Geochemical characteristics and exploration significance of ultra-deep Sinian oil and gas from Well Tashen 5,Tarim Basin,NW China

The Well Tashen 5(TS5),drilled and completed at a vertical depth of 9017 m in the Tabei Uplift of the Tarim Basin,NW China,is the deepest well in Asia.It has been producing both oil and gas from the Sinian at a depth of 8780e8840 m,also the deepest in Asia in terms of oil discovery.In this paper,the geochemical characteristics of Sinian oil and gas from the well were investigated and compared with those of Cambrian oil and gas discovered in the same basin.The oil samples,with Pr/Ph ratio of 0.78 and a whole oil carbon isotopic value of31.6‰,have geochemical characteristics similar to those of Ordovician oils from the No.1 fault in the North Shuntuoguole area(also named Shunbei area)and the Middle Cambrian oil from wells Zhongshen 1(ZS1)and Zhongshen 5(ZS5)of Tazhong Uplift.The maturity of light hydrocarbons,diamondoids and aromatic fractions all suggest an approximate maturity of 1.5%e1.7%Ro for the samples.The(4-+3-)methyldiamantane concentration of the samples is 113.5 mg/g,indicating intense cracking with a cracking degree of about 80%,which is consistent with the high bottom hole temperature(179℃).The Sinian gas samples are dry with a dryness coefficient of 0.97.The gas is a mixture of kerogen-cracking gas and oil-cracking gas and has Ro values ranging between 1.5%and 1.7%,and methane carbon isotopic values of41.6‰.Based on the equivalent vitrinite reflectance(R_(eqv)=1.51%e1.61%)and the thermal evolution of source rocks from the Cambrian Yu'ertusi Formation of the same well,it is proposed that the Sinian oil and gas be mainly sourced from the Cambrian Yu'ertusi Formation during the Himalayan period but probably also be joined by hydrocarbon of higher maturity that migrated from other source rocks in deeper formations.The discovery of Sinian oil and gas from Well TS5 suggests that the ancient ultra-deep strata in the northern Tarim Basin have the potential for finding volatile oil or condensate reservoirs.

Design of artificial neural networks using a genetic algorithm to predict saturates of vacuum gas oil

Accurate prediction of chemical composition of vacuum gas oil （VGO） is essential for the routine operation of refineries. In this work, a new approach for auto-design of artificial neural networks （ANN） based on a genetic algorithm （GA） is developed for predicting VGO saturates. The number of neurons in the hidden layer, the momentum and the learning rates are determined by using the genetic algorithm. The inputs for the artificial neural networks model are five physical properties, namely, average boiling point, density, molecular weight, viscosity and refractive index. It is verified that the genetic algorithm could find the optimal structural parameters and training parameters of ANN. In addition, an artificial neural networks model based on a genetic algorithm was tested and the results indicated that the VGO saturates can be efficiently predicted. Compared with conventional artificial neural networks models, this approach can improve the prediction accuracy.

Application of Discrete Lumped Kinetic Modeling on Vacuum Gas Oil Hydrocracking

The kinetic model of vacuum gas oil （VGO） hydrocracking based on discrete lumped approach was investigated, and some improvement was put forward at the same time in this article. A parallel reaction scheme to describe the conver- sion of VGO into products （gases, gasoline, and diesel） proposed by Orochko was used. The different experimental data were analyzed statistically and then the product distribution and kinetic parameters were simulated by available data. Fur- thermore, the kinetic parameters were correlated based on the feed property, reaction temperature, and catalyst activity. An optimization code in Matlab 2011b was written to fine-me these parameters. The model had a favorable ability to predict the product distribution and there was a good agreement between the model predictions and experiment data. Hence, the ki- netic parameters indeed had something to do with feed properties, reaction temperature and catalyst activity.

Egyptian heavy vacuum gas oil hydrotreating over Co-Mo/CNT and Co-Mo/γ-Al2O3 catalysts

The catalytic activity of CoMoS /CNT towards the Egyptian heavy vacuum gas oil hydrotreating was studied. The delivered CNT was functionalized with 6 mol /L HNO_3. The CNT were loaded with 12% MoO_3( by weight) and 0.7 Co /Mo atomic ratio with impregnation methods. The γ-Al_2O_3 catalyst was also prepared by impregnation method to compare both catalysts activities.The analysis tools such XRD,Raman spectroscopy,TEM,and BET were used to characterize the catalysts. The autoclave reactor was used to operate the hydrotreating experiments. The hydrotreating reactions were tested at various operating conditions of temperature 325-375 ℃,pressure 2-6 MPa,time 2-6 h,and catalyst /oil ratio( by weight) of 1 ∶75,1 ∶33 and 1 ∶10. The results revealed that the CoMoS /CNT was highly efficient for the hydrotreating more than the CoMoS /γ-Al_2O_3. Also, the hydrodesulfurization( HDS) increased with increasing catalyst /oil ratio. Additionally,results showed that the optimum condition was temperature 350℃,pressure 4 MPa,catalyst /oil ratio of 1 ∶75 for 2 h. Furthermore,even at low CoMoS /CNT catalyst /oil ratio of 1 ∶75,an acceptable HDS of 77.1% was achieved.

Molecular reconstruction of vacuum gas oils using a general molecule library through entropy maximization

Vacuum gas oil(VGO)is the most important feedstock for hydrocracking processes in refineries,but its molecular composition cannot be fully acquired by current analysis techniques owing to its complexity.In order to build an accurate and reliable molecular-level kinetic model for reactor design and process optimization,the molecular composition of VGO has to be reconstructed based on limited measurements.In this study,a modified stochastic reconstruction-entropy maximization(SR-REM)algorithm was applied to reconstruct VGOs,with generation of a general molecule library once and for all via the SR method at the first step and adjustment of the molecular abundance of various VGOs via the REM method at the second step.The universality of the molecule library and the effectiveness of the modified SR-REM method were validated by fifteen VGOs(three from the literature)from different geographic regions of the world and with different properties.The simulated properties(density,elemental composition,paraffin-naphthene-aromatics distribution,boiling point distribution,detailed composition of naphthenes and aromatics in terms of ring number as well as composition of S-heterocycles)are in good agreement with the measured counterparts,showing average absolute relative errors of below 10%for each property.

Adsorption of Naphthenic Acids from Dewaxed Vacuum Gas Oil by Activated Clay: Kinetics, Equilibrium and Thermodynamic Studies

This work was mainly concentrated on the removal of naphthenic acids(NAs) from dewaxed vacuum gas oil(VGO) by adsorption using a commercial grade activated clay(AC) adsorption during lube base oil refining. The NAs in dewaxed VGO cut-4 were identified by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry(ESI FT-ICR MS). The AC sample from a refinery was characterized by XRD, BET, TG/DTA, and SEM. A series of experiments were carried out to investigate the performance of NAs adsorption by AC using a batch adsorption technique, in which some key experimental parameters such as temperature, contact time, initial concentration of NA in oil sample as well as the dosage of adsorbent were investigated. Equilibrium isotherms were analyzed using the Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich(D-R) adsorption models. The pseudo-first order, the pseudo-second order, and intraparticle diffusion models were employed to describe the kinetics data. The results revealed that the D-R isotherm provided a better fit to the experimental data than other isotherms, and the adsorption kinetics followed the pseudo-first order kinetic equation. The thermodynamic data indicated that the adsorption process was feasible and spontaneous as an endothermic process. The results could provide a clear understanding of the NAs adsorption by AC during lube base oil processing at refineries.

Solubility and mass transfer of H2, CH4, and their mixtures in vacuum gas oil: An experimental and modeling study

In this work,the solubility data and liquid-phase mass transfer coefficients of hydrogen(H2),methane(CH4)and their mixtures in vacuum gas oil(VGO)at temperatures(353.15-453.15 K)and pressures(1-7 MPa)were measured,which are necessary for catalytic cracking process simulation and design.The solubility of H2 and CH4 in VGO increases with the increase of pressure,but decreases with the increase of temperature.Henry’s constants of H2 and CH4 follow the relation of In H=-413.05/T+5.27 and In H=-990.67/T+5.87,respectively.The molar fractions of H2 and system pressures at different equilibrium time were measured to estimate the liquid-phase mass transfer coefficients.The results showed that with the increase of pressure,the liquid-phase mass transfer coefficients increase.Furthermore,the solubility of H2 and CH4 in VGO was predicted by the predictive COSMO-RS model,and the predicted values agree well with experimental data.In addition,the gas-liquid equilibrium(GLE)for H2+CH4+VGO system at different feeding gas ratios in volume fraction(i.e.,H285%+CH415%and H290%+CH410%)was measured.The selectivity of H2 to CH4 predicted by the COSMO-RS model agrees well with experimental data.This work provides the basic thermodynamic and dynamic data for fuel oil catalytic cracking processes.

Development of Dispersion Models for the Simulation of Fluid Catalytic Cracking of Vacuum Gas Oil in Riser Reactor

Dispersion models for the simulation of an industrial Fluid Catalytic Cracking Riser Reactor have been developed. The models were developed based on the principle of conservation of mass and energy on the reacting species due to bulk flow and axial dispersion. The four-lump kinetic scheme was used to describe the cracking reactions occurring in the reactor. The model equations were a set of parabolic Ordinary Differential Equations which were reduced to first order differential equations by appropriate substitutions and integrated numerically using 4th order Runge Kutta algorithm using Visual Basic 6.0. Results obtained showed a maximum percentage deviation ranging from 0.31% to 5.7% between model predictions and industrial plant data indicating reasonable agreement. Simulation of model at various operating parameters gave optimum gasoline yield of 45.6% of the most significant variable of temperature (658 K), superficial velocity (0.1 m/s), catalyst to gas oil ratio (7.0) and diffusion coefficient of 0.23 m2/s.

FCC Study of Canadian Heavy Gas Oils—Comparisons of Product Yields and Qualities between Reactors

Several series of cracking tests in a comprehensive study were conducted on separate occasions involving all or parts of ten Canadian vacuum gas oils (VGOs) and two catalysts with bottoms-cracking or octane-barrel capability. VGOs were cracked in fixed- and/or fluid-bed microactivity test (MAT) units, in an Advanced Cracking Evaluation (ACE) unit, and in a modified ARCO riser reactor. Individual yields of gas, liquid, and coke from the MATs at 55, 65, 70, and 81 wt% conversion levels were compared with their respective pilot plant data. Good linear correlations could be established between MAT and riser yields except for liquefied petroleum gas (LPG) and light cycle oil (LCO). At a given conversion, correlations existed among the fixed- and fluid-bed MAT units and the ACE for each product yield. Liquid products from the fixed or fluid-bed MAT were analyzed for hydrocarbon types, sulfur, nitrogen and density, most of which showed good agreement with those obtained from the riser study. When cracking Canadian oil-sands-derived VGOs, the bottoms-cracking catalyst containing a large-pore active matrix was found to be more suitable than the octane-barrel catalyst with smaller pores to produce higher yields of valuable distillates, but with less superior qualities (in terms of sulfur and nitrogen contents). The advantages of hydrotreating some poor feeds to improve product yields and qualities were demonstrated and discussed.

香樟木屑真空热解蒸气催化前后产物对比分析(英文)

在两段式反应器上开展了对香樟木屑真空热解蒸气的在线催化提质研究。对比分析了催化前后各相产物产率和气体组成的变化,以及催化前后液相产物理化特性和化学组成。结果表明,催化后液相产物产率降低,但生物油出现分层,上层为油相,下层为水相。油相的H/C物质的量之比、pH值和高位热值(湿基)分别为1.712、4.93和37.15 MJ/kg;油相中烃类和轻质酚类等目标产物含量明显增加,而酸类、醛类和酮类等具有腐蚀性和不稳定性的化合物含量则显著降低,燃料品质较生物原油有显著提升;水相中仍含有少量腐蚀性和不稳定化合物,但其干基的高位热值达32.98 MJ/kg,除去水分后亦可将其用作替代燃料。热解蒸气中非目标产物在HZSM-5分子筛的活性位点上发生转化反应生成期望化合物,各类反应遵循碳正离子反应机理。

减五线生产70~#食品级微晶蜡的技术方案

为了提高炼油厂微晶蜡资源的利用率,对中国石油抚顺石化公司石油一厂减五线生产微晶蜡的工艺条件进行了优化,结果表明:通过酮苯脱蜡脱油、白土预精制、高压加氢精制工艺过程,生产出70#微晶蜡625t,其各项指标均达到食品级要求。通过对生产中存在问题的分析,提出了具体的改进建议。

The Shanghai Wuzheng Engineering Technology LimitedLiability Company in collaboration with China HuanqiuContracting and Engineering Corporation will providethe technology and project design to the commercial andengineering scale-up project for manufacture of ethyleneglycol （EG） from syngas launched by the Zhejiang RongshengHolding Group Company. Currently the projectdesign activity is being carried out successfully.

In this study, the heteroatom classes and molecular structures of nitrogen compounds in vacuum residue arecharacterized by the electrospray ionization （ESI） Fourier transform ion cyclotron resonance mass spectrometry （FT-ICRMS） combined with the Fourier transform infrared （FT-IR） spectroscopy. The results demonstrate that three basic nitrogencompounds, N1 （in which a molecule contains one nitrogen atom, similarly hereinafter）, N1O1 and N2, are identified bytheir positive-ion mass spectra, and three non-basic nitrogen compounds, N1, N1O1, and N1S1, are characterized by theirnegative-ion mass spectra. Among these nitrogen compounds, the N1 class species are the most predominant. Combinedwith the data of ESI FT-ICR MS and FT-IR, the basic N1 class species are likely alkyl quinolines, naphthenic quinolines,acridines, benzonacridines, while the abundant non-basic N1 class species are derivatives of benzocarbazole. In comparisonwith CGO, the N1 basic nitrogen compounds in VR exhibit a higher average degree of condensation and have much longeralkyl side chains.