一株分离自输油管线中的硫酸盐还原菌生理生化特性及腐蚀行为研究

从塔里木某输油管线中分离出一株硫酸盐还原菌(SRB),并对其生理生化特性及腐蚀行为进行研究。结果表明:该株SRB在不同碳源培养基中生长速率存在明显差异,最适生长温度为35℃左右,最适p H在7.5左右,最适Na Cl浓度在0.5%左右;接菌溶液中Q235钢片的腐蚀速率达到0.043 6 mm/a,远大于其在无菌溶液中的腐蚀速率。     

Novel Imidazolium-Based Gemini Surfactants: Synthesis, Surface Properties, Corrosion Inhibition and Biocidal Activity Against Sulfate-Reducing Bacteria

Three novel imidazolium-based gemini surfactants had been synthesized and characterized using different spectroscopic techniques. The surface properties of the synthesized surfactants were determined using surface tension measurements at 20 °C. The surface parameters including critical micelle concentration (CMC), π _CMC, Pc₂₀, Γ_max and A _min were determined. The synthesized compounds were evaluated as corrosion inhibitors for carbon steel in 0.5 M HCl solution using the weight loss and polarization techniques. The biological activity of these surfactants was evaluated against sulfate reducing bacteria using most probable number method. The results indicate that the synthesized compounds have good surface properties and are proper corrosion inhibitors for low carbon steel, with a high inhibition efficiency observed around their CMC. These compounds exhibit a significant biocidal activity against sulfate reducing bacteria.     

Mono‐, Di‐ and Tetra‐Cationic Surfactants as Carbon Steel Corrosion Inhibitors

Corrosion inhibition of three new synthesized cationic surfactants, N‐(2‐(((Z)‐4‐(pyridin‐4‐yl)but‐3‐en‐1‐yl)amino)ethyl)‐N‐(2‐((E)‐(pyridin‐4‐ylmethylene)amino)ethyl)dodecan‐1‐aminium bromide I(4N), N¹,N²‐didodecyl‐N¹‐((Z)‐4‐(pyridin‐4‐yl)but‐3‐en‐1‐yl)‐N²‐(2‐((E)‐(pyridin‐4‐ylmethylene)amino)ethyl)ethane‐1,2‐diaminium bromide II(4N) and 1‐dodecyl‐4‐((E)‐((2‐(dodecyl(2‐(dodecyl((Z)‐4‐(1‐dodecylpyridin‐1‐ium‐4‐yl)but‐3‐en‐1‐yl)ammonio)ethyl)ammonio)ethyl)imino)methyl)pyridin‐1‐ium bromide IV(4N) on carbon steel was investigated by weight loss, electrochemical impedance spectroscopy and polarization measurements. Results show that the synthesized cationic surfactants inhibit corrosion of carbon steel in 1 M HCl. The inhibitive action occurs by virtue of adsorption on the metal surface following a Langmuir adsorption isotherm model. Polarization curves reveal that the investigated cationic surfactants can be classified as mixed inhibitor types. The variations in the corrosion inhibition efficiency between three cationic surfactants are correlated with their chemical structures, with more hydrophobic surfactants yielding higher inhibition efficiency.     

Enhancing of Corrosion Inhibition and the Biocidal Effect of Phosphonium Surfactant Compounds for Oil Field Equipment

It is well known that tetra hydroxymethyl phosphonium sulfate (THPS) is commonly used in oil fields as a biocide for sulfate-reducing bacteria (SRB), but it has low corrosion inhibition. In this study, four phosphonium surfactant compounds were synthesized via a coupling reaction between THPS and different fatty acids namely: decanoic, dodecanoic, palmitic and stearic acids to produce the corresponding surfactants. The chemical structure of the synthesized surfactants was confirmed using FTIR and ¹H-NMR spectroscopy. The surface activity of the prepared compounds was determined by surface tension measurements. The critical micelle concentration (CMC) of each surfactant compound was determined. The corrosion inhibition of the synthesized compounds on carbon steel in 0.5 M HCl was studied by weight loss measurements, potentiodynamic and electrochemical impedance spectroscopy. The effect of the inhibitor concentration and hydrophobic chain length on the their efficiency was also studied. It was found that the CMC of each compound depends on its chemical structure. It was also found that the corrosion inhibition efficiency depends on both of concentration and molecular structure of the inhibitors. Polarization curves revealed that the inhibitors used represent mixed-type inhibitors, which hinder the cathodic and anodic parts of the corrosion reaction in acidic media. Adsorption of used inhibitors leads to a reduction in the double layer capacitance and an increase in the charge transfer resistance. Also the biocidal effect of these compounds was enhanced.     

Interactions between anionically modified hydroxyethyl cellulose and cationic surfactants

Macroscopic properties of aqueous solutions of several modified hydroxyethyl cellulose (HEC) samples and their interactions with cationic surfactants are studied by solubility, light scattering, electric birefringence, rheology, and surface tension measurements. Modified HEC samples carry anionic groups (an-HEC D0) and anionic and hydrophobic groups in random distribution (HM-an-HEC D1–D4). The molar substitution of anionic (an) groups is about 0.07 in all samples while that of the hydrophobic (HM) groups ranges from 0 in an-HEC D0 to 0.012 in HM-an-HEC D4. In a 1 wt% solution this corresponds to 2.7 mM anionic and 0 to 0.46 mM hydrophobic groups. In the dilute concentration range the polymers behave like typical polyelectrolytes whereas in the semi-dilute range they resemble uncharged polymers. On addition of oppositely charged surfactants the phase behavior of all polyelectrolytes is similar. With increasing surfactant concentrations the transparent solutions become turbid and the phases separate. Finally, resolubilization takes place with excess surfactant concentrations. With the HM-an-HEC compounds viscoelastic solutions are formed with cationic surfactants. The intermolecular interaction between hydrophobic parts of the polymers and the surfactants and interactions of oppositely charged ionic groups of the two components lead to formation of a temporary network with gel-like properties. With an-HEC the interaction can only take place via charges. Viscosity enhancement with increasing surfactant concentration is therefore lower with an-HEC than with HM-an-HEC compounds.     

海水冷却器硫酸盐还原菌腐蚀状况与对策

海水中有淤泥、海生物和细菌等，所造成的微生物腐蚀大大加剧了设备的损坏，而且海水冷却器的泄漏具有季节性。由于所用海水污染，形成适合厌氧细菌一硫酸盐还原菌的繁殖环境。导致了设备的加快腐蚀。实验证实了硫酸盐还原菌的大量存在。     

反硝化抑制油田采出水中SRB的效果研究

以硫酸去除率及硫酸盐还原菌(sulfate reducing bacteria,SRB)的数量为指标,研究硝酸盐和反硝化细菌(denitrifying bacteria,DNB)对油田采出水中SRB的抑制作用。结果表明:在单独接种DNB (5%,体积分数)或投加硝酸盐浓度为100mg/L条件下,采出水中SRB的生长均受到有效抑制,其数量从104个/mL可降至10个/mL,硫酸盐去除率从25.5%分别降至6.8%和7.8%;当DNB (12.5%,体积分数)和硝酸盐(100mg/L)共同作用于采出水可使SRB的数量降至10个/mL以下,其硫酸盐去除率降至2.4%,两者对SRB的抑制作用具有协同作用。     

Synthesis and evaluation of new imidazolium‐based aromatic ether functionalized cationic mono and gemini surfactants

Synthesis of a novel series of imidazolium‐based surfactants, [(ROArCH₂MIm)Br] with aromatic ether functionalized hydrophobic tail of varying chain lengths and also their gemini counterparts were conducted in the present work. Synthesis involves initial conversion of 4‐hydroxy benzoic acid to its methyl ester followed by its O‐alkylation with long chain fatty alcohols, which was subsequently reduced and brominated to get 4‐alkyloxy benzyl bromide. For the synthesis of monocationic surfactant, 4‐alkyloxy benzyl bromide is quaternized with N‐methylimidazole. Gemini surfactants are synthesized by initial coupling of imidazole to 4‐alkyloxy benzyl bromide followed by its quaternization with dibromoalkane. The surface properties of all the synthesized surfactants were determined using surface tensiometry. Within the same homologous series, expected decrease in critical micelle concentration (cmc) with the increase in hydrophobicity was observed for shorter chain homologs. However, the deviation in cmc value from regularity was observed when the number of carbon atoms in the hydrophobic chain exceeded a certain number. The cmc values of the geminis were found to be remarkably low compared to their monomeric counterparts.     

Characterization,surface properties and biological activity of new prepared cationic surfactants

Three cationic surfactants were prepared. A condensation reaction between dimethylaminopropylamine (DMAPA) and benzaldehyde was performed. The produced Schiff base was quaternization with three fatty alkyl bromide with different carbon chain length separately to form the desired cationic surfactants. The chemical structure of synthesized cationic surfactants was confirmed by FTIR, ¹H NMR and mass spectroscopy. It was found that the chemical structure of prepared compounds has an effect on surface properties, where increasing the hydrophobic chain length decrease the values of CMC, Г_max while A_min value was increased. The thermodynamic parameters showed that adsorption and micellization processes are spontaneous. It is clear that the prepared cationic surfactants at first tend to adsorb at surface, then it aggregate to form micelle. The prepared surfactants showed good biological activity against gram positive and negative bacteria and fungi in the following order of II (C12) > I (C10) > III (C16). The serial dilution method was used to evaluate the inhibiting effect of these compounds on the sulfate reducing bacteria growth.     

Adsorptive and stripping behavior of methylene blue at gold electrodes in the presence of cationic gemini surfactants

The adsorptive and stripping behavior of methylene blue (i.e. methylene blue chloride, MB) at a gold electrode has been studied with voltammetry, alternating current impedance spectra (ACIS) and quartz crystal microbalance (QCM). MB exhibits a pair of cyclic voltammetry peaks at about −0.3 V (versus SCE) in 0.05 M pH 6.9 phosphate buffer solutions. In the presence of cationic gemini surfactants such as C₁₆H₃₃N(CH₃)₂-C₄H₈-N(CH₃)₂C₁₆H₃₃Br₂ (C₁₆-C₄-C₁₆), C₁₆H₃₃N(CH₃)₂-C₄H₇OH-N(CH₃)₂C₁₆H₃₃Br₂ (C₁₆-C₄OH-C₁₆), C₁₆H₃₃N(CH₃)₂-CH₂-C₆H₄-CH₂-N(CH₃)₂C₁₆H₃₃Br₂ (C₁₆-ph-C₁₆) and C₁₆H₃₃N(CH₃)₂-C₁₂H₂₄-N(CH₃)₂C₁₆H₃₃Br₂ (C₁₆-C₁₂-C₁₆), the anodic peak grows rapidly and moves in positive direction, but the cathodic peak gradually decreases, due to the association adsorption and electrostatic interaction of the geminis with MB and its reduced product (i.e. leuko methylene blue, LMB). With the aid of geminis the adsorption amount of MB increases under open-circuit, but the impedance of the mixed adsorption film to Fe(CN)₆^3−/4− almost keeps unchanged, compared with either bare gold electrodes or MB film, while the adsorption film of geminis exhibits greater impedance. This probably is due to the electron medium action of MB in the film. Gemini surfactants with same alkyl-chain (i.e. -(CH₂)₁₅CH₃) but different molecular structure, exhibit different influence. The enhancing action of geminis studied follows such order as: C₁₆-ph-C₁₆ > C₁₆-C₄-C₁₆ > C₁₆-C₄OH-C₁₆ > C₁₆-C₁₂-C₁₆. The change of peak potential was ascribed to the interaction between MB and surfactants, as well as the blocking action of surfactant film. For comparison, the influence of dihexadecyldimethylammonium bromide (DCAB) and cetyltrimethylammonium bromide (CTAB) was studied, and the influence of other factors is discussed as well.     

Corrosion inhibition of carbon steel in hydrochloric acid by some polyethylene glycols

The inhibition effect of some PEGs on carbon steel corrosion at 25 °C in 0.5N hydrochloric acid as corroding solution was evaluated by weight loss method and polarization and electrochemical impedance spectroscopy (EIS) techniques. In order to study the effect of polyethylene glycols’ structure on the inhibition efficiency, different molecular weights (400, 1000, 4000, and 10,000 g mol⁻¹) were selected. This work has demonstrated that polyethylene glycols have inhibition effect on corrosion process and their inhibition efficiencies are between 50 and 90%. The inhibition efficiencies are increased by increase of the inhibitors’ concentration and molecular weight.     

Synthesis and some studies on fluorinated cationic surfactants: surface and biocidal activities

Three fluorinated cationic surfactants were prepared by condensing N-(2-bromoethyl)perfluoroalkylamides with stoichiometric amounts of pyridine, triethanolamine, and triethylamine to produce three quaternary ammonium salts. The surface and biocidal properties of these surfactants were investigated to find the relation between the structure of the hydrophilic portion of the compounds and their efficiency as biocides. The properties studied included critical micelle concentration (CMC), effectiveness (II_CMC), surface excess concentration (T_max), and area occupied by a molecule (A_min). Free energies of micellization (ΔG _mic ^o) and adsorption (ΔG _ads ^o) of the surfactants in aqueous solution were calculated. The minimal inhibitory concentrations of the prepared compounds were tested against five strains as representative group of microorganisms.     

Corrosion inhibition of iron in 1 M HCl by some gemini surfactants in the series of alkanediyl-α,ω-bis-(dimethyl tetradecyl ammonium bromide)

Three new gemini surfactants in the series of alkanediyl-α,ω-bis-(dimethylalkyl ammonium bromide) were synthesised and tested as corrosion inhibitors of iron in hydrochloric acid medium using gravimetric, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) measurements. Results obtained show that the surfactants studied are good cathodic inhibitors and act on the cathodic hydrogen reaction without modifying its mechanism. EIS results show that the changes in the impedance parameters (R_T and C_dl) with concentration of surfactants studied is indicative of the adsorption of molecules of surfactant leading to the formation of a protective layer on the surface of iron. The effect of the temperature on the iron corrosion in both 1 M HCl and 1 M HCl with addition of various concentrations of 1,2-ethane bis-(dimethyl tetradecyl ammonium bromide) in the range of temperature 20–60 °C was studied. The associated apparent activation corrosion energy has been determined.     

Primary aerobic biodegradation of cationic and amphoteric surfactants

The primary aerobic biodegradation of several cationic and amphoteric surfactants has been studied by using the shaking-flask degradation test and orange II spectrophotometric analysis. The results show that cationic and amphoteric surfactants can be readily biodegraded, with their degradation exceeding 94%. The degradation kinetics can be accurately described by the Boltzmann model. The relationship between structure and biodegradability is discussed. The presence of hydrophobic groups has a strong effect on the biodegradability of these surfactants. Biodegradability decreases with increasing chain length. The presence of hydrophilic groups mainly affects the degradation rate of these surfactants, but not their ultimate biodegradeability. Bio-degradability is deterred and degradation is slowed as steric hindrance increases. Degradation rates increase markedly when hydrophilic groups containing an amide bond are pres-ent.     

Physiochemical interactions of chiral Schiff bases on high carbon steel surface: Corrosion inhibition in acidic media

(S)1-N-(1-hydroxy-1,1-diphenyl-3-methylbut-2-yl)-2-hydroxybenzaldimine (DPV) and (S)1-N-(1-hydroxy-3-methylbut-2-yl)-2-hydroxybenzaldimine (LV) were synthesized and investigated as inhibitors for the corrosion of the high carbon steel (HCS) in 1.0 M HCl by electrochemical measurements. According to the electrochemical methods, inhibitor DPV showed higher efficiency in comparison to that of LV. The Tafel polarization method revealed the mixed-mode inhibition of chiral Schiff bases with predominant control of the anodic reaction. The adsorption of the inhibitor molecules onto the HCS surface was found to follow the Langmuir adsorption isotherm. The values of the Gibbs free energy of adsorption strongly supported spontaneous physicochemical adsorption of inhibitor molecules on the HCS surface. The adsorption mechanism for inhibition was supported by Fourier transforms infrared (FTIR), wide-angle X-ray diffraction (WAXD), scanning electron microscopy–energy-dispersive X-ray (SEM–EDS) spectroscopic methods, and adsorption isotherms.     

Corrosion inhibition and adsorption behavior of new Schiff base surfactant on steel in acidic environment: Experimental and theoretical studies

Synthesis, adsorption and corrosion inhibiting effect of new Schiff base surfactant named 4-hydroxy-3-(3-phenyl-allylideneamino)-benzene sulphonic acid2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethyl ether (abbreviated as PAAB) on mild steel in 1.0 M HCl were investigated using weight loss, and potentiodynamic polarization techniques. The results revealed that this compound inhibited the corrosion reaction in HCl environment. The results indicated that this inhibitor was adsorbed on the metal/solution interface. Theoretical study of the adsorption behavior of this compound was carried out in the framework of the semiempirical (SE) and molecular dynamics (MD).     

Kinetics of precipitation of surfactants. I. Anionic surfactants with calcium and with cationic surfactants

Isoperibol calorimetry was used to measure the rates of precipitation for aqueous solutions of several anionic surfactants with calcium and of anionic and cationic surfactants. A monomer concentration-dependent supersaturation ratio was used to describe the relative rates of precipitation for the surfactant systems studied. This supersaturation ratio allows for the relative rates of precipitation of any surfactant solution to be compared whether micelles are present in solution or not. In general, as the supersaturation ratio increases, the rate of precipitation decreases and the induction time decreases, bot above and below the critical micelle concentration (CMC). The rate of precipitation of sodium dodecyl sulfate (SDS) with dodecyl pyridinium chloride is much slower than the rate of precipitation of the anionic surfactants with calcium for similar supersaturation ratios. The rate of precipitation of SDS with calcium is slightly faster than the rate of precipitation of sodium octyl benzene sulfonate for similar supersaturation ratios. Studies of precipitate crystals, conducted using image analysis, showed that size and shape dependent on the initial supersaturation, the precipitating surfactant molecule, and the extent of aging (until an equilibrium size and shape was reached). Also, differences in the appearance of crystals formed from solutions above and below the CMC were observed. These were most likely due to the difference in supersaturation of these solutions. The crystals formed due to precipitation of SDS with calcium at a concentration above the CMC formed flat trapezoidal, rhombic and hexagonal shapes. These aged into clusters by 1 wk. For a solution that was precipitated at concentrations beginning below the CMC, the crystals began as elongated and rhombic flat plates and aged into trapezoidal, rhombic, and needle-like structures.     

Zinc Corrosion in Acidic Solutions Containing Single and Mixed Surfactants

The influence of surfactant synergism on Zn corrosion inhibition in 0.1-M HCl aqueous solutions has been determined at room temperature. Solutions of single and mixed surfactants consisting of sodium dodecylsulfate (SDS) and N,N-dimethyldodecan-1-amine oxide (DDAO) in water and in 0.1-M HCl were also prepared at room temperature. Critical micelle concentration (CMC) data were obtained through surface tension measurements as a function of mixing composition. A regular solution model was considered to analyze CMC values. The interaction parameter (β), the composition of mixed micelles (x) and the activity coefficients (f) were estimated by a regular solution model for all amphoteric–anionic mixed systems. β Vvalues showed synergism for the binary mixtures of these solutions in the absence and presence of 0.1-M HCl at all investigated compositions. Zinc corrosion in single and binary SDS/DDAO mixed solutions at 5-mM total surfactant concentrations in the presence of 0.1-M HCl was also investigated at static and dynamic conditions. The weight loss data revealed corrosion inhibition activity obeyed the following order: binary (0.75 DDAO + 0.25 SDS) > binary (0.50 DDAO + 0.50 SDS) > single DDAO > single SDS, suggesting an enhancement in the corrosion inhibition activity of DDAO in the presence of a proper amount of SDS. Conductivity time measurements show a similar trend as that obtained by a weight loss method at (0.50 DDAO + 0.50 SDS). The results were illustrated on the basis of synergistic interaction between the mixed surfactants.     

Effects of surfactants and their mixtures on inhibition of the corrosion process of ferritic stainless steel

The corrosion inhibition characteristics regarding mixtures of cationic/zwitterionic types of surfactant (Myristyltrimethylammonium bromide/Palmitylsulfo-betaineas), and non-ionic surfactant TRITON-X-405 mixed with 1 mM of KBr, as corrosion inhibitors for stainless steel (SS) (type X4Cr13) in aqueous solutions of 2 M H₂SO₄ were investigated using potentiodynamic polarisation measurements. The polarisation data showed that mixtures of the surfactants used in this study acted as mixed-type inhibitors, adsorbing on the stainless steel surface in agreement with the Flory-Huggins adsorption isotherm. The tensiometric results of this study suggest the existence of a second state of aggregation for zwitterionic/cationic surfactant mixtures. From these values of the free energy of adsorption, which in both mixtures decreased with respect to a single surfactant, we concluded that the adsorption in mixtures was stronger. The mixtures studied here showed good inhibition properties for ferritic stainless steel type X4Cr13 in 2 M H₂SO₄ solution.