate as well as calcium hydroxide and calcium carbonate to selectively remove the dilute carbon dioxide from the air. Other than filtered air, the only other output of this process is a stream of gaseous water and carbon dioxide at an elevated temperature, which is fed to a SOEC stack. The SOEC model assumes that carbon dioxide is converted to carbon monoxide by the reverse water gas shift reaction and water is converted to hydrogen and oxygen through electrolysis. The different components of the SOEC and their inherent flows of materials and heat are simulated using unit operations available in Aspen Plus. The gas mixture from the SOEC (mixture of H2/CO/CO2/H2O) is further transformed into profitable fuels such as methane and methanol, whose respective processes are also simulated in Aspen Plus. Clean electricity sources are considered for the model and energy requirements are minimized through process synthesis; for example, there exists some good synergies between the direct air capture process and the SOEC to minimize the energy necessary to bring the SOEC feed to its operating temperature of ca. 800°C. Sensitivity analysis are performed on the entire process (direct air capture/SOEC/fuel synthesis) to reveal the effect of key operating parameters (e.g. conversion inside the SOEC, composition of SOEC inlet) on the production of fuels or amount of electricity requirement per amount of fuel produced.

Production of Carbon Neutral Methanol Using Co-Electrolysis of CO2 and Steam in Solid Oxide Electrolysis Cell in Tandem with Direct Air Capture

The increasing concentration of carbon dioxide (CO2) in the atmosphere since the industrial revolution is a major contributor to climate change. Among the several options to tackle this issue, the removal of CO2 from the atmosphere and its subsequent use is becoming increasingly attractive. This paper presents a techno-economic feasibility study and quantification of the environmental benefits of combining direct air capture (i.e. capturing CO2 from the atmosphere) with co-electrolysis of water and the captured CO2 in a solid oxide electrolyser cell (SOEC). It was found that the fuel methanol could be modelled to be produced in a carbon negative manner but is not profitable due to current SOEC capital cost. The capital cost of the SOEC is expected to be cut in half by 2030. This would allow for profitable production of methanol.

JM technology selected for world's first climate neutral methanol plant, advancing production of sustainable fuels

JM technology selected for world's first climate neutral methanol plant, advancing production of sustainable fuels

Systematic Tuning of the Optical Properties of Discrete Complexes of EuII in Solution Using Counterions and Solvents.

We describe a systematic study of the influence of halides and solvents on the optical properties of EuII-containing complexes in solution starting from well-defined crystalline precursors. Anionic halides, chloride and bromide, blue-shift the spectroscopic properties of EuII, whereas neutral ligands, methanol and acetonitrile, cause a red shift. This system provides evidence that EuII has a stronger affinity for chloride, and to some extent bromide, relative to acetonitrile but not methanol. We also describe a simple procedure using an ion-exchange resin for the exchange of iodide counterions to hexafluorophosphate. These findings are a step toward designing ligands that can tune the optical properties of EuII-containing complexes for solution-based applications.

The Effect of the Methanol–Water Interaction on the Surface Layer on Titanium in CH3OH-H2O-LiClO4 Solutions

The purpose of this study was to explain the mechanism of formation and to examine the composition of the anodic film formed on the surface of titanium in an anhydrous neutral methanol solution of electrolytes. In an environment deprived of water molecules, the growth of a 3D-phase titanium oxide layer is not possible. Electrochemical investigations demonstrated that the Ti surface in CH3OH-LiClO4 solutions experienced a pseudo-passivation with the formation of a methoxy layer, which resulted from the reaction of the metal surface with alcohol molecules. The presence of this methoxy surface film was confirmed through XPS and in situ FTIR measurements. The layer blocked the Ti anodic dissolution at the potential range corresponding to the stability of methanol and methoxy ions (i.e., <0.55 V). At potentials over 0.55 V, the methoxy layer was oxidised, which caused the “depassivation” of the metal surface and the etching of titanium. The addition of water changed the properties of Ti in CH3OH-LiClO4 solutions, but only with a water content above 0.2 mole fraction. Below this concentration of water, titanium behaved like it would in an anhydrous solution of methanol. In the range of water concentration of 0.2 to 0.7 mole fraction, the structure of the solution is strengthened because both components of the solvent formed separate percolating networks. The strengthening of the solution structure resulted in a strengthening of the surface layer of Ti(OH)m(OCH3)n. Such a layer had strong barrier properties similar to the properties of an organic polymer film. The formation and growth of a stable layer of TiO2 were possible only in a solvent when the water concentration was higher than ≈0.7 mole fraction.

Simultaneous analysis of current-use pesticides and their transformation products in water using mixture-sorbent solid phase extraction and high-performance liquid chromatography-tandem mass spectrometry.

Pesticides have posed significant threats to aquatic ecosystems, yet little is known about their transformation products. The challenge is to simultaneously analyze various pesticides and transformation products in water as they have distinct physicochemical properties. A mix-mode solid phase extraction method was established to simultaneously analyze current-use pesticides and their transformation products using a mixture of hydrophile-lipophile balance, weak anion, and cation exchange resins (2:1:1, w/w/w) in combination with high-performance liquid chromatography and tandem mass spectrometry for chemical quantification. Neutral, acidic, and alkaline methanol were used as the elution solvent. Box-Behnken design was applied to optimize extraction conditions. Optimal conditions were as follows: sorbent mass, 200mg; volume of elution solvent, 5mL × 3; pH 4. The method was validated for compounds at concentrations from 20 to 1000ng/L in different types of water samples, with recovery being from 43.5 ± 3.1 to 141 ± 35%. Low method detection limits (0.02-5.6ng/L) implied that the developed method was sensitive. Finally, the method was applied to monitor current-use pesticides and their transformation products in natural waters. Frequent detection of transformation products of pesticides indicated that their contribution to aquatic risk should not be ignored.

Syntheses, crystal structures, and antibacterial activity of oxidovanadium(V) and dioxidomolybdenum(VI) complexes derived from N′-(2-hydroxy-4-methoxybenzylidene)isonicotinohydrazide

N’-(2-Hydroxy-4-methoxybenzylidene)isonicotinohydrazide (H2L) was used as ligand to prepare new oxidovanadium(V) complex [VOL(OMe)(MeOH)] (1) and new dioxidomolybdenum(VI) complex [MoO2L(MeOH)] (2). The two complexes were characterized on the basis of their FT-IR, UV, 1H NMR spectra, and molar conductivity. Crystal structures of 1 and 2 have been determined by single crystal X-ray diffraction techniques, which show that the hydrazone ligand coordinates as a di-valent anion with its tridentate O, N, O donors derived from the enolic and phenolic oxygen and azomethine nitrogen. The V ion in 1 is in octahedral coordination, with three donors of the hydrazone ligand and with the remaining sites furnished by one deprotonated methanol oxygen, one neutral methanol oxygen, and one oxo oxygen. The Mo ion in 2 is in octahedral coordination, with three donors of the hydrazone ligand and with the remaining sites furnished by one neutral methanol oxygen and two oxo oxygen atoms. Molecular structures of 1 and 2 are stabilized by hydrogen bonds. The hydrazone and the complexes were screened for their antimicrobial activity and showed good activity.

A DFT study on radical-cationic methanol clusters: Structure, bonding and H-transfer

Radical-cationic methanol clusters (CH3OH) +n, n = 2–5, are studied in the gas phase and solvent methanol using hybrid B3LYP, CAM-B3LYP and BHandHLYP exchange-correlation functionals. The CAM-B3LYP predictions are the most consistent. Ionization of parental neutral rings and chains yields distonic radical cations with spin residing on the CH3O link. Higher energy OO hemibonded structures are also located. The intra-cluster H-transfer from the methyl group of the CH3OH-terminus of the protonated moiety to the O-atom of the CH3O terminus in chain radical cations leads to the lowest-energy distonic isomers with the CH2OH terminus. The CAM-B3LYP activation enthalpies for this reaction in the gas phase are 9.5, 11.1, 13.7, and 17.1 kcal/mol for n = 5, 4, 3, 2, respectively. The inter-cluster H-transfer from the CH3O terminus to a neutral methanol cluster occurs spontaneously, with formation of a protonated cluster weakly bound to the radical cluster. The protonated cluster may serve as a proton carrier.

Mechanisms of sequential ion-molecule reactions in protonated methanol using mass spectrometry, ab initio methods, and statistical modeling

We present mass spectrometry results for reactions of protonated methanol clusters, (CH3OH)nH+. Mass spectra indicate a preference for association over condensation at our experimental conditions and are used in conjunction with computational methods to probe the reaction mechanisms involved. We find that the reaction for the protonated monomer with neutral methanol consists of two entrance complexes that are in equilibrium due to a very small barrier between them. Statistical modeling indicates that competition between proton transfer, condensation, and association are dictated by the depth of the proton-bound complex and the height of the SN2 transition state. For the reaction of the protonated dimer we determine condensation is not energetically favorable at thermal energies as a solvation effect raises the SN2 barrier. Geometries for protonated methanol clusters (CH3OH)nH+ up to n = 6 are also provided, which allow us to examine the role of entropy and hydrogen bonding in these structures.