The influence of NaOH on the stability of paraffinic crude oil emulsion

The alkaline–surfactant–polymer flooding using sodium hydroxide as the alkali component to enhance oil recovery at the on shore oil fields at Daqing in China has brought new problems for the oil industry. Even though, the reservoir contained paraffinic crude oil, the alkali added formed stable water-in-crude oil emulsion and de-emulsification process was necessary to separate oil and water.The problems related in the enhanced oil recovery process using the alkaline–surfactant–polymer flooding technique in the Daqing oil field have been investigated in the laboratory using fractions of Daqing crude oil. The oil was separated into asphaltene and aliphatic fractions and then used in an additive free jet oil to form model oils. The emulsion stability of each of the water-in-model oil emulsions formed between water or 0.6% sodium hydroxide solution and model oil was investigated. The interfacial properties such as interfacial tension and interfacial pressure of the systems were also measured. These in combination with the chemical nature of the fractions were used to get insight into the problem related to the ASP flooding technique using sodium hydroxide as the alkaline component.The study reveals that the sodium hydroxide solution reacts with fatty acids in the aliphatic fraction of the crude oil and/or with the fatty acids formed from the slow oxidation of long chain hydrocarbons, and form soap like interfacially active components. These accumulate at the crude oil–water interface and contribute to the stability of the oil/water emulsion.     

三元复合驱中原油乳化作用研究

通过乳状液稳定实验考察了大庆油田碱-表面活性剂-聚合物三元复合驱过程乳状液的形成机理、乳状液类型及稳定性。结果表明,大庆原油与碱反应1d时,测得其浓相体积分数为25%,所形成的乳状液为O/W型乳状液,而随着原油与碱作用时间的增加,其浓相体积分数达到40%以上,形成W/O型乳状液,且乳状液稳定性随作用时间增加而增强。大庆原油与水溶性表面活性剂ORS-41溶液作用时,所形成的乳状液为O/W型,且乳状液的稳定性与原油和ORS-41作用时间的长短关系较小。原油与NaOH和ORS-41混合溶液作用时,形成上层为W/O型乳状液,下层为O/W型乳状液的混合体系。     

MICROWAVE DEMULSIFICATION

The laboratory and field tests have demonstrated that microwave radiation can break oil-water-solid emulsions, and recover oil from oily sludge and bottoms sediment and water (BS&W). As a result, this innovative microwave technology provides a new option in the minimization of waste and resource recovery in petroleum industry. Test samples include crude oil-water emulsions and waste sludge from a gas compressor station.

Separations of oil from water by the gravity sedimentation, conventional heating and microwave radiation are compared. There are cases that microwave radiation shows faster separation than that by other two conventional methods.     

Functions of Demulsifiers in the Petroleum Industry

There are an increasing number of crude oil fields that are now producing both crude oil and water emulsions; such fields are both onshore and offshore. These emulsions are formed during oil exploitation due to the presence of natural surfactants, such as asphaltenes and resins. These molecules strongly stabilize the water/oil interface and prevent coalescence of water droplets. As water/oil phase separation is necessary before oil transportation and refining, demulsifiers are used to break water-in-oil emulsions. This review presents the crude oil emulsion formation, factors affecting demulsification of crude oil emulsion such as demulsifier chemical structure, water content, partition coefficient (K_P), and demulsifier concentration. This review also covers the kinetics and mechanism of the demulsification process.     

石油磺酸盐对原油界面性质及其乳状液稳定性的影响

The influence of petroleum sulphonate （TRS） on interfacial properties and stability of the emulsions formed by formation water and asphaltene, resin and crude model oils from Gudong crude oil was investigated by measurement of interfacial shear viscosity, interfacial tension （IFT） and emulsion stability. With increasing petroleum sulphonate concentration, IFT between the formation water and the asphaltene, resin and crude model oils decreases significantly. The interfacial shear viscosity and emulsion stability of asphaltene and crude model oil system increase for the petroleum sulphonate concentration in the range 0.1% to 0.3%, and decrease slightly when the concentration of the surfactant is 0.5%. There exists a close correlation between the interfacial shear viscosity and the stability of the emulsions formed by asphaltene or crude model oils and petroleum sulphonate solution. The stability of the emulsions is determined by the strength of the interfacial film formed of petroleum sulphonate molecules and the natural interfacial active components in the asphaltene fraction and the crude oil. The asphaltene in the crude oil plays a major role in determining the interfacial properties and the stability of the emulsions.     

Rheology and stability of phospholipid-stabilized emulsions

Lecithin in cosmetic emulsions produces a unique “skin feel,” which can be related to its rheological properties. In this study, water-in-oil (w/o) and oil-in-water (o/w) emulsions were made from a cosmetic-grade caprylic/capric triglyceride with deoiled lecithin and hydroxylated lecithin. Synthetic surfactants commonly used in commercial cosmetic products were used as controls. Optical light microscope investigation showed significant differences in the structures of the w/o and o/w emulsions made with the lecithins. Freeze/thaw tests were conducted to evaluate emulsion stability. The o/w emulsion (oil/water = 20:80) was stable with 3% hydroxylated lecithin at room temperature. However, 4% hydroxylated lecithin was needed for stabilizing the emulsion with an oil-to-water ratio of 20:80 or 30:70 through the freeze/thaw treatments. With 4% deoiled lecithin, the w/o emulsion showed a water-holding capacity up to 80%, which was also stable through two freeze/thaw cycles. All emulsions in this study exhibited pseudoplastic flow, in which a minimum shearing stress, a yield value, was required before flow became linear. In general, the emulsion viscosity increased as lecithin content increased. Changing the oil-to-water ratio also affected the emulsion viscosity. The deoiled lecithin-based w/o emulsions had higher yield values than hydroxylated lecithin-based o/w emulsions. Therefore, more force was needed to spread the w/o emulsions. In addition, because w/o emulsions had more viscous continuous phases and a greater volume of internal phases, the w/o emulsions were more viscous than the o/w emulsions.     

Peel Adhesion of Solid Films-The Surface and Bulk Effects

The peel strength of rubber and paint films has been measured over a range of peeling velocities using a dead weight method. At low peel rates the peel force is fairly constant but rises rapidly at higher peeling speeds.

Experiments show that the peel strength is a function both of the energy of interfacial bonds which must be broken as peeling proceeds and of bulk energy losses in a viscoelastic peeling material.

The interfacial effect has two components: an equilibrium surface force which accounts for the peel strength at low velocities, and a viscous peeling force which depends on the peeling rate. This viscous interfacial force explains the increase in peel strength of purely elastic films at higher peeling velocities.

The energy loss in the bulk of the peeling film introduces two additional effects: a magnification of the peel strength in steady peeling over a certain velocity range, and a slowing down or stopping of peeling as transient relaxation occurs shortly after the application of the peel force.     

稠油O/W型乳状液稳定性的研究

以大庆黑帝庙稠油为研究对象，依据稠油乳化降粘原理及O／W型乳状液的形成机制，考察了表面活性剂类型及添加量，碱的添加量，温度、油／水比、振荡方式等因素对稠油O／W型乳状液稳定性的影响。为筛选降粘剂复合配方及选择降低粘工艺提供了必要的基础数据。     

SYNTHESIS OF AMPHIPHILIC COPOLYMERS HAVING CAPABILITY AS EMULSIFIERS AND THEIR SURFACE CHEMICAL PROPERTIES

Some comblike terpolymers composed of methyl methacrylate (MMA), methoxypolyethyleneglycol methacrylate (MPEGMA) as a hydrophilic component, and methoxypolypropyleneglycol methacrylate (MPPGMA) as a hydrophobic component were synthesized by both living radical photopolymerization and ordinary radical polymerization. Since these terpolymers showed a high surface activity, it was suggested that they could be utilized as good polymeric emulsifiers. The polymeric emulsions containing these emulsifiers also showed comparatively good emulsion and mechanical properties as an adhesive. From these facts, it was found that these terpolymers had almost the same emulsification capability as commercially available low molecular weight emulsifiers. Conversely, a difference in surface tension behavior of these terpolymers could be observed. We think that it was due to the chain arrangements (random or block sequence) of the terpolymer.

Amphiphilic copolymer Emulsion polymerization Polymeric emulsifier Micelle formation     

VISCOSITY OF GLYCEROL AND ITS AQUEOUS SOLUTIONS MEASURED BY A TANK-TUBE VISCOMETER

In this paper we demonstrate several series of experiments for the measurement of viscosity of neat glycerol and its aqueous solutions using a tank-tube viscometer. Measuring viscosity of highly viscous liquids with the tank-tube viscometer is easier than other types of viscometers. This inexpensive viscometer continuously generates numerous reproducible viscosity data of highly viscous neat glycerol and its aqueous solutions under given experimental conditions such as a desired temperature and a desired concentration of water in aqueous glycerol solutions.

Fabricating the tank-tube viscometer is inexpensive, since this viscometer does not need sophisticated accessories such as a high-pressure liquid pump, a sensitive pressure sensor, and an accurate flow meter. The tank-tube viscometer consists of a large-diameter reservoir and a long, small-diameter, vertical tube.

The viscosity equation was developed under the following assumptions. Both the quasi steady state approach and the negligible friction loss due to a sudden contraction between the reservoir tank and the tube are valid. The kinetic energy of the emerging stream from the bottom end of the vertical tube of the tank-tube viscometer also is assumed to be negligible. Very viscous glycerol and its aqueous solutions were used to test the viscometer by comparing viscosity values from the viscometer with those from literatures.

The main objective of this study is to demonstrate effects of water as well as temperature on viscosity of aqueous glycerol solutions, applying experimental data of accumulated amounts of aqueous glycerol solutions at various drain durations to the newly-developed viscosity equation for the fabricated tank-tube viscometer.     

孤岛原油乳状液稳定性影响因素研究

通过乳状液稳定性实验考察了孤岛原油乳状液稳定性影响因素。结果表明,低剪切作用下,部分水解聚丙烯酰胺(HPAM)与原油作用1d和54d,所测得其浓相体积分数很快接近零,即HPAM与原油所形成的乳状液稳定性较低。而当溶液中存在50μg/g固体颗粒蒙脱土时,测得其与原油作用1d和54d后的浓相体积分数都约0.08。当溶液中同时含有固体颗粒与HPAM时,测得其与原油作用后所形成的乳状液浓相体积分数很快达到零,固体颗粒与HPAM的协同作用对原油乳状液稳定性有较大影响。另外,随着盐浓度、温度的增加,孤岛原油所形成的乳状液稳定性降低。在30000r/min高速剪切作用下,测得聚合物、固体颗粒模拟水体系与原油间所形成的乳状液浓相体积分数约为0.3,可形成较稳定的乳状液。     

聚合物3530S对坨一原油各组分油水界面性质及乳状液稳定性影响

用界面张力仪、表面粘弹性仪和Zeta电位仪研究了聚合物3530S对胜利坨一原油各组分模型油与模拟水间的界面特性及乳状液稳定性的影响规律。结果表明,沥青质及胶质模型油与模拟水间的界面张力低于蜡组分模型油,原油中的界面活性组分主要为沥青质和胶质。聚合物加入模拟水后,含有聚合物的模拟水与沥青质、胶质及蜡组分模型油之间的界面剪切粘度与界面张力均上升,油滴表面的Zeta电位降低。沥青质和胶质模型油与含聚合物3530S的模拟水所形成的W/O乳状液较蜡组分模型油所形成的W/O乳状液更稳定。     

FLASH CALCULATIONS FOR A CRUDE OIL BY CONTINUOUS THERMODYNAMICS

Continuous thermodynamics is a suitable concept for performing phase equilibrium calculations of complex multi-component mixtures. In contrast to the traditional pseudo-component method, the continuous distribution density function obtained by the characterization experiment is used directly for the thermodynamic calculations.

This paper describes the application of continuous thermodynamics to flash calculations for a crude oil. In the simple version the coexisting phases are assumed to behave ideally. In the refined version the real behavior is accounted for describing non-aromatics and aromatics as two different continuous ensembles.

It proves possible to separate in the calculations the problem of the compositions in the coexisting vapor and liquid phases from the problem of the equilibrium temperatures. For the compositions exact explicit equations are provided.

To obtain the equilibrium temperatures the numerical solution of only one equation (in the simple version) or of a system of only three equations (in the refined version) is required. The refined as well as the simple version lead to good coincidence with experimental data     

Food Drying and Dewatering

Food drying and dewatering raises a growing interest because of increasing requirements in quality, specially in the production of ingredients and additives for food formulation. Heat and mass transfers, as well as mechanical phenomena and reactions kinetics induced by these transfers must be more and more carefully controlled during drying and storage.

This chapter relates recent advances in

- drying of solids

- spray-drying

- drum-dryine

- superheateded steam drying

- osmotice dehydration

- hot oil immersion drying     

VISCOMETRIC MEASUREMENT OF CHROMIUM(III)-POLYACRYLAMIDE GELS†

Gelled polymers are being used increasingly to modify the movement of injected fluids in secondary and enhaced oil recovery processes. A common gelation process involves the reduction of Cr(VI) to Cr(III) in the presence of polyacrylamide. The Cr(III) reacts or interacts with the polymer to form a gel network. Although correlations of gelation time with principal process variables have been obtained, viscometric data have not been reported during or after gelation. These data are needed for fluid flow calculations in surface equipment and estimation of flow behaviour in reservoir rocks.

A Weissenberg Rheogoniometer, with cone and plate geometry, was used to obtain viscometric data for the gelation of polyacrylamide and chromium (III). Solutions consisting of polyacrylamide polymer, sodium dichromate-dihydrate and sodium bisulfite were gelled under a steady shear field at constant temperature. The shear stress versus time profile for the galation process was interpreted to define a gelation time and to determine the apparent viscosity of the gelled fluid. The gelation time decreased as the applied shear rate increased up to about 14.25 sec^-1 and was affected by shear rate history. Viscometric properties of the gelled solutions were determined. Apparent viscosity of the gelled solutions decreased as the shear rate under which they were formed increased.

Post gelation studies indicated that gels exhibited a residual stress at zero shear rate and behaved as Bingham plastics under steady shear. Gels formed at low shear rates were more viscous than gels formed at high shear rates. However, the structure of these gels was susceptible to shear degradation.     

TRANSITION OF FLOW REGIME IN FLUIDIZED BEDS WITH SLANTING BLADE BAFFLES

A flow model is proposed to investigate the transition of flow regime from bubbling to turbulent fluidization postulating that the flow in the emulsion phase follows the Richardson-Zaki equation.

Void fraction of the whole bed ε_f and the mean velocity of bubbles U_b were measured in fluidized beds of 0.3 and 0.5 m ID, in which slanting blade baffles were positioned. Mo-catalyst, silica gel, sand and glass beads with size between 135-443 μm were fluidized by air.

Void fraction of the emulsion phase ε _e was calculated on the basis of the above model. Correlating ε _e with superficial gas velocity U_ƒ, we found that ε _e was very close to ε _mƒ in the bubbling regime and that e, increased with increasing U_ƒ in the turbulent regime.

Calculated values of the volume fraction of bubble phase δ were correlated with U_ƒ, from which apparent transition point from bubbling to turbulent regime was estimated. Combining information obtained, transition of flow regime in the above type of fluidized beds is discussed     

Hg REMOVAL FROM HYDROCARBON LIQUID USING POLYSULFIDE

Some crudes and condensates are known to contain a small quantity of Hg. A process has been devised to remove up to 80-90% of this Hg from the oil. In the process, the oil is washed with an aqueous solution containing 50 to 1000ppm of Na₂S_x.

The efficacy and the feasibility of the process concept have been demonstrated in the laboratory using both batch and flow systems. When the Na₂S_x concentration in the treating solution was higher than 100ppm, the Hg removal reaction was mass transfer limited. By increasing mixing intensity and the number of contacting stages, Hg was removed from 200 to 10ppb using a solution of 500 ppm Na₂S_x. The mixing can be accomplished using one on-line centrifugal pump and preferably two in series.

Phase separation between the aqueous solution and the oil product was rapid. In the process, the sulfur contamination of the oil product, due to Na₂S_x, was low.     

大庆油田三元复合驱采出液的油水分离特性

采用室内配制的模拟三元 (碱、表面活性剂、聚合物 )复合驱采出液研究了大庆油田三元复合驱采出液的油水分离特性 ,以模拟采出液为介质采用均匀设计方法研制了一种针对大庆油田三元复合驱采出液的破乳剂并测试了该破乳剂对模拟三元复合驱采出液和实际三元复合驱采出液的破乳效果。     

Corona-discharge Treatment of Polypropylene films-Effects of Process Parameters

Corona treatment of films, mainly polypropylene (PP)-copolymers, was studied at commercial levels in a 2.7 kVA treater. The films were produced on a flat-film extruder with chill rolls. Degree of treatment was characterized by power of the generator divided by web speed and width of film (m Ws/cm²).

The effectiveness of the treatment was measured in terms of the polar and dispersion components of surface-energy, the peel adhesion of pressure sensitive tape (similar to ASTM Adhesion Ratio) and the peel adhesion of polyurethane adhesives.

The polar component of surface energy is a measure of the effectiveness of corona pretreatment. For a given degree of treatment, the polar surface energy component becomes greater as the film cooling rate increases (and the degree of crystallization falls).

A comparison of homopolymers and copolymers does, however, reveal that even where these have the same density or the same degree of crystallization one cannot count on them having equally-sized polar components.

Peel strengths of pressure-sensitive tapes and polyurethane-bonded patches confirm the influence of cooling conditions on wetting properties.

Contrary to the case for tape adhesion, the polyurethane adhesive strengths reach their maximum value at much lower treatment intensities, i.e. with much lower polar surface energy components, and thus question the validity of the ASTM tests for adhesion properties.