Multi-functional oilfield production chemicals: maleic-based polymers for gas hydrate and corrosion inhibition

Several chemical problems can occur during the production of oil and gas through flow lines. This includes corrosion, scale deposition and gas hydrate plugging. Three separate chemicals may be needed to treat these issues. Kinetic hydrate inhibitors (KHIs) are used in cold oil or natural gas production flow lines to prevent the formation and plugging of the line with gas hydrates. They are often injected concomitantly with other production chemicals such as corrosion and scale inhibitors. KHIs are specific low molecular weight water-soluble polymers with amphiphilic groups formulated with synergists and solvents. However, many corrosion inhibitors (CIs) are antagonistic to the KHI polymer, severely reducing the KHI performance. It would be preferable and economic if the KHI also could act as a CI. We have explored the use of maleic-based copolymers as KHIs as well as their use as film-forming CIs. KHIs were tested using a natural gas mixture in high pressure rocking cells using the slow constant cooling test method. A terpolymer from reaction of vinyl acetate:maleic anhydride copolymer with cyclohexy lamine and 3,3-di-n-butylaminopropylamine (VA:MA-60% cHex-40% DBAPA), gave excellent performance as a KHI, better than the commercially available poly(N-vinyl caprolactam) (PVCap). CO2 corrosion inhibition was measured by Linear Polarization Resistance (LPR) in a 1 litre CO2 bubble test equipment using C1018 steel coupons. The new terpolymer gave good CO2 corrosion inhibition in 3.6 wt% brine, significantly better than PVCap, but not as good as a commercial imidazoline-based surfactant corrosion inhibitor. The terpolymer also showed good corrosion inhibition efficiency at high salinity conditions, (density 1.12 g/cm3). VA:MA-60% cHex-40% DBAPA shifted the open-circuit potential to more positive values and significantly decreased the corrosion rate.publishedVersio

Effect of halogen substitution on the enthalpies of solvation and hydrogen bonding of organic solutes in chlorobenzene and 1,2-dichlorobenzene derived using multi-parameter correlations

Article on the effect of halogen substitution on the enthalpies of solvation and hydrogen bonding of organic solutes in chlorobenzene and 1,2-dichlorobenzene derived using multi-parameter correlations

Performance of Waterborne Polyurethanes in Inhibition of Gas Hydrate Formation and Corrosion: Influence of Hydrophobic Fragments

The design of new dual-function inhibitors simultaneously preventing hydrate formation and corrosion is a relevant issue for the oil and gas industry. The structure-property relationship for a promising class of hybrid inhibitors based on waterborne polyurethanes (WPU) was studied in this work. Variation of diethanolamines differing in the size and branching of N-substituents (methyl, n-butyl, and tert-butyl), as well as the amount of these groups, allowed the structure of polymer molecules to be preset during their synthesis. To assess the hydrate and corrosion inhibition efficiency of developed reagents pressurized rocking cells, electrochemistry and weight-loss techniques were used. A distinct effect of these variables altering the hydrophobicity of obtained compounds on their target properties was revealed. Polymers with increased content of diethanolamine fragments with n- or tert-butyl as N-substituent (WPU-6 and WPU-7, respectively) worked as dual-function inhibitors, showing nearly the same efficiency as commercial ones at low concentration (0.25 wt%), with the branched one (tert-butyl; WPU-7) turning out to be more effective as a corrosion inhibitor. Commercial kinetic hydrate inhibitor Luvicap 55 W and corrosion inhibitor Armohib CI-28 were taken as reference samples. Preliminary study reveals that WPU-6 and WPU-7 polyurethanes as well as Luvicap 55 W are all poorly biodegradable compounds; BODt/CODcr (ratio of Biochemical oxygen demand and Chemical oxygen demand) value is 0.234 and 0.294 for WPU-6 and WPU-7, respectively, compared to 0.251 for commercial kinetic hydrate inhibitor Luvicap 55 W. Since the obtained polyurethanes have a bifunctional effect and operate at low enough concentrations, their employment is expected to reduce both operating costs and environmental impact.publishedVersio

Effect of halogen substitution on the enthalpies of solvation and hydrogen bonding of organic solutes in chlorobenzene and 1,2-dichlorobenzene derived using multi-parameter correlations

Article on the effect of halogen substitution on the enthalpies of solvation and hydrogen bonding of organic solutes in chlorobenzene and 1,2-dichlorobenzene derived using multi-parameter correlations

The Death Effector Domains of Caspase-8 Induce Terminal Differentiation

The differentiation and senescence programs of metazoans play key roles in regulating normal development and preventing aberrant cell proliferation, such as cancer. These programs are intimately associated with both the mitotic and apoptotic pathways. Caspase-8 is an apical apoptotic initiator that has recently been appreciated to coordinate non-apoptotic roles in the cell. Most of these functions are attributed to the catalytic domain, however, the amino-terminal death effector domains (DED)s, which belong to the death domain superfamily of proteins, can also play key roles during development. Here we describe a novel role for caspase-8 DEDs in regulating cell differentiation and senescence. Caspase-8 DEDs accumulate during terminal differentiation and senescence of epithelial, endothelial and myeloid cells; genetic deletion or shRNA suppression of caspase-8 disrupts cell differentiation, while re-expression of DEDs rescues this phenotype. Among caspase-8 deficient neuroblastoma cells, DED expression attenuated tumor growth in vivo and proliferation in vitro via disruption of mitosis and cytokinesis, resulting in upregulation of p53 and induction of differentiation markers. These events occur independent of caspase-8 catalytic activity, but require a critical lysine (K156) in a microtubule-binding motif in the second DED domain. The results demonstrate a new function for the DEDs of caspase-8, and describe an unexpected mechanism that contributes to cell differentiation and senescence

Molecular mechanisms of cell death: recommendations of the Nomenclature Committee on Cell Death 2018.

Over the past decade, the Nomenclature Committee on Cell Death (NCCD) has formulated guidelines for the definition and interpretation of cell death from morphological, biochemical, and functional perspectives. Since the field continues to expand and novel mechanisms that orchestrate multiple cell death pathways are unveiled, we propose an updated classification of cell death subroutines focusing on mechanistic and essential (as opposed to correlative and dispensable) aspects of the process. As we provide molecularly oriented definitions of terms including intrinsic apoptosis, extrinsic apoptosis, mitochondrial permeability transition (MPT)-driven necrosis, necroptosis, ferroptosis, pyroptosis, parthanatos, entotic cell death, NETotic cell death, lysosome-dependent cell death, autophagy-dependent cell death, immunogenic cell death, cellular senescence, and mitotic catastrophe, we discuss the utility of neologisms that refer to highly specialized instances of these processes. The mission of the NCCD is to provide a widely accepted nomenclature on cell death in support of the continued development of the field

Thermal characterization of crude oils by pressurized differential scanning calorimeter (PDSC)

In this research, pressurized differential scanning calorimeter (PDSC) were used to estimate the thermal and kinetic behaviour of two different crude oils from Tatarstan oil fields under three different pressures (100, 600, 2000 kPa) at a constant heating rate (10 degrees C/min). The heat flow curves of both crude oils indicated two reaction regions known as low temperature oxidation (LTO) and high temperature oxidation (HTO). The reaction intervals were shifted to lower temperature regions with the increase in pressure. The activation energies were calculated according to Borchardt & Daniels and Roger & Morris methods and it was observed that the activation energies were decreasing at elevated pressures

Determination of SARA fractions of crude oils by NMR technique

In this research, four different crude oils from Tatarstan oil fields with wide range of API gravities (from 16.6 to 32.5 degrees API) were used for hydrogen and carbon nuclear magnetic resonance spectroscopy (H NMR and C NMR) determinations. The hydrogen and carbon aromaticity factors were calculated by using the results of H NMR and C NMR spectroscopy results. The results show that the aromaticity factors were high for heavy crude oils. For predicting SARA fractions, the correlations were developed as a function of aromaticity factors. The developed correlations showed high accuracy for predicting SARA fractions for four crude oils

Wax appearance temperature (WAT) determinations of different origin crude oils by differential scanning calorimetry

In this research, wax appearance temperatures (WAT) of eight different crude oils from south-eastern region of Turkey were determined by differential scanning calorimetry. The experiments were performed at a heating/ cooling-rate of 2 degrees C/min from 60 to -20 degrees C It was observed that the wax appearance temperature of different origin crude oils was varied between 14.2 and 37.8 degrees C depending on the API gravity and wax content. It was also observed that the crude oils have enthalpy of precipitation ranging from -3.42 to + 6.39 mW and melting enthalpy from - 2.5 to + 7.46 mW, respectively

Thermal characterization of crude oils in the presence of limestone matrix by TGA-DTG-FTIR

In present work oxidation of two heavy oils in limestone matrix was studied using simultaneous thermo-gravimetry (TGA), derivative thermogravimetry (DTG) and FTIR-spectroscopy techniques in the temperature range from 25 to 900 degrees C. Before the measurements, the composition and properties of crude oils and limestone were evaluated. Obtained TG and DTG curves shows four different reaction regions: low temperature oxidation (LTO), fuel deposition (FD), high temperature oxidation (HTO) and decomposition of limestone. LTO reactions were accompanied by evaporation of light hydrocarbons, which was confirmed by appearance of stretching vibration bands of C-H groups in FTIR-spectra of evolved gases. Formation of carbon dioxide was observed for all oxidation reaction regions according to spectroscopic data. At the same time, CO was formed only in HTO region for both studied crude oils. Despite the different composition two crude oils have practically the same reactions intervals and peak temperatures. However, crude oil with higher API-gravity has a greater mass loss at the LTO and evaporation regions. The conversion of heavier oil with higher content of asphaltenes is larger during the high-temperature oxidation step