The Friction-Reducing, Antiwear and Antioxidation Properties of an Organo-Molybdenum Lube Additive without Sulfur and Phosphorus

The engine oil specifications of ILSAC GF - 4 （ implemented 2004 ） and GF - 5 （ expected 2010 ） have in common three important OEM needs： （1） improved fuel economy and its retention, （2） emissions system compatibility （related to phosphorus and sulfur content）, and （3） improved oil robustness for extended oil life capability （e. g., reduced high temperature deposits and engine sludge, improved oxidative stability, and better valve train wear protec- tion）. For emission systems compatibility, there is a trend towards lower phosphorus and sulfur content in engine oils while maintaining high anti - oxidation and anti - wear performances. In this paper, the friction - reducing, antiwear and antioxidant properties of a sulfurfree and phosphorusfree molybdate ester compound as lubricant additive are discussed. The investigation showed that the molybdate ester enables good frictionreducing ability of the lubricant, and maintains low friction coefficients even after period of severe oil oxidation, which indicates the potential for excellent fuel economy retention in passenger car vehicles. For other organomolybdenum additives, the investigation showed their frictionreducing ability decreased greatly after oxidation of the oil, although the performance appeared to be very good with the fresh oil before aging. In addition, the molybdate ester demonstrated a synergistic effect in anti - wear protection with zinc dialkyl dithiophosphate （ZDDP）, a well- known commonly used additive in engine oils; this suggests that excellent wear protection is possible for an engine oil with reduced sulfur and phosphorus content. Moreover, the molybdate ester is also a strong synergist with arylamine antioxidants, which can retard its depletion in oxidized oil, extend its oxidative induction time, and reduce its high temperature deposit - forming tendency. Thus, this type of sulfur - free and phosphorus - free organo- molybdenum lubricant additive truly provides multifunctional performances, reducing friction, wear, and oxidation of an engine oil when combined with other suitable additives. Due to its phosphorus - free, sulfur- free and multifunctional properties, the molybdate ester compound can be extremely useful in formulat- ing modem engine oils with low phosphorus and sulfur content.     

Effect of Different Aromatic Fractions on Colloidal Property of Tahe Atmospheric Residue

Different amounts of FCC slurry oil and HVGO were added to Tahe atmospheric residue respectively.The colloidal stability and asphaltene agglomeration of atmospheric residue and mixed oils were characterized by means of the mass fraction normalized conductivity and the small-angle X-ray scattering technology(SAXS).The results indicated that the stability of Tahe atmospheric residue decreased with an increasing amount of these oil fractions.It was found that the decline of the colloidal stability was attributed to the component polarity difference between oil fractions and the atmospheric residue.Though the aromaticity of FCC slurry oil was higher than that of HVGO,the polarity of aromatics and resins of FCC slurry oil was lower than those of HVGO.So the degree of the colloidal stability was more seriously destroyed by FCC slurry oil.The dispersion of asphaltenes in Tahe atmospheric residue was changed by adding FCC slurry oil and HVGO.The particle size of asphaltenes increased along with the decline of the colloidal stability.     

Effect of active species in crude oil on the interfacial tension behavior of alkali/synthetic surfactants/crude oil systems

The effect of active species present in crude oil on the interfacial tension （IFT） behavior of alkali/synthetic surfactants/crude oil systems was studied. The system consisted of heavy alkyl benzene sulfonate, sodium chloride, sodium hydrate and Daqing crude oil. Experimental results indicated that active species would diffuse from oil/aqueous interface to aqueous phase and finally an equilibrium could be reached in the system with increasing contact time. Moreover, the minimum IFT and equilibrium IFT values increased with increasing contact time and a linear relationship existed between dynamic IFT and f^-1/2 when IFT value approaching the minimum and after the minimum IFT was reached. This indicated that the dynamic IFT-time behavior was diffusion controlled. The oil and aqueous phases were analyzed by infrared （IR） spectroscopy. IR spectra of oil and aqueous phases illustrated that the content of active species in the oil phase decreased, but the content of active species in the aqueous phase increased after alkali reacted with crude oil. This indicated that the active species present in oil played an important role in reducing IFT.     

Aminated Copolymers as Flow Improvers for Super-viscous Crude Oils

The new flow improvers for super-viscous crude oils were developed via esterification of polybasic high carbon alcohol with methacrylate and copolymerizafion of monomers followed by amination of copolymers. The structure of the synthesized polymer flow improver additive was confirmed by IR spectroscopy and the crystal structure of the flow improver additives were determined by X-ray diffrac- tion analysis. The structure of wax crystals was also studied at the same time. The results showed that the wax crystal structure was closely related with the crystal structure of the flow improver, which could change the pour point depression and viscosity reduction behavior of the crude oil. When the wax crystal structure matched well with that of the additive, the wax crystals were dispersed satisfactorily, resulting in favorable effects in terms of pour point depression and viscosity reduction. The new synthe- sized aminated polymer flow improver additive was most efficient for treating super-viscous crude oils. The super-viscous crude oil had a high content of resins and asphaltenes, which might aggregate onto the surface of wax crystals to form blocks to limit the crude oil fluidity. However, amination of copolymers having similar structure with the resins and asphaltenes contained in crude oil could dissolve the huge polar groups to make the deposit formation difficult.     

Study on Novel HIGEE Technology for Synthesis of Overbased Petroleum Sulfonate Detergent

An innovative idea was proposed to prepare the overbased nano-sized calcium carbonate-calcium petroleum sulfonate in-situ the HIGEE reactor. The test sample prepared by this technology could meet the requirement of the industry standard SH0042-91 for the first-grade product on a par with similar overseas product. The test results obtained upon observation under microscope after freezing etching of specimen revealed that the crystal size of colloidal calcium sulfonate was in the range of 10-30 nm with an average size of 20 nm. The size of the detergent additive was uniform with good transmittance and fluidity. The HIGEE technology possesses five specific features as shown below: Firstly, the carbonation reaction is completed in one step with the reaction time reduced by more than 50% as compared to traditional batch reactor process along with enhanced reaction efficiency, good operability of the process and stabilized product quality. Secondly, ammonia emitted from the reaction is used as the co- promoter without the need for adding ammonia and water as promoters to simplify the promoter system along with effective and strong coupling of reactions. Thirdly, the utilization rate of Ca(OH)2 and CO2 is increased by 15% and 30%, respectively, with product yield increased by 15%, and calcium residue decreased by 65%. Fourthly, the HIGEE technology is environmental benign because of gasoline is used in this technology instead of toxic toluene and xylene. Fifthly, the dimension of HIGEE reactor is reduced by above two-thirds. The success in development of this new technology will offer new ideas and technology platform for the synthesis of metal detergent additive to lubricating oils in China.     

The SINOPEC RIPP to Keep Abreast of Latest ACEA C5 Grade Engine Oil Technology

正Recently the engine oil with its additive formulation independently developed by the SINOPEC Research Institute of Petroleum Processing (RIPP) has successfully passed a whole series of engine tests for the ACEA C5 grade oil, incarnating that RIPP has known well the latest technique for formulating the engine oil in compliance with the ACEA C5 grade oil quality requirements, which is a genuine breakthrough in formulating the ACEA C5 grade engine oil with domestically-made independent additive package.     

Using the TEOST~ MHT-4 to Identify Robust Antioxidant Systems for Modern Engine Oils

A research tool has been developed that utilizes the Thermo-Oxidation Engine Oil Simulation Test (TEOST) MHT-4 to collect information on engine oil oxidation and deposit formation. The technique capitalizes on the traditional TEOST features as a deposit formation test, but also generates additional oxidation information by monitoring peak increase in the carbonyl region of the Fourier Transform Infrared Spectrum (FT-IR) of TEOST used oils and volatiles. The data on overall oxidation and deposit formation is used to generate a "robustness" model for modern engine oil degradation. The tool is used to study low phosphorus Group Ⅱ passenger car engine oils formulated with different types of antioxidants and a molybdenum dithiocarbamate (MoDTC). The model shows that improved oxidation and deposit control can be achieved by formulating with the molybdenum compound, and that the most effective stabilization system is composed of the organo-molybdenum compound,an alkylated diphenylamine (NDPA), and the hindered phenolic antioxidant 4,4′-methylenebis(2,6-di-tert-butylphenol) (MBDTBP).     

板带钢冷轧轧制液及其润滑性能研究

Appropriate base oils and homologous additives such as extreme pressure and anti-wear agents,oiliness agents and antioxidants were selected,and experiments testing the compatibility performance between additive,base oil and other components were carried out to develop the SK and SD series of rolling oils for cold rolling of stainless steel.The developed oils were used in the stainless steel cold rolling lubrication experiments,and were successfully applied in the actual cold rolling operation of stainless steel.Compared with a foreign product,the tribological properties,the thermal oxidation stability,and the rolling lubrication performance of the developed stainless steel cold rolling oils were studied.Test results showed that the tribological properties of the thereby developed rolling oils and the reference one were almost at the same level,and to some extent the performance of rolling was even better than the foreign product,at the same time the stainless steel sheet could retain its well annealed performance.Meanwhile,within a certain range,the lubrication of the rolling oil became better as its viscosity increased at the same level of saponification value,which could provide a lower friction coefficient,so that a higher maximum reduction ratio of the rolled piece through a constant roll gap and a minimum thickness could be secured.Also,similar phenomena appeared as the saponification value increased at a same viscosity level of the rolling oils.     

Study of asphaltene deposition from Tahe crude oil

Borehole blockage caused by asphaltene deposition is a problem in crude oil production in the Tahe Oilfield, Xinjiang, China. This study has investigated the influences of crude oil compositions, temperature and pressure on asphaltene deposition. The asphaltene deposition trend of crude oil was studied by saturates, aromatics, resins and asphaltenes (SARA) method, and the turbidity method was applied for the first time to determine the onset of asphaltene flocculation. The results showed that the asphaltene deposition trend of crude oil by the turbidity method was in accordance with that by the SARA method. The asphaltene solubility in crude oil decreased with decreasing temperature and the amount of asphaltene deposits of T739 crude oil (from well T739, Tahe Oilfield) had a maximum value at 60 o C. From the PVT results, the bubble point pressure of TH10403CX crude oil (from well TH10403CX, Tahe Oilfield) at different temperatures can be obtained and the depth at which the maximum asphaltene flocculation would occur in boreholes can be calculated. The crude oil PVT results showed that at 50 , 90 and 130 o C, the bubble point pressure of TH10403CX crude oil was 25.2, 26.4 and 27.0 MPa, respectively. The depth of injecting asphaltene deposition inhibitors for TH10403CX was determined to be 2,700 m.     

Diffusion coefficients of natural gas in foamy oil systemsunder high pressures

The diffusion coefficient of natural gas in foamy oil is one of the key parameters to evaluate the feasibility of gas injection for enhanced oil recovery in foamy oil reservoirs.In this paper,a PVT cell was used to measure diffusion coefficients of natural gas in Venezuela foamy oil at high pressures,and a new method for determining the diffusion coefficient in the foamy oil was developed on the basis of experimental data.The effects of pressure and the types of the liquid phase on the diffusion coefficient of the natural gas were discussed.The results indicate that the diffusion coefficients of natural gas in foamy oil,saturated oil,and dead oil increase linearly with increasing pressure.The diffusion coefficient of natural gas in the foamy oil at 20 MPa was 2.93 times larger than that at 8.65 MPa.The diffusion coefficient of the natural gas in dead oil was 3.02 and 4.02 times than that of the natural gas in saturated oil and foamy oil when the pressure was20 MPa.However,the gas content of foamy oil was 16.9times higher than that of dead oil when the dissolution time and pressure were 20 MPa and 35.22 h,respectively.     

散射光浊度仪用于金属清净剂浊度的测定研究

采用HACH2100和M-151型散射浊度仪,对润滑油金属清净剂烷基苯磺酸钙、硫化烷基酚钙、烷基水杨酸钙、环烷酸钙样品的浊度进行测定及研究。结果表明,用HACH2100AN测定时,随着样品中金属清净剂浓度的增加,浊度呈现增加、减少、有最大值3种变化趋势,其中转换模式开启时增加的数量多,当样品中清净剂质量分数为20%时,仪器的测定结果更加接近真实值。此外,考察了基础油种类、样品温度对测定结果的影响,发现随着基础油种类变化,测定结果有较大的变化,温度的变化对浊度影响不大。最后结合润滑油金属清净剂胶体颗粒尺寸测定数据,验证了HACH2100测试方法的可靠性。     

高碱值清净剂的抗磨性研究

高碱值清净剂是内燃机油中不可或缺的一种添加剂,主要用于提高内燃机油的性能。近年来的研究发现,高碱值清净剂具有良好的抗磨性能。文章总结了高碱值清净剂的抗磨性,以高碱值磺酸钙为例,介绍了摩擦后高碱值磺酸钙在金属表面形成的含钙保护膜,包括保护膜的形态、组成及结构。列举了其他种类清净剂的抗磨性,并对全配方汽油机油中不同种类高碱值清净剂的抗磨性做了比较。介绍了方解石型高碱值磺酸钙抗磨性要优于无定形高碱值磺酸钙,二烷基二硫代磷酸锌与高碱值清净剂复合后抗磨性的变差。通过综述高碱值清净剂的抗磨性,为其抗磨性的发挥和内燃机油的配制提供参考。     

ANALYSIS OF USED OIL BY IR-SFECTROSCOPIC AND SYNTHESIS OF DISPERSIONS OF A HIGHLY BASIC PETROLEUM CALCIUM SULFONATE ADDITIVE

Infrared absorptions of TLC subtractions of used motor oil, original oil, base oil and the additive, indicate the transformation of the polar and nonpolar components by further oxidation and oxidative degradation of carbonyl compounds into acids, esters and peroxides. Organic nitrates and nitro compounds were also detected after 2000Km and 3000Km service. The effects of basic calcium sulfonate additives, starting with used oil l000Km, 2000Km, 3000Km service, vacuum distillates of used oils and base oil, were studied. It has been found that the dispersant properties of these sulfonates are profoundly influenced by their structure. The alkalinity of the calcium sulfonate additive was determined by spectroscopic-IR method.     

ANALYSIS OF USED OIL BY IR-SFECTROSCOPIC AND SYNTHESIS OF DISPERSIONS OF A HIGHLY BASIC PETROLEUM CALCIUM SULFONATE ADDITIVE

ABSTRACT

Infrared absorptions of TLC subtractions of used motor oil, original oil, base oil and the additive, indicate the transformation of the polar and nonpolar components by further oxidation and oxidative degradation of carbonyl compounds into acids, esters and peroxides. Organic nitrates and nitro compounds were also detected after 2000Km and 3000Km service. The effects of basic calcium sulfonate additives, starting with used oil l000Km, 2000Km, 3000Km service, vacuum distillates of used oils and base oil, were studied. It has been found that the dispersant properties of these sulfonates are profoundly influenced by their structure. The alkalinity of the calcium sulfonate additive was determined by spectroscopic-IR method.     

高碱值石油磺酸钙生产过程废弃物的利用

分析了高碱值石油磺酸钙生产工艺及生产过程废弃物的主要特征,经中试生产实践,提出了废弃物的有效利用途径。结果表明：将生产高碱值石油磺酸钙的废液进行精馏分离,得到的低分子醇作为生产破乳剂的原料,其产品的使用性能与采用新醇生产出的产品相当;用溶剂从高碱值石油磺酸钙离心废渣中萃取出的“低品质”添加剂既可以作为产品进行直接销售,也可以作为高碱值添加剂的调合组分,提高添加剂产品的综合经济效益;萃取添加剂后剩余的碳酸钙经干燥后能作为生产复合磺酸钙基润滑脂的转相剂,进一步降低了磺酸钙基润滑脂的生产成本。     

清净剂磺酸钙结构对其分水性能影响研究

由于不同厂家不同牌号的磺酸钙清净剂其合成原料、加工工艺不同,会导致其使用性能存在较大的差异。实验将5种不同牌号磺酸钙清净剂分别溶于同一种基础油,并按SH／T0619中方法对其分水性能分别进行了考察,发现不同牌号的磺酸钙盐分水结果存在较大差异。为此,从磺酸钙的硫含量、烷基碳链结构方面分析了造成磺酸钙分水性能差异的原因。结果表明,清净剂磺酸钙烷基碳链的支化度是影响其分水性能差异的主要原因,而清净剂中的硫含量对其分水性能影响较小。     

钻井液用页岩防塌剂中磺化度测定方法的改进

磺化沥青中磺酸钠基含量为衡量其质量好坏的重要指标,其含量越高,性能越好。采用离子色谱与元素分析仪相结合,建立了1种快捷地测定磺化沥青中磺酸钠基含量的方法。此方法测定每个样品结果的相对标准偏差（RSD）均小于1%（n=5）,表明该方法具有良好重复性。经实验表明,此方法简单快速可靠,可便捷地应用于磺化沥青中磺酸钠基含量的测定。      

添加剂生产过程中酸性尾气处理方法

通过设计一套吸收装置和吸收塔,利用氨水或NaOH,对生产石油磺酸钙润滑油添加剂上道工序产生的酸性气体进行有效回收,变废为宝,为企业增创效益,为人类保护环境。     

Thermal Conductivity of Transformer Oil From 253 K to 363 K

Transport properties of transformer oil are important parameters for electric equipment designing. In this work, thermal conductivity was measured from 253 K to 363 K by single transient hot-wire technique. And influence of transformer oil's thermal conductivity was investigated. It is found that the thermal conductivity decreases linearly with increasing temperature. When different oils are mixed together, the thermal conductivity shows additive property. For different oils with about the same viscosities, their thermal conductivities are directly related to alkane and aromatic content, while for oils with the same oil source, oil refinery process, similar carbon type, and different boiling range, the thermal conductivity increases with its viscosity.     

碱性石油磺酸钡防锈剂的研制和性能初步评价

磺酸铵与氢氧化钡反应制备石油磺酸钡防锈剂的工艺,可避免直接中和法和复分解法的缺点,易于大规模生产,环境污染很小;该工艺产品的钡含量13．9％,有效组分62．7％,与Texaco公司的TLA－107相当,同时具有良好的油溶性,60℃可溶于矿物油中,降低了防锈油的调和难度。通过对产品结构分析和盐雾性能评价试验,碱性磺酸钡有更好防锈性能,原因是胶体胶束结构中存在氢氧化钡,磺酸钡生成会更完全,残存的亲水性一价磺酸盐少,在金属表面形成的吸附膜强度更高。