Gas-hydrate formation, agglomeration and inhibition in oil-based drilling fluids for deep-water drilling

One of the main challenges in deep-water drilling is gas-hydrate plugs, which make the drilling unsafe. Some oil-based drilling fluids (OBDF) that would be used for deep-water drilling in the South China Sea were tested to investigate the characteristics of gas-hydrate formation, agglomeration and inhibition by an experimental system under the temperature of 4 ℃ and pressure of 20 MPa, which would be similar to the case of 2000 m water depth. The results validate the hydrate shell formation model and show that the water cut can greatly influence hydrate formation and agglomeration behaviors in the OBDF. The oleophobic effect enhanced by hydrate shell formation which weakens or destroys the interfacial films effect and the hydrophilic effect are the dominant agglomeration mechanism of hydrate particles. The formation of gas hydrates in OBDF is easier and quicker than in water-based drilling fluids in deep-water conditions of low temperature and high pressure because the former is a W/O dispersive emulsion which means much more gas-water interfaces and nucleation sites than the later. Higher ethylene glycol concentrations can inhibit the formation of gas hydrates and to some extent also act as an anti-agglomerant to inhibit hydrates agglomeration in the OBDF.     

Determination of calcium ion in oil-based drilling fluids with an ion-selective electrode

Calcium ion is determined in the internal phase of oil-based drilling fluids with a calcium ion-selective electrode after treatment with a 1:1 (v/v) xylene/isopropanol mixture and 4 M potassium chloride. Results obtained by this potentiometric method and by the Magcobar titration on laboratory-prepared muds and on a North Sea field mud (Statfjord) were in satisfactory agreement.     

Synthesis and plugging effect of inverse emulsion polymerization microspheres (OPME) for oil-based drilling fluids

It is difficult to seal oil-based drilling fluids in the large pore and micro-fracture formation, and there are few suitable materials for the oil phase with good sealing ability at present. In order to solve the problem of the lack of sealing ability of oil-based drilling fluids, acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, and acryloyl morpholine were used as monomers, N'N-methylenebisacrylamide was used as a cross-linking agent, Span-80 and Tween-60 were used as emulsifiers, and 2,2′-azobis(2-methylpropionamidine) dihydrochloride was used as an initiator. Polymer microsphere emulsion OPME was synthesized by inverse emulsion polymerization. The structure of polymer microspheres was characterized by infrared spectroscopy, scanning electron microscopy, electron microscopy, H NMR, laser particle size analysis and thermogravimetric analysis. The optimal synthesis conditions were determined by the control variable method: the monomer ratio of acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, and acryloyl morpholine was 45:20:15, the amount of emulsifier was 8%, and the reaction temperature was 55℃. The synthetic polymer microspheres were added to the oil-based drilling fluids to perform filtration and loss plugging at atmospheric pressure and high-temperature and high-pressure, as well as pore and artificial fracture core plugging evaluation. The evaluation results show that the permeability reduction rate of pore core can reach 82%, and that of fracture core can reach 100% by adding polymer microspheres with 3% dosage. Finally, the pressure transmission experiment proves that the addition of polymer microspheres can slow the pressure transmission and filtrate intrusion, and enhance the stability of wellbore. Therefore, polymer microspheres are a micron-level plugging agent with good compatibility and high performance with oil-based drilling fluids, and the 3% dosage can better seal the formation of large pores and micro-fractures, which has a good potential for field application.     

Comparison and application of different empirical correlations for estimating the hydrate safety margin of oil-based drilling fluids containing ethylene glycol

As the oil and gas industries continue to increase their activity in deep water, gas hydrate hazards will become more serious and challenging, both at present and in the future. Accurate predictions of the hydrate-free zone and the suitable addition of salts and/or alcohols in preparing drilling fluids are particularly important both in preventing hydrate problems and decreasing the cost of drilling operations. In this paper, we compared several empirical correlations commonly used to estimate the hydrate inhibition effect of aqueous organic and electrolyte solutions using experiments with ethylene glycol (EG) as a hydrate inhibitor. The results show that the Najibi et al. correlation (for single and mixed thermodynamic inhibitors) and the Ostergaard et al. empirical correlation (for single thermodynamic inhibitors) are suitable for estimating the hydrate safety margin of oil-based drilling fluids (OBDFs) in the presence of thermodynamic hydrate inhibitors. According to the two correlations, the OBDF, composed of 1.6 L vaporizing oil, 2% emulsifying agent, 1% organobentonite, 0.5% SP-1, 1% LP-1, 10% water and 40% EG, can be safely used at a water depth of up to 1900 m. However, for more accurate predictions for drilling fluids, the effects of the solid phase, especially bentonite, on hydrate inhibition need to be considered and included in the application of these two empirical correlations.     

Emulsification properties of a star-shaped anionic surfactant in oil-based drilling fluid

A novel star-shaped sulfonate surfactant, synthesized with triethanolamine, was identified as a hydrophilic emulsifier which could form a stable water-in-oil emulsion. The interfacial film strength was measured by suspension drop method. The emulsification properties of emulsions were obtained by the emulsification rate experiment and demulsification voltage measurement. The emulsion shows an excellent emulsification effect when the addition of star-shaped anionic surfactant into oil-based drilling fluid was 2.0?wt%. In addition, the properties of surfactant in drilling fluid with different adding amounts were studied by rheological properties, thermal stability analysis and filtration experiments. The results show that star-shaped anionic surfactant used as emulsifier can improve the performance in oil-based drilling fluid, which maybe provides a new idea for this type of surfactant.     

Cluster formation in two-Yukawa fluids

We present a different and efficient method for implementing the analytical solution of Ornstein-Zernike equation for two-Yukawa fluids in the mean spherical approximation. We investigate, in particular, the conditions for the formation of an extra low-Q peak in the structure factor, which we interpret as due to cluster formation in the two-Yukawa fluid when the interparticle potential is composed of a short-range attraction and a long-range repulsion. We then apply this model to interpret the small angle neutron scattering data for protein solutions at moderate concentrations and find out that the presence of a peak centered at Q=0 (zero-Q peak) besides the regular interaction peak due to charged proteins implies an existence of long-range attractive interactions besides the charge repulsion.     

Application of polymeric drilling fluids for reducing wearing of drill bit

The drill bit or cutting tool is a very important part of the rock drilling operation, it is directly associated with the rate of penetration. Bit wearing has significant involvement of time, labor, and wealth. By identifying the effect of various machine and rock parameters on bit wearing, the optimum working condition can be adopted to achieve high drilling efficiency. In this experimental work, the rate of penetration and parameters of drilling fluids (i.e. type, additives, and concentration, etc.) were optimized to identify their respective impact on the bit wearing of impregnated core diamond bit. The study has been conducted on a laboratory rotary drilling setup. The role of aqueous solutions of carboxymethyl cellulose (CMC), guar gum (GG), and polyacrylamide (PAM) has been examined as polymeric drilling fluid additives on sandstone rock samples and compared with the results of tap water alone as drilling fluid. A significant decrement in bit wearing has been noticed with all additives and the maximum reduction of 70.02% was achieved with CMC fluid additive.     

Preparation and application of an environmentally friendly compound lubricant based biological oil for drilling fluids

As the basic raw material of bio-oil based eco-friendly lubricant, a special selected by-product vegetable acidified oil (AO) was modified by vulcanization, esterification, or vulcanization followed by esterification. The optimized vulcanization process conditions are 1% sulfur powder catalyzed, temperature 130 ℃, reaction time 2 h, while the optimized esterification process requires 20% glycerol and 1% H₂SO₄ catalysis, reaction temperature 220 ℃, reaction time 3 h. We compounded modified AO, diluent, pour point depressant and emulsifier into an advanced drilling lubricant F-1. F-1 has excellent performances in bentonite drilling fluids, the extreme pressure lubrication coefficient reduction rate (Δf) in fresh water mud is 86.84%, and 85.76% in 4% NaCl salt water mud. After aging at 150 ℃ for 16 h, its Δf is improved compared with room temperature. Adding F-1 to the basic bentonite mud system, the filtration loss of drilling fluids decreased from 10 mL to 6.5 mL, the apparent viscosity and plastic viscosity experienced little change before and after aging. The new bio-oil compound lubricant has an excellent temperature resistance, a high salt contamination resistance and cost-effective. Vulcanization and esterification processes help to improve the lubricity and reduce foaming rates.     

Extended-range order, diverging static length scales, and local structure formation in cold Lennard-Jones fluids

We report molecular-dynamics simulations on a three-dimensional, two-component Lennard-Jones fluid. We used 125 000 particles (equal numbers of A and B) at density N/V=1.29 and 34 temperatures T covering 5 x 10(4) > or =T > or =0.56. The pair potential was 4epsilon[(sigma(ij)/r)(12)-(sigma(ij)/r)(6)] with sigma(AA)=1, sigma(AB)=11/12, and sigma(BB)=5/6. We computed specific and generic radial distribution functions g(ij)(r), and several density-momentum dynamic correlation functions whose static (t=0) parts vanish by symmetry. Evidence is presented that our systems were adequately annealed to eliminate remnant initial order and were adequately equilibrated at each temperature. Static spatial correlations in cold Lennard-Jones liquids have longer ranges than are often reported: g(r)-1 unequal to 0 is found out to r > or =7 at T=2 and out to r > or =10 at T=0.56. |g(r)-1| has an envelope function that simultaneously fits both crests and troughs of g(r). The envelope function implies a temperature-dependent static length scale l(1); over (0.56 < or =T< or =100), l(1) approximately T(-0.3), contrary to suggestions that g(r) is temperature independent as the glass is approached. The highest-melting-point crystal that we identified melts at T(m) approximately 1.08. In the fluid phase, we observe short-range noncrystalline local structure formation in g(r) as the glass is approached. Local structure is only found below a local structure melting temperature T(mc)=2.0. Local structure vanishes above T=2. Local structure becomes more pronounced as temperature is reduced. However, at all temperatures at which there is local structure in g(r), the local structure is confined to r < or =4. Within the region r < or =4, the amplitude of the local structure diminishes with distance r from the central atom approximately as exp(-r/l(2)), thereby defining a second distance scale in the fluid. l(2), while more difficult to measure, appears to scale with temperature as l(2) approximately T(-0.6); l(2) is not the same as l(1). The static and dynamic properties of the local structure match properties assigned by Kivelson's glass model [S. A. Kivelson et al., J. Chem. Phys. 101, 2391 (1994)] to that model's frustration-limited local clusters.     

Carboxylated cellulose nanocrystals as environmental-friendly and multi-functional additives for bentonite water-based drilling fluids under high-temperature conditions

Cellulose - During the oil and gas drilling engineering, the selection of drilling fluids must take account of the technical and environmental factors. This study investigated the effectiveness of...     

Molecular kinetics of cluster formation in the dense fluids

In this paper we report on molecular dynamics (MD) simulations of the cluster formation kinetics in dense systems. We suggest a cluster identification procedure for dense systems that takes into account the interactions between particles. Problems of cluster existence in unsaturated compressed gas are considered and cluster formation in saturated compressed gas is studied. Molecular dynamics models of adsorbed gas condensation on the surface and the kinetics of the adsorption layer formation have been considered.     

Water-based drilling fluids: the contribution of xanthan gum and carboxymethylcellulose on filtration control

This study aimed mainly to evaluate the influence of xanthan gum (XG) and carboxymethylcellulose (CMC) in the filtration process of water-based drilling fluids, considering the conformational changes suffered by the polyelectrolyte with the addition of salt (NaCl) in different concentrations (0.17, 0.34 and 0.51 M). It was also evaluated the behavior of the fluid by the addition of calcite (calcium carbonate, CaCO₃). Sixteen drilling fluids were prepared with the same xanthan gum concentration (major application as thickener to transport the cuttings), but different salinities and having or not CMC and calcite at constant concentrations. This strategy was adopted to evaluate the real contribution of each additive in the control of filtration performance, frequently unclear in the papers. In general, the fluids prepared in all brines showed lower viscosities and higher filtrate loss compared to fluids of sweet water. This effect was more strong in fluids containing only XG. The addition of CMC enhanced the viscosity and reduced the filtrate loss. However, the best results were obtained when calcite was added. The results indicated that XG contribution as thickener is not enough to control efficiently the fluid filtration even in the presence of calcite. However, the addition of CMC and calcite to XG salt solution increased the viscosity and decreased significantly the filtrate loss. This result was attributed to synergistic interactions between XG, CMC and calcite.     

Liquid-vapor phase diagram and cluster formation of two-dimensional ionic fluids

Direct molecular dynamics simulations on interfaces at constant temperature are performed to obtain the liquid-vapor phase diagram of the two-dimensional soft primitive model, an equimolar mixture of equal size spheres carrying opposite charges. Constant temperature and pressure simulations are also carried out to check consistency with interface simulations results. In addition, an analysis of the cluster formation of mixtures of particles with charge asymmetry in the range 1:1 to 1:36 at low and high densities is performed. The number of free ions, when plotted as a function of the positive ion charge, Z(+), has an oscillatory behavior and is independent of the density. The formation of aggregates is analyzed in terms of the attraction and repulsion between ions.     

Configurational probabilities for monomers, dimers and trimers in fluids

A new analytical approach is proposed to model aggregation of molecules with isotropic, nearest-neighbor, attractive interactions. By treating the clustering process as a chain reaction, equations with the exact high temperature limit are derived by evaluating the occupation probabilities of nearest neighbors based on the Ono-Kondo approach for a hexagonal lattice to calculate the configurational probabilities of i-mers (i = 1, 2, 3). Equilibrium constants for dimers and trimers are calculated based on the configurational probability data. The proposed model agrees well with Monte Carlo simulations at medium and high temperatures. At low temperatures, the model can be improved by considering the full set of site densities in the first shell of a central trimer. Approximate analytical solutions derived from exact calculations of the grand partition function for monomer adsorption on a 4 x N hexagonal lattice with cylindrical boundary conditions also are presented.     

钻井液添加剂对形成天然气水合物的影响

针对深水钻井中水基钻井液易形成天然气水合物从而导致钻井作业无法正常进行的问题,利用自行设计研制的气体水合物反应装置,模拟深水钻井温度压力条件,对水基钻井液添加剂进行了天然气水合物形成的实验研究。分析了各实验体系形成水合物的过冷度。以过冷度为评价指标,评价了各种钻井液添加剂在深水钻井水合物形成过程中的作用。结果表明,在钻井液使用的加量范围内,阳离子聚丙烯酰胺CPAM、两性离子聚合物FA367等对天然气水合物的形成有抑制作用,且随着加量的增加抑制作用增强;磺甲基丹宁SMT、木质素磺酸盐FCLS对天然气水合物的形成有微弱的促进作用,但影响不大。聚合物添加剂的离子类型对天然气水合物的形成影响不大。     

Influence of coagulant and free stabilizer on formation of aggregates in magnetic fluids

The influence of coagulant (isopropanol) and free oleic acid on the formation of quasi-spherical aggregates in a colloidal magnetite solution in kerosene is studied experimentally. It is revealed that the mean sizes of these aggregates fit the 60–90-nm range and are independent of the concentrations of coagulant and free oleic acid provided that these concentrations do not exceed 10–12 vol %. The independence of the mean sizes of aggregates on temperature and disperse composition of particles is considered as a supplementary argument in favor of hypothesis that the main reason for their formation are the defects of protective layers, whereas magnetodipole interactions play a secondary role. It is shown that an excess of oleic acid causes a disproportional decrease in the initial susceptibility of magnetic fluid that is interpreted as a result of the formation of droplet aggregates with characteristic sizes of a few micrometers or more. Apparently, isopropanol leads to an analogous effect, but only at low temperatures.     

Spectrophotometric determination of diphenhydramine hydrochloride in pharmaceutical preparations and biological fluids via ion-pair formation

A simple, sensitive and accurate spectrophotometric method has been described for the assay of diphenhydramine hydrochloride (DPH) in raw material and in biological samples. The method is based on extraction of DPH into dichloromethane as ion-pair complexes with patent blue (PB), eriochrome black T (EBT), methyl orange (MO) and bromocresol purple (BCP) in acidic medium. The coloured species exhibited absorption maxima at 632, 514, 428 and 414 nm for PB, EBT, MO and BCP, with molar absorptivity values of 1.32 × 10⁵, 2.36 × 10⁴, 3.68 × 10⁴ and 3.07 × 10⁴ l mol^?1 cm^?1, respectively. The reaction conditions were optimized to obtain the maximum colour intensity. Beer’s law was obeyed with a good correlation coefficient (0.9982–0.9993) in the concentration ranges 0.5–3, 2.0–16, 2.0–10 and 1.0–10 μg ml^?1 for PB, EBT, MO and BCP methods, respectively. The composition ratio of the ion-association complexes was found to be 1:1 in all cases as established by Job’s method. The conditional stability constant (K_f) and the free energy changes (ΔG°) were determined for all complexes formed. The proposed method was successfully applied for the determination of DPH in tablets and human urine with good accuracy and precision. Statistical comparison of the results with those obtained by the official method showed good agreement and indicated no significant difference in accuracy and precision.     

Communication: thermodynamic signatures of cluster formation in fluids with competing interactions

Convergent theoretical evidence, based on self-consistent integral equations for the pair structure and on Monte Carlo simulations, is presented for the existence of small simultaneous jump discontinuities of several thermodynamic and structural properties of systems of colloidal particles with competing short-range attractive and long-range repulsive interactions, under physical conditions close to the onset of particle clustering. The discontinuities thus provide a signature of the transition from a homogeneous fluid phase to a locally inhomogeneous cluster phase.     

Identification and quantification of alkene-based drilling fluids in crude oils by comprehensive two-dimensional gas chromatography with flame ionization detection

Comprehensive two-dimensional gas chromatography with flame ionization detection (GC x GC-FID) was used to measure alkene-based drilling fluids in crude oils. Compared to one-dimensional gas chromatography, GC x GC-FID is more robust for detecting alkenes due to the increased resolution afforded by second dimension separations. Using GC x GC-FID to analyze four oil samples from one reservoir contaminated with the same drilling fluid, C(15), C(16), C(17), C(18) and C(20) alkenes were identified. The drilling fluid that contaminated these samples also differed from another commercially obtained fluid, which only contained C(16) and C(18) alkenes. These results should motivate the petroleum industry to consider GC x GC-FID for measuring drilling fluids.